ALBERT

Description: Solar radiation incident at the Earth’s surface (Rs) is an essential component of the total energy exchange between the atmosphere and the surface. Reanalysis data have been widely used, but a comprehensive validation using surface measurements is still highly needed. In this study, we evaluated the Rs estimates from six current representative global reanalyses (NCEP–NCAR, NCEP-DOE; CFSR; ERA-Interim; MERRA; and JRA-55) using surface measurements from different observation networks [GEBA; BSRN; GC-NET; Buoy; and CMA] (674 sites in total) and the Earth’s Radiant Energy System (CERES) EBAF product from 2001 to 2009. The global mean biases between the reanalysis Rs and surface measurements at all sites ranged from 11.25 W/m2 to 49.80 W/m2. Comparing with the CERES-EBAF Rs product, all the reanalyses overestimate Rs, except for ERA-Interim, with the biases ranging from −2.98 W/m2 to 21.97 W/m2 over the globe. It was also found that the biases of cloud fraction (CF) in the reanalyses caused the overestimation of Rs. After removing the averaged bias of CERES-EBAF, weighted by the area of the latitudinal band, a global annual mean Rs values of 184.6 W/m2, 180.0 W/m2, and 182.9 W/m2 were obtained over land, ocean, and the globe, respectively.

Description: Based on observations of the chlorofluorocarbons CFC-13 (chlorotrifluoromethane), ΣCFC-114 (combined measurement of both isomers of dichlorotetrafluoroethane), and CFC-115 (chloropentafluoroethane) in atmospheric and firn samples, we reconstruct records of their tropospheric histories spanning nearly 8 decades. These compounds were measured in polar firn air samples, in ambient air archived in canisters, and in situ at the AGAGE (Advanced Global Atmospheric Gases Experiment) network and affiliated sites. Global emissions to the atmosphere are derived from these observations using an inversion based on a 12-box atmospheric transport model. For CFC-13, we provide the first comprehensive global analysis. This compound increased monotonically from its first appearance in the atmosphere in the late 1950s to a mean global abundance of 3.18 ppt (dry-air mole fraction in parts per trillion, pmol mol−1) in 2016. Its growth rate has decreased since the mid-1980s but has remained at a surprisingly high mean level of 0.02 ppt yr−1 since 2000, resulting in a continuing growth of CFC-13 in the atmosphere. ΣCFC-114 increased from its appearance in the 1950s to a maximum of 16.6 ppt in the early 2000s and has since slightly declined to 16.3 ppt in 2016. CFC-115 increased monotonically from its first appearance in the 1960s and reached a global mean mole fraction of 8.49 ppt in 2016. Growth rates of all three compounds over the past years are significantly larger than would be expected from zero emissions. Under the assumption of unchanging lifetimes and atmospheric transport patterns, we derive global emissions from our measurements, which have remained unexpectedly high in recent years: mean yearly emissions for the last decade (2007–2016) of CFC-13 are at 0.48 ± 0.15 kt yr−1 (〉 15 % of past peak emissions), of ΣCFC-114 at 1.90 ± 0.84 kt yr−1 (∼ 10 % of peak emissions), and of CFC-115 at 0.80 ± 0.50 kt yr−1 (〉 5 % of peak emissions). Mean yearly emissions of CFC-115 for 2015–2016 are 1.14 ± 0.50 kt yr−1 and have doubled compared to the 2007–2010 minimum. We find CFC-13 emissions from aluminum smelters but if extrapolated to global emissions, they cannot account for the lingering global emissions determined from the atmospheric observations. We find impurities of CFC-115 in the refrigerant HFC-125 (CHF2CF3) but if extrapolated to global emissions, they can neither account for the lingering global CFC-115 emissions determined from the atmospheric observations nor for their recent increases. We also conduct regional inversions for the years 2012–2016 for the northeastern Asian area using observations from the Korean AGAGE site at Gosan and find significant emissions for ΣCFC-114 and CFC-115, suggesting that a large fraction of their global emissions currently occur in northeastern Asia and more specifically on the Chinese mainland.

