Christina M. Harth

A history of chemically and radiatively important gases in air deduced from ALE/GAGE/AGAGE

We describe in detail the instrumentation and calibrations used in the Atmospheric Lifetime Experiment (ALE), the Global Atmospheric Gases Experiment (GAGE), and the Advanced Global Atmospheric Gases Experiment (AGAGE) and present a history of the majority of the anthropogenic ozone-depleting and climate-forcing gases in air based on these experiments. Beginning in 1978, these three successive automated high-frequency in situ experiments have documented the long-term behavior of the measured concentrations of these gases over the past 20 years, and show both the evolution of latitudinal gradients and the high-frequency variability due to sources and circulation. We provide estimates of the long-term trends in total chlorine contained in long-lived halocarbons involved in ozone depletion. We summarize interpretations of these measurements using inverse methods to determine trace gas lifetimes and emissions. Finally, we provide a combined observational and modeled reconstruction of the evolution of chlorocarbons by latitude in the atmosphere over the past 60 years which can be used as boundary conditions for interpreting trapped air in glaciers and oceanic measurements of chlorocarbon tracers of the deep oceanic circulation. Some specific conclusions are as follows: (1) International compliance with the Montreal Protocol is so far resulting in chlorofluorocarbon and chlorocarbon mole fractions comparable to target levels; (2) mole fractions of total chlorine contained in long-lived halocarbons (CCl 2 F 2 , CCl 3 F, CH 3 CCl 3 , CCl 4 , CHClF 2 , CCl 2 FCClF 2 , CH 3 Cl, CH 2 Cl 2 , CHCl 3 , CCl 2 =CCl 2 ) in the lower troposphere reached maximum values of about 3.6 ppb in 1993 and are beginning to slowly decrease in the global lower atmosphere; (3) the chlorofluorocarbons have atmospheric lifetimes consistent with destruction in the stratosphere being their principal removal mechanism; (4) multiannual variations in chlorofluorocarbon and chlorocarbon emissions deduced from ALE/GAGE/AGAGE data are consistent approximately with variations estimated independently from industrial production and sales data where available (CCl 2 F 2 (CFC-12) and CCl 2 FCClF 2 (CFC-113) show the greatest discrepancies); (5) the mole fractions of the hydrochlorofluorocarbons and hydrofluorocarbons, which are replacing the regulated halocarbons, are rising very rapidly in the atmosphere, but with the exception of the much longer manufactured CHClF 2 (HCFC-22), they are not yet at levels sufficient to contribute significantly to atmospheric chlorine loading. These replacement species could in the future provide independent estimates of the global weighted-average OH concentration provided their industrial emissions are accurately documented; (6) in the future, analysis of pollution events measured using high-frequency in situ measurements of chlorofluorocarbons and their replacements may enable emission estimates at the regional level, which, together with industrial end-use data, are of sufficient accuracy to be capable of identifying regional noncompliance with the Montreal Protocol.

Emissions of halogenated compounds in East Asia determined from measurements at Jeju Island, Korea.

High-frequency in situ measurements at Gosan (Jeju Island, Korea) during November 2007 to December 2008 have been combined with interspecies correlation analysis to estimate national emissions of halogenated compounds (HCs) in East Asia, including the chlorofluorocarbons (CFCs), halons, hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), sulfur hexafluoride (SF(6)), and other chlorinated and brominated compounds. Our results suggest that overall China is the dominant emitter of HCs in East Asia, however significant emissions are also found in South Korea, Japan and Taiwan for HFC-134a, HFC-143a, C(2)F(6), SF(6), CH(3)CCl(3), and HFC-365mfc. The combined emissions of CFCs, halon-1211, HCFCs, HFCs, PFCs, and SF(6) from all four countries in 2008 are 25.3, 1.6, 135, 42.6, 3.6, and 2.0 kt/a, respectively. They account for approximately 15%, 26%, 29%, 16%, 32%, and 26.5% of global emissions, respectively. Our results show signs that Japan has successfully phased out CFCs and HCFCs in compliance with the Montreal Protocol (MP), Korea has started transitioning from HCFCs to HFCs, while China still significantly consumes HCFCs. Taiwan, while not directly regulated under the MP, is shown to have adapted the use of HFCs. Combined analysis of emission rates and the interspecies correlation matrix presented in this study proves to be a powerful tool for monitoring and diagnosing changes in consumption of HCs in East Asia.

