Methane is a significant greenhouse gas with 25-32 times the global warming potential of carbon dioxide. Global sources and sinks of methane are understood to be 550 ± 60 Tg a-1. The possible causes of changing decadal trends in atmospheric methane concentrations since the 1990's is not well understood, since this requires a precision in global emissions quantification better than 20 Tg a-1. Atmospheric observations at the local, regional, or national scale can provide "top-down" constraints on emissions to verify "bottom-up" emissions that may not be well characterized. Cavity ring down spectroscopy (CRDS) instruments deliver highly precise in-situ measurements of methane, with 1 Hz precision better than 2 ppb. A comprehensive aircraft campaign in the Athabasca Oil Sands Region of Alberta (AOSR) in summer 2013, led by Environment and Climate Change Canada (ECCC), deployed a CRDS alongside a suite of instrumentation to measure atmospheric pollutants and meteorological parameters. These observations allowed for the comprehensive identification and quantification of methane emissions from unconventional oil extraction. Emissions estimates were 48% higher than those reported in the national greenhouse gas inventory. A series of lower cost follow up campaigns in 2014 and 2017 using a CRDS instrument mobilized with a vehicle allowed for cold season monitoring of emissions and select quantification where atmospheric parameters were favorable, showing continued discrepancies with inventory reporting. To estimate emissions across Canada at the national scale, methane measurements from ECCC long-term monitoring stations over 2010-2015 were utilized in conjunction with satellite remote sensing observations from the Greenhouse Gas Observing Satellite (GOSAT) operated by the Japanese Aerospace Agency (JAXA). These atmospheric observations were assimilated in the GEOS-Chem chemical transport model to constrain emissions using a Bayesian inverse modelling methodology. Results showed 42% higher emissions from anthropogenic sources and 21% lower emissions from natural sources, which are mostly wetlands, when compared to the prior estimate. Through the combinations of all studies presented herein, approximately 2-4 Tg a-1 of methane emissions in Canada were reallocated for the year of 2013, where 1-3 Tg a-1 was added to anthropogenic sources and 2-4 Tg a-1 was deducted from natural sources, which is substantial relative to the anthropogenic inventory in Canada which is 4-5 Tg a-1. This reallocation is 0.4-0.8% of the entire global budget of 550 Tg a-1, where only a ~3% change in the source-sink balance can cause the observed trends in atmospheric methane. These results show that atmospheric observations from surface, aircraft and satellites are critical for constraining the methane budget in Canada, and improvements are necessary to these types of atmospheric observations over the world to constrain the methane cycle within the precision needed to understand decadal trends.

Understanding, quantifying, and tracking atmospheric methane and emissions is essential for addressing concerns and informing decisions that affect the climate, economy, and human health and safety. Atmospheric methane is a potent greenhouse gas (GHG) that contributes to global warming. While carbon dioxide is by far the dominant cause of the rise in global average temperatures, methane also plays a significant role because it absorbs more energy per unit mass than carbon dioxide does, giving it a disproportionately large effect on global radiative forcing. In addition to contributing to climate change, methane also affects human health as a precursor to ozone pollution in the lower atmosphere. Improving Characterization of Anthropogenic Methane Emissions in the United States summarizes the current state of understanding of methane emissions sources and the measurement approaches and evaluates opportunities for methodological and inventory development improvements. This report will inform future research agendas of various U.S. agencies, including NOAA, the EPA, the DOE, NASA, the U.S. Department of Agriculture (USDA), and the National Science Foundation (NSF).