Description: We reconstruct atmospheric abundances of the potent greenhouse gas c-C4F8 (perfluorocyclobutane, perfluorocarbon PFC-318) from measurements of in situ, archived, firn, and aircraft air samples with precisions of ~ 1–2 % reported on the SIO-14 gravimetric calibration scale. Combined with inverse methods, we found near zero atmospheric abundances from the early 1900s to the early 1960s, after which they rose sharply, reaching 1.66 ppt (parts per trillion dry-air mole fraction) in 2017. Global c-C4F8 emissions rose from near zero in the 1960s to ~ 1.2 Gg yr−1 in the late 1970s to late 1980s, then declined to ~ 0.8 Gg yr−1 in the mid-1990s to early 2000s, followed by a rise since the early 2000s to ~ 2.2 Gg yr−1 in 2017. These emissions are significantly larger than inventory based emission estimates. Estimated emissions from eastern Asia rose from 0.36 Gg yr−1 in 2010 to 0.73 Gg yr−1 in 2016 and 2017, 31 % of global emissions, mostly from eastern China. We estimate emissions of 0.14 Gg yr−1 from Northern and Central India in 2016 and find evidence for significant emissions from Russia. In contrast, recent emissions from North Western Europe and Australia are estimated to be small (≤ 1 % each). We conclude that emissions from China, India and Russia are likely related to production of polytetrafluoroethylene (PTFE, “Teflon”) and other fluoropolymers that are based on the pyrolysis of hydrochlorofluorocarbon HCFC-22 (CHClF2) in which c-C4F8 is a known by-product. The semiconductor sector, where c-C4F8 is used, is estimated to be a small source. Without an obvious correlation with population density, incineration of waste containing fluoropolymers is probably a minor source, and we find no evidence of emissions from electrolytic production of aluminum in Australia. While many possible emissive uses of c-C4F8 are known, the start of significant emissions may well be related to the advent of commercial PTFE production in 1947. Process controls or abatement to reduce c-C4F8 by-product were probably not in place in the early decades, explaining the increase in emissions. With the advent of by-product reporting requirements to the United Nations Framework Convention on Climate Change (UNFCCC) in the 1990s, concern about climate change and product stewardship, abatement, and perhaps the collection of c-C4F8 by-product for use in the semiconductor industry where it can be easily abated, it is conceivable that emissions in developed countries were stabilized and then reduced, explaining the observed emission reduction in the 1980s and 1990s. Concurrently, production of PTFE in China began to increase rapidly. Without emission reduction requirements, it is plausible that global emissions today are dominated by China and other developing countries, in agreement with our analysis. We predict that c-C4F8 emissions will continue to rise and that c-C4F8 will become the second most important emitted PFC in terms of CO2-equivalent emissions within a year or two. The 2017 radiative forcing of c-C4F8 (0.52 mW m−2) is small but emissions of c-C4F8 and other PFCs, due to their very long atmospheric lifetimes, essentially permanently alter Earth's radiative budget and should be reduced. Significant emissions outside of the investigated regions clearly show that observational capabilities and reporting requirements need to be improved to understand global and country scale emissions of PFCs and other synthetic greenhouse gases and ozone depleting substances.

Description: Based on observations of three chlorofluorocarbons, CFC-13 (chlorotrifluoromethane), CFC-114 (dichlorotetrafluoroethane) and CFC-115 (chloropentafluoroethane) in atmospheric and firn samples, we reconstruct records of their tropospheric histories spanning nearly eight decades. These compounds were measured in polar firn air samples, in ambient air archived in canisters, and in-situ at the AGAGE (Advanced Global Atmospheric Gases Experiment) network and affiliated sites. Global emissions to the atmosphere are derived from these observations using an inversion based on a 12-box atmospheric transport model. For CFC-13, we provide the first comprehensive global analysis. This compound increased monotonically from its first appearance in the atmosphere in the late 1950s to a mean global abundance of 3.18 ppt (dry air mole fraction in parts-per-trillion, pmol mol−-1) in 2016. Its growth rate has decreased since the mid 1980s but has remained at a surprisingly high level of 0.02 ppt yr−1 since the late 2000s. CFC-114 increased from its appearance in the 1950s to a maximum of 16.6 ppt in the early 2000s, and has since slightly declined to 16.3 ppt in 2016. CFC-115 increased monotonically from its first appearance in the 1960s and reached a global mean mole fraction of 8.52 ppt in 2016. Growth rates of all three compounds over the past years are significantly larger than would be expected from zero emissions. Under the assumption of unaltered lifetimes and atmospheric transport patterns, we derive global emissions from our measurements, which have remained unexpectedly high in recent years: Mean yearly emissions for the last decade (2007–2016) of CFC-13 are at 0.48 ± 0.15 kt yr−1 (〉 15 % of past peak emissions), of CFC-114 at 1.90 ± 0.84 kt yr−1 (~ 10 % of peak emissions), and of CFC-115 at 0.80 ± 0.50 kt yr−1 (〉 5 % of peak emissions). Mean yearly emissions of CFC-115 for 2014–2016 are 1.08 ± 0.50 kt yr−1 and have more than doubled compared to 2009. Cumulative global emissions for CFC-114 derived from observations through 2016 exceed the global cumulative production derived from reported inventory data by 〉 10 % while those for CFC-115 agree well. We find CFC-13 emissions from aluminum smelters and impurities of CFC-115 in the refrigerant HFC-125 (CHF2CF3) but if extrapolated to global emissions neither of them can account for the lingering global emissions determined from the atmospheric observations. We also conduct regional inversions for the years 2012–2016 for the north-east Asian area using observations from the Korean Gosan AGAGE site and find significant emissions for CFC-114 and CFC-115, suggesting that a large fraction of their global emissions currently occur in north-eastern Asia and more specifically on the Chinese mainland.