Recent and future trends in synthetic greenhouse gas radiative forcing

Natural Environment Research Council (Great Britain) (Advanced Research Fellowship NE/I021365/1)

Role of atmospheric oxidation in recent methane growth

Significance Methane, the second most important greenhouse gas, has varied markedly in its atmospheric growth rate. The cause of these fluctuations remains poorly understood. Recent efforts to determine the drivers of the pause in growth in 1999 and renewed growth from 2007 onward have focused primarily on changes in sources alone. Here, we show that changes in the major methane sink, the hydroxyl radical, have likely played a substantial role in the global methane growth rate. This work has significant implications for our understanding of the methane budget, which is important if we are to better predict future changes in this potent greenhouse gas and effectively mitigate enhanced radiative forcing caused by anthropogenic emissions. The growth in global methane (CH4) concentration, which had been ongoing since the industrial revolution, stalled around the year 2000 before resuming globally in 2007. We evaluate the role of the hydroxyl radical (OH), the major CH4 sink, in the recent CH4 growth. We also examine the influence of systematic uncertainties in OH concentrations on CH4 emissions inferred from atmospheric observations. We use observations of 1,1,1-trichloroethane (CH3CCl3), which is lost primarily through reaction with OH, to estimate OH levels as well as CH3CC3 emissions, which have uncertainty that previously limited the accuracy of OH estimates. We find a 64–70% probability that a decline in OH has contributed to the post-2007 methane rise. Our median solution suggests that CH4 emissions increased relatively steadily during the late 1990s and early 2000s, after which growth was more modest. This solution obviates the need for a sudden statistically significant change in total CH4 emissions around the year 2007 to explain the atmospheric observations and can explain some of the decline in the atmospheric 13CH4/12CH4 ratio and the recent growth in C2H6. Our approach indicates that significant OH-related uncertainties in the CH4 budget remain, and we find that it is not possible to implicate, with a high degree of confidence, rapid global CH4 emissions changes as the primary driver of recent trends when our inferred OH trends and these uncertainties are considered.

Reconciling reported and unreported HFC emissions with atmospheric observations

Significance Hydrofluorocarbons (HFCs) are among the atmosphere’s fastest growing, and most potent, greenhouse gases. Proposals have been made to phase down their use over the coming decades. Such initiatives may largely be informed by existing emissions inventories, which, we show, are the subject of significant uncertainty. In this work, we use atmospheric models and measurements to examine the accuracy of these inventories for five major HFCs. We show that, when aggregated together, reported emissions of these HFCs from developed countries are consistent with the atmospheric measurements, and almost half of global emissions now originate from nonreporting countries. However, the agreement between our results and the inventory breaks down for individual HFC emissions, suggesting inaccuracies in the reporting methods for individual compounds. We infer global and regional emissions of five of the most abundant hydrofluorocarbons (HFCs) using atmospheric measurements from the Advanced Global Atmospheric Gases Experiment and the National Institute for Environmental Studies, Japan, networks. We find that the total CO2-equivalent emissions of the five HFCs from countries that are required to provide detailed, annual reports to the United Nations Framework Convention on Climate Change (UNFCCC) increased from 198 (175–221) Tg-CO2-eq⋅y–1 in 2007 to 275 (246–304) Tg-CO2-eq⋅y–1 in 2012. These global warming potential-weighted aggregated emissions agree well with those reported to the UNFCCC throughout this period and indicate that the gap between reported emissions and global HFC emissions derived from atmospheric trends is almost entirely due to emissions from nonreporting countries. However, our measurement-based estimates of individual HFC species suggest that emissions, from reporting countries, of the most abundant HFC, HFC-134a, were only 79% (63–95%) of the UNFCCC inventory total, while other HFC emissions were significantly greater than the reported values. These results suggest that there are inaccuracies in the reporting methods for individual HFCs, which appear to cancel when aggregated together.

Sulfuryl fluoride in the global atmosphere

United States. National Aeronautics and Space Administration (NASA) (Upper Atmospheric Research Program)

Nitrogen trifluoride global emissions estimated from updated atmospheric measurements

Nitrogen trifluoride (NF3) has potential to make a growing contribution to the Earth’s radiative budget; however, our understanding of its atmospheric burden and emission rates has been limited. Based on a revision of our previous calibration and using an expanded set of atmospheric measurements together with an atmospheric model and inverse method, we estimate that the global emissions of NF3 in 2011 were 1.18 ± 0.21 Gg⋅y−1, or ∼20 Tg CO2-eq⋅y−1 (carbon dioxide equivalent emissions based on a 100-y global warming potential of 16,600 for NF3). The 2011 global mean tropospheric dry air mole fraction was 0.86 ± 0.04 parts per trillion, resulting from an average emissions growth rate of 0.09 Gg⋅y−2 over the prior decade. In terms of CO2 equivalents, current NF3 emissions represent between 17% and 36% of the emissions of other long-lived fluorinated compounds from electronics manufacture. We also estimate that the emissions benefit of using NF3 over hexafluoroethane (C2F6) in electronics manufacture is significant—emissions of between 53 and 220 Tg CO2-eq⋅y−1 were avoided during 2011. Despite these savings, total NF3 emissions, currently ∼10% of production, are still significantly larger than expected assuming global implementation of ideal industrial practices. As such, there is a continuing need for improvements in NF3 emissions reduction strategies to keep pace with its increasing use and to slow its rising contribution to anthropogenic climate forcing.