Ice cores are considered the gold standard for recording past climate and biogeochemical changes. However, gas records derived from ice core analysis have until now been largely limited to centennial and longer timescales because sufficient temporal resolution and analytical precision have been lacking, except during rare times when atmospheric concentrations changed rapidly. In this thesis I used a newly developed methane measurement line to make high-resolution, high-precision measurements of methane during the late Holocene (2800 years BP to present). This new measurement line is capable of an analytical precision of 3 ppb using ~120 g samples whereas the previous highest resolution measurements attained a precision of ± 4.1 ppb using 500-1500g samples [MacFarling Meure et al., 2006]. The reduced sample size requirements as well as automation of a significant portion of the analysis process have enabled me to make1500 discrete ice core methane measurements and construct the highest resolution records of methane available over the late Holocene. Ice core samples came from the recently completed West Antarctic Ice Sheet (WAIS) Divide ice core which has as one of its primary scientific objectives to produce the highest resolution records of greenhouse gases, and from the Greenland Ice Sheet Project (GISP2) ice core which is a proven paleoclimate archive. My thesis has the following three components. I first used a shallow ice core from WAIS Divide (WDC05A) to produce a 1000 year long methane record with a ~9 year temporal resolution. This record confirmed the existence of multidecadal scale variations that were first observed in the Law Dome, Antarctica ice core. I then explored a range of paleoclimate archives for possible mechanistic connections with methane concentrations on multidecadal timescales. In addition, I present a detailed description of the analytical methods used to obtain high-precision measurements of methane including the effects of solubility and a new chronology for the WDC05A ice core. I found that, in general, the correlations with paleoclimate proxies for temperature and precipitation were low over a range of geographic regions. Of these, the highest correlations were found from 1400-1600 C.E. during the onset of the Little Ice Age and with a drought index in the headwater region of the major East Asian rivers. Large population losses in Asia and the Americas are also coincident with methane concentration decreases indicating that anthropogenic activities may have been impacting multidecadal scale methane variability. In the second component I extended the WAIS Divide record back to 2800 years B.P. and also measured methane from GISP2D over this time interval. These records allowed me to examine the methane Inter-Polar Difference (IPD) which is created by greater northern hemispheric sources. The IPD provides an important constraint on changes in the latitudinal distribution of sources. We used this constraint and an 8-box global methane chemical transport model to examine the Early Anthropogenic Hypothesis which posits that humans began influencing climate thousands of years ago by increasing greenhouse gas emissions and preventing the onset of the next ice age. I found that most of the increase in methane sources over this time came from tropical regions with a smaller contribution coming from the extratropical northern hemisphere. Based on previous modeling estimates of natural methane source changes, I found that the increase in the southern hemisphere tropical methane emissions was likely natural and that the northern hemispheric increase in methane emissions was likely due to anthropogenic activities. These results also provide new constraints on the total magnitude of pre-industrial anthropogenic methane emissions, which I found to be between the high and low estimates that have been previously published in the literature. For the final component of my thesis I assembled a coalition of scientists to investigate the effects of layering on the process of air enclosure in ice at WAIS Divide. Air bubbles are trapped in ice 60-100m below the surface of an ice sheet as snow compacts into solid ice in a region that is known as the Lock-In Zone (LIZ). The details of this process are not known and in the absence of direct measurements previous researchers have assumed it to be a smooth process. This project utilized high-resolution methane and air content measurements as well as density of ice, [delta] 15N of N2, and bubble number density measurements to show that air entrapment is affected by high frequency (mm scale) layering in the density of ice within the LIZ. I show that previous parameterizations of the bubble closure process in firn models have not accounted for this variability and present a new parameterization which does. This has implications for interpreting rapid changes in trace gases measured in ice cores since variable bubble closure will impact the smoothing of those records. In particular it is essential to understand the details of this process as new high resolution ice core records from Antarctica and Greenland examine the relative timing between greenhouse gases and rapid climate changes.

"Methane is a powerful greenhouse gas and is estimated to be responsible for approximately one-fifth of man-made global warming. Per kilogram, it is 25 times more powerful than carbon dioxide over a 100-year time horizon -- and global warming is likely to enhance methane release from a number of sources. Current natural and man-made sources include many where methane-producing micro-organisms can thrive in anaerobic conditions, particularly ruminant livestock, rice cultivation, landfill, wastewater, wetlands and marine sediments. This timely and authoritative book provides the only comprehensive and balanced overview of our current knowledge of sources of methane and how these might be controlled to limit future climate change. It describes how methane is derived from the anaerobic metabolism of micro-organisms, whether in wetlands or rice fields, manure, landfill or wastewater, or the digestive systems of cattle and other ruminant animals. It highlights how sources of methane might themselves be affected by climate change. It is shown how numerous point sources of methane have the potential to be more easily addressed than sources of carbon dioxide and therefore contribute significantly to climate change mitigation in the 21st century."--Publisher's description.