Description: We present the organization, instrumentation, datasets, data interpretation, modeling, and accomplishments of the multinational, global atmospheric measurement program AGAGE (Advanced Global Atmospheric Gases Experiment). AGAGE is distinguished by its capability to measure globally, at high frequency and multiple sites, all the important species in the Montreal Protocol and all the important non-carbon dioxide (CO2) gases assessed by the Intergovernmental Panel on Climate Change (CO2 is also measured at several sites). The scientific objectives of AGAGE are important in furthering understanding of global chemical and climatic phenomena. They are to: (1) measure accurately the temporal and spatial distributions of anthropogenic gases that contribute the majority of reactive halogen to the stratosphere and/or are strong infrared absorbers [chlorocarbons, chlorofluorocarbons (CFCs), bromocarbons, hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs) and polyfluorinated compounds (perfluorocarbons (PFCs), nitrogen trifluoride (NF3), sulfuryl fluoride (SO2F2), and sulfur hexafluoride (SF6)), and use these measurements to determine the global rates of their emission and/or destruction (i.e. lifetimes); (2) measure accurately the global distributions and temporal behaviors and determine sources and sinks of non-CO2 biogenic-anthropogenic gases important to climate change and/or ozone depletion [methane (CH4), nitrous oxide (N2O), carbon monoxide (CO), molecular hydrogen (H2), methyl chloride (CH3Cl) and methyl bromide (CH3Br); (3) identify new long-lived greenhouse and ozone-depleting gases [e.g. SO2F2, NF3, heavy PFCs (C4F10, C5F12, C6F14, C7F16, and C8F18) and hydrofluoro-olefins (HFOs, e.g. CH2 = CFCF3) have been identified in AGAGE], initiate real-time monitoring of these new gases, and reconstruct their past histories from AGAGE, air-archive and firn-air measurements; (4) determine the average concentrations and trends of tropospheric hydroxyl radicals (OH) from the rates of destruction of atmospheric trichloroethane (CH3CCl3), HFCs and HCFCs, and estimates of their emissions; (5) determine from atmospheric observations and estimates of their destruction rates, the magnitudes, and distributions by region of surface sources/sinks of all measured gases; (6) provide accurate data on the global accumulation of many of these trace gases, that are used to test the synoptic/regional/global-scale circulations predicted by three-dimensional models; and (7) provide global and regional measurements of methane, carbon monoxide and molecular hydrogen, and estimates of hydroxyl levels, to test primary atmospheric oxidation pathways at mid-latitudes and the tropics. Network Information and Data Repository: http://agage.mit.edu/data or http://cdiac.esd.ornl.gov/ndps/alegage.html