Growth in stratospheric chlorine from short‐lived chemicals not controlled by the Montreal Protocol

Abstract We have developed a chemical mechanism describing the tropospheric degradation of chlorine containing very short‐lived substances (VSLS). The scheme was included in a global atmospheric model and used to quantify the stratospheric injection of chlorine from anthropogenic VSLS ( ClyVSLS) between 2005 and 2013. By constraining the model with surface measurements of chloroform (CHCl3), dichloromethane (CH2Cl2), tetrachloroethene (C2Cl4), trichloroethene (C2HCl3), and 1,2‐dichloroethane (CH2ClCH2Cl), we infer a 2013 ClyVSLS mixing ratio of 123 parts per trillion (ppt). Stratospheric injection of source gases dominates this supply, accounting for ∼83% of the total. The remainder comes from VSLS‐derived organic products, phosgene (COCl2, 7%) and formyl chloride (CHClO, 2%), and also hydrogen chloride (HCl, 8%). Stratospheric ClyVSLS increased by ∼52% between 2005 and 2013, with a mean growth rate of 3.7 ppt Cl/yr. This increase is due to recent and ongoing growth in anthropogenic CH2Cl2—the most abundant chlorinated VSLS not controlled by the Montreal Protocol.

Instruments and Methods - A novel method for obtaining very large ancient air samples from ablating glacial ice for analyses of methane radiocarbon

We present techniques for obtaining large (� 100 L STP) samples of ancient air for analysis of 14 C of methane ( 14 CH4) and other trace constituents. Paleoatmospheric 14 CH4 measurements should constrain the fossil fraction of past methane budgets, as well as provide a definitive test of methane clathrate involvement in large and rapid methane concentration ((CH4)) increases that accompanied rapid warming events during the last deglaciation. Air dating to the Younger Dryas-Preboreal and Oldest Dryas-Bolling abrupt climatic transitions was obtained by melt extraction from old glacial ice outcropping at an ablation margin in West Greenland. The outcropping ice and occluded air were dated using a combination of d 15 No f N 2, d 18 Oo f O 2, d 18 Oice and (CH4) measurements. The (CH4) blank of the melt extractions was <4 ppb. Measurements of d 18 O and d 15 N indicated no significant gas isotopic fractionation from handling. Measured Ar / N2, CFC-11 and CFC-12 in the samples indicated no significant contamination from ambient air. Ar / N2, Kr /Ar and Xe /Ar ratios in the samples were used to quantify effects of gas dissolution during the melt extractions and correct the sample (CH4). Corrected (CH4) is elevated over expected values by up to 132 ppb for most samples, suggesting some in situ CH4 production in ice at this site.

Minimal geological methane emissions during the Younger Dryas–Preboreal abrupt warming event

Methane (CH4) is a powerful greenhouse gas and plays a key part in global atmospheric chemistry. Natural geological emissions (fossil methane vented naturally from marine and terrestrial seeps and mud volcanoes) are thought to contribute around 52 teragrams of methane per year to the global methane source, about 10 per cent of the total, but both bottom-up methods (measuring emissions) and top-down approaches (measuring atmospheric mole fractions and isotopes) for constraining these geological emissions have been associated with large uncertainties. Here we use ice core measurements to quantify the absolute amount of radiocarbon-containing methane (14CH4) in the past atmosphere and show that geological methane emissions were no higher than 15.4 teragrams per year (95 per cent confidence), averaged over the abrupt warming event that occurred between the Younger Dryas and Preboreal intervals, approximately 11,600 years ago. Assuming that past geological methane emissions were no lower than today, our results indicate that current estimates of today’s natural geological methane emissions (about 52 teragrams per year) are too high and, by extension, that current estimates of anthropogenic fossil methane emissions are too low. Our results also improve on and confirm earlier findings that the rapid increase of about 50 per cent in mole fraction of atmospheric methane at the Younger Dryas–Preboreal event was driven by contemporaneous methane from sources such as wetlands; our findings constrain the contribution from old carbon reservoirs (marine methane hydrates, permafrost and methane trapped under ice) to 19 per cent or less (95 per cent confidence). To the extent that the characteristics of the most recent deglaciation and the Younger Dryas–Preboreal warming are comparable to those of the current anthropogenic warming, our measurements suggest that large future atmospheric releases of methane from old carbon sources are unlikely to occur.