We compare modeled and observed atmospheric methane (CH4) between 1996 and 2001, focusing on the role of interannually varying (IAV) transport. The comparison uses observations taken at 13 high-frequency (~hourly) in situ and 6 low-frequency (~weekly) flask measurement sites. To simulate atmospheric methane, we use the global 3-D chemical transport model (MATCH) driven by NCEP reanalyzed winds at T62 resolution (~1.8° x 1.8°). For the simulation, both methane surface emissions and atmospheric sink (OH destruction) are prescribed as annually repeating fields; thus, atmospheric transport is the only IAV component in the simulation. MATCH generally reproduces the amplitude and phase of the observed methane seasonal cycles. At the high-frequency sites, the model also captures much of the observed CH4 variability due to transient synoptic events, which are sometimes related to global transport events. For example, the North Atlantic Oscillation (NAO) and El Niño are shown to influence year-to-year methane observations at Mace Head (Ireland) and Cape Matatula (Samoa), respectively. Simulations of individual flask measurements are generally more difficult to interpret at certain sites, partially due to observational undersampling in areas of high methane variability. A model-observational comparison of methane monthly means at seven coincident in situ and flask locations shows a better comparison at the in situ sites. Additional simulations conducted at coarser MATCH resolution (T42, ~2.8° x 2.8°) showed differences from the T62 simulation at sites near strong emissions. This study highlights the importance of using consistent observed meteorology to simulate atmospheric methane, especially when comparing to high-frequency observations.

Methane is an important greenhouse gas that can cause global warming. The present concentrations of methane are nearly three times higher than several hundred years ago. Today, more than 60% of the atmospheric methane comes from human activities, including rice agriculture, coal mining, natural gas usage, biomass burning, and raising of cattle. Methane affects the stratospheric ozone layer and the oxidizing capacity of the atmosphere, which in turn control the concentrations of many man-made and natural gases in the atmosphere. This book brings together our knowledge of the trends and the causes behind the increased levels of methane. Based on the scientific information on the sources and sinks, and the role of methane in global warming, strategies to limit emissions can be designed as part of a program to control future global warming.

(Cont.) increases rice and biomass burning emissions. The optimized seasonal emission has a strong peak in July, largely due to increased emissions from rice producing regions. The inversion also attributes the large 1998 increase in atmospheric CH4 to global wetland emissions, consistent with a bottom-up study based on a wetland process model. The current observational network can significantly constrain northern emitting regions, but is less effective at constraining tropical emitting regions due to limited observations. We further assessed the inversion sensitivity to different observing sites and model sampling strategies. Better estimates of global OH fluctuations are also necessary to fully describe the interannual behavior of methane observations. Carbon dioxide inversions were conducted as part of the Transcom 3 (Level 1) modeling intercomparison. We further explored the sensitivity of our CO2 inversion results to different parameters.

Methane is a short-lived greenhouse gas that is released during the production and transport of coal, natural gas, and oil; the raising of livestock and other agricultural practices; and the decay of organic waste in municipal solid waste landfills and some wastewater treatment systems. Although it is short-lived, methane has more than 20 times the atmospheric warming effect of carbon dioxide. However, it is a primary component of natural gas, so efforts to reduce methane emissions can take advantage of technologies that capture and reuse the gas as a fuel, potentially bringing about cost-effective reductions in emissions. The Global Methane Initiative (GMI) is a voluntary international partnership that promotes methane recovery and reuse activities in developing and transition economies. Program partners and funders include national governments, private-sector firms, development banks, and nongovernmental organizations. As a founding member of the partnership, the U.S. government contributes funding and other types of support to GMI primarily through the U.S. Department of State (specifically, its Bureau of Oceans and International Environmental and Scientific Affairs and its Office of Global Change) and the U.S. Environmental Protection Agency. To help gauge the effects and value added of its support for the program, the Department of State requested an evaluation of GMI0́9s activities and outcomes relative to its contributions in fiscal years 20060́32010. The evaluation employed a mixed-methods approach that combined quantitative and qualitative information to document program resources and activities and to illustrate program outcomes, including information from in-country site visits.. The report also presents some recommendations for how data collection could be improved to answer more sophisticated questions in the future about the effectiveness of GMI and the value added by the department0́9s contributions.