Description: We present the organization, instrumentation, datasets, data interpretation, modeling, and accomplishments of the multinational global atmospheric measurement program AGAGE (Advanced Global Atmospheric Gases Experiment). AGAGE is distinguished by its capability to measure globally, at high frequency, and at multiple sites all the important species in the Montreal Protocol and all the important non-carbon-dioxide (non-CO2) gases assessed by the Intergovernmental Panel on Climate Change (CO2 is also measured at several sites). The scientific objectives of AGAGE are important in furthering our understanding of global chemical and climatic phenomena. They are the following: (1) to accurately measure the temporal and spatial distributions of anthropogenic gases that contribute the majority of reactive halogen to the stratosphere and/or are strong infrared absorbers (chlorocarbons, chlorofluorocarbons – CFCs, bromocarbons, hydrochlorofluorocarbons – HCFCs, hydrofluorocarbons – HFCs and polyfluorinated compounds (perfluorocarbons – PFCs), nitrogen trifluoride – NF3, sulfuryl fluoride – SO2F2, and sulfur hexafluoride – SF6) and use these measurements to determine the global rates of their emission and/or destruction (i.e., lifetimes); (2) to accurately measure the global distributions and temporal behaviors and determine the sources and sinks of non-CO2 biogenic–anthropogenic gases important to climate change and/or ozone depletion (methane – CH4, nitrous oxide – N2O, carbon monoxide – CO, molecular hydrogen – H2, methyl chloride – CH3Cl, and methyl bromide – CH3Br); (3) to identify new long-lived greenhouse and ozone-depleting gases (e.g., SO2F2, NF3, heavy PFCs (C4F10, C5F12, C6F14, C7F16, and C8F18) and hydrofluoroolefins (HFOs; e.g., CH2 = CFCF3) have been identified in AGAGE), initiate the real-time monitoring of these new gases, and reconstruct their past histories from AGAGE, air archive, and firn air measurements; (4) to determine the average concentrations and trends of tropospheric hydroxyl radicals (OH) from the rates of destruction of atmospheric trichloroethane (CH3CCl3), HFCs, and HCFCs and estimates of their emissions; (5) to determine from atmospheric observations and estimates of their destruction rates the magnitudes and distributions by region of surface sources and sinks of all measured gases; (6) to provide accurate data on the global accumulation of many of these trace gases that are used to test the synoptic-, regional-, and global-scale circulations predicted by three-dimensional models; and (7) to provide global and regional measurements of methane, carbon monoxide, and molecular hydrogen and estimates of hydroxyl levels to test primary atmospheric oxidation pathways at midlatitudes and the tropics. Network Information and Data Repository: http://agage.mit.edu/data or http://cdiac.ess-dive.lbl.gov/ndps/alegage.html (https://doi.org/10.3334/CDIAC/atg.db1001).

Description: We reconstruct atmospheric abundances of the potent greenhouse gas c-C4F8 (perfluorocyclobutane, perfluorocarbon PFC-318) from measurements of in situ, archived, firn, and aircraft air samples with precisions of ∼1 %–2 % reported on the SIO-14 gravimetric calibration scale. Combined with inverse methods, we found near-zero atmospheric abundances from the early 1900s to the early 1960s, after which they rose sharply, reaching 1.66 ppt (parts per trillion dry-air mole fraction) in 2017. Global c-C4F8 emissions rose from near zero in the 1960s to 1.2±0.1 (1σ) Gg yr−1 in the late 1970s to late 1980s, then declined to 0.77±0.03 Gg yr−1 in the mid-1990s to early 2000s, followed by a rise since the early 2000s to 2.20±0.05 Gg yr−1 in 2017. These emissions are significantly larger than inventory-based emission estimates. Estimated emissions from eastern Asia rose from 0.36 Gg yr−1 in 2010 to 0.73 Gg yr−1 in 2016 and 2017, 31 % of global emissions, mostly from eastern China. We estimate emissions of 0.14 Gg yr−1 from northern and central India in 2016 and find evidence for significant emissions from Russia. In contrast, recent emissions from northwestern Europe and Australia are estimated to be small (≤1 % each). We suggest that emissions from China, India, and Russia are likely related to production of polytetrafluoroethylene (PTFE, “Teflon”) and other fluoropolymers and fluorochemicals that are based on the pyrolysis of hydrochlorofluorocarbon HCFC-22 (CHClF2) in which c-C4F8 is a known by-product. The semiconductor sector, where c-C4F8 is used, is estimated to be a small source, at least in South Korea, Japan, Taiwan, and Europe. Without an obvious correlation with population density, incineration of waste-containing fluoropolymers is probably a minor source, and we find no evidence of emissions from electrolytic production of aluminum in Australia. While many possible emissive uses of c-C4F8 are known and though we cannot categorically exclude unknown sources, the start of significant emissions may well be related to the advent of commercial PTFE production in 1947. Process controls or abatement to reduce the c-C4F8 by-product were probably not in place in the early decades, explaining the increase in emissions in the 1960s and 1970s. With the advent of by-product reporting requirements to the United Nations Framework Convention on Climate Change (UNFCCC) in the 1990s, concern about climate change and product stewardship, abatement, and perhaps the collection of c-C4F8 by-product for use in the semiconductor industry where it can be easily abated, it is conceivable that emissions in developed countries were stabilized and then reduced, explaining the observed emission reduction in the 1980s and 1990s. Concurrently, production of PTFE in China began to increase rapidly. Without emission reduction requirements, it is plausible that global emissions today are dominated by China and other developing countries. We predict that c-C4F8 emissions will continue to rise and that c-C4F8 will become the second most important emitted PFC in terms of CO2-equivalent emissions within a year or two. The 2017 radiative forcing of c-C4F8 (0.52 mW m−2) is small but emissions of c-C4F8 and other PFCs, due to their very long atmospheric lifetimes, essentially permanently alter Earth's radiative budget and should be reduced. Significant emissions inferred outside of the investigated regions clearly show that observational capabilities and reporting requirements need to be improved to understand global and country-scale emissions of PFCs and other synthetic greenhouse gases and ozone-depleting substances.

Description: To prevent the spread of the COVID-19 epidemic, restrictions such as “lockdowns” were conducted globally, which led to a significant reduction in fossil fuel emissions, especially in urban areas. However, CO2 concentrations in urban areas are affected by many factors, such as weather, biological sinks and background CO2 fluctuations. Thus, it is difficult to directly observe the CO2 reductions from sparse ground observations. Here, we focus on urban ground transportation emissions, which were dramatically affected by the restrictions, to determine the reduction signals. We conducted six series of on-road CO2 observations in Beijing using mobile platforms before (BC), during (DC) and after (AC) the implementation of COVID-19 restrictions. To reduce the impacts of weather conditions and background fluctuations, we analyze vehicle trips with the most similar weather conditions possible and calculated the enhancement metric, which is the difference between the on-road CO2 concentration and the “urban background” CO2 concentration measured at the tower of the Institute of Atmospheric Physics (IAP), Chinese Academy of Sciences. The results showed that the DC CO2 enhancement was decreased by 41 (±1.3) parts per million (ppm) and 26 (±6.2) ppm compared to those for the BC and AC trips, respectively. Detailed analysis showed that, during COVID-19 restrictions, there was no difference between weekdays and weekends during working hours (09:00–17:00 local standard time; LST). The enhancements during rush hours (07:00–09:00 and 17:00–20:00 LST) were almost twice those during working hours, indicating that emissions during rush hours were much higher. For DC and BC, the enhancement reductions during rush hours were much larger than those during working hours. Our findings showed a clear CO2 concentration decrease during COVID-19 restrictions, which is consistent with the CO2 emissions reductions due to the pandemic. The enhancement method used in this study is an effective method to reduce the impacts of weather and background fluctuations. Low-cost sensors, which are inexpensive and convenient, could play an important role in further on-road and other urban observations.

Description: Atmospheric CO2 mole fractions are observed at Beijing (BJ), Xianghe (XH), and Xinglong (XL) in North China using Picarro G2301 cavity ring-down spectroscopy instruments. The measurement system is described comprehensively for the first time. The geographical distances among these three sites are within 200 km, but they have very different surrounding environments: BJ is inside the megacity; XH is in the suburban area; XL is in the countryside on a mountain. The mean and standard deviation of CO2 mole fractions at BJ, XH, and XL between October 2018 and September 2019 are 448.4±12.8, 436.0±9.2, and 420.6±8.2 ppm, respectively. The seasonal variations of CO2 at these three sites are similar, with a maximum in winter and a minimum in summer, which is dominated by the terrestrial ecosystem. However, the seasonal variations of CO2 at BJ and XH are more affected by human activities as compared to XL. Using CO2 at XL as the background, CO2 enhancements are observed simultaneously at BJ and XH. The diurnal variations of CO2 are driven by the boundary layer height, photosynthesis, and human activities at BJ, XH, and XL. We also compare the CO2 measurements at BJ, XH, and XL with five urban sites in the USA, and it is found that the CO2 mean concentration at BJ is the largest. Moreover, we address the impact of the wind on the CO2 mole fractions at BJ and XL. This study provides an insight into the spatial and temporal variations of CO2 mole fractions in North China.