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Abstract. Nitrous oxide is a potent greenhouse gas (GHG) and ozone-depleting substance, whose atmospheric abundance has risen throughout the contemporary record. In this work, we carry out the first global hierarchical Bayesian inversion to solve for nitrous oxide emissions, which includes prior emissions with truncated Gaussian distributions and Gaussian model errors, in order to examine the drivers of the atmospheric surface growth rate. We show that both emissions and climatic variability are key drivers of variations in the surface nitrous oxide growth rate between 2011 and 2020. We derive increasing global nitrous oxide emissions, which are mainly driven by emissions between 0 and 30∘ N, with the highest emissions recorded in 2020. Our mean global total emissions for 2011–2020 of 17.2 (16.7–17.7 at the 95 % credible intervals) Tg N yr−1, comprising of 12.0 (11.2–12.8) Tg N yr−1 from land and 5.2 (4.5–5.9) Tg N yr−1 from ocean, agrees well with previous studies, but we find that emissions are poorly constrained for some regions of the world, particularly for the oceans. The prior emissions used in this and other previous work exhibit a seasonal cycle in the extra-tropical Northern Hemisphere that is out of phase with the posterior solution, and there is a substantial zonal redistribution of emissions from the prior to the posterior. Correctly characterizing the uncertainties in the system, for example in the prior emission fields, is crucial for deriving posterior fluxes that are consistent with observations. In this hierarchical inversion, the model-measurement discrepancy and the prior flux uncertainty are informed by the data, rather than solely through “expert judgement”. We show cases where this framework provides different plausible adjustments to the prior fluxes compared to inversions using widely adopted, fixed uncertainty constraints.

Abstract. Emissions of the potent greenhouse gas perfluorocyclobutane(c-C4F8, PFC-318, octafluorocyclobutane) into the global atmosphereinferred from atmospheric measurements have been increasing sharply sincethe early 2000s. We find that these inferred emissions are highly correlatedwith the production of hydrochlorofluorocarbon-22 (HCFC-22, CHClF2) forfeedstock (FS) uses, because almost all HCFC-22 FS is pyrolyzed to produce(poly)tetrafluoroethylene ((P)TFE) and hexafluoropropylene (HFP), a processin which c-C4F8 is a known by-product, causing a significantfraction of global c-C4F8 emissions. We find a global emissionfactor of ∼0.003 kg c-C4F8 per kilogram of HCFC-22 FSpyrolyzed. Mitigation of these c-C4F8 emissions, e.g., throughprocess optimization, abatement, or different manufacturing processes, suchas refined methods of electrochemical fluorination and waste recycling,could reduce the climate impact of this industry. While it has been shownthat c-C4F8 emissions from developing countries dominate globalemissions, more atmospheric measurements and/or detailed process statisticsare needed to quantify c-C4F8 emissions at country to facilitylevels.

Abstract. The emissions of hydrofluorocarbons (HFCs) have increased significantly in the past 2 decades, primarily as a result of the phaseout of ozone-depleting substances under the Montreal Protocol and the use of HFCs as their replacements. In 2015, large increases were projected in HFC use and emissions in this century in the absence of regulations, contributing up to 0.5 ∘C to global surface warming by 2100. In 2019, the Kigali Amendment to the Montreal Protocol came into force with the goal of limiting the use of HFCs globally, and currently, regulations to limit the use of HFCs are in effect in several countries. Here, we analyze trends in HFC emissions inferred from observations of atmospheric abundances and compare them with previous projections. Total CO2 eq. inferred HFC emissions continue to increase through 2019 (to about 0.8 GtCO2eq.yr-1) but are about 20 % lower than previously projected for 2017–2019, mainly because of the lower global emissionsof HFC-143a. This indicates that HFCs are used much less in industrial and commercial refrigeration (ICR) applications than previously projected. This is supported by data reported by the developed countries and the lower reported consumption of HFC-143a in China. Because this time period preceded the beginning of the Kigali provisions, this reduction cannot be linked directly to the provisions of the Kigali Amendment. However, it could indicate that companies transitioned away from the HFC-143a with its high global warming potential (GWP) for ICR applications in anticipation of national or global mandates. There are two new HFC scenarios developed based (1) on current trends in HFC use and Kigali-independent (K-I) control policies currently existing in several countries and (2) current HFC trends and compliance with the Kigali Amendment (KA-2022). These current policies reduce projected emissions in 2050 from the previously calculated 4.0–5.3 GtCO2eq.yr-1 to 1.9–3.6 GtCO2eq.yr-1. The added provisions of the Kigali Amendment are projected toreduce the emissions further to 0.9–1.0 GtCO2eq.yr-1 in 2050. Without any controls, projections suggest a HFC contribution of0.28–0.44 ∘C to global surface warming by 2100, compared to a temperature contribution of 0.14–0.31 ∘C that is projectedconsidering the national K-I policies current in place. Warming from HFCs is additionally limited by the Kigali Amendment controls to a contribution of about 0.04 ∘C by 2100.

Global and regional atmospheric measurements and modeling can play key roles in discovering and quantifying unexpected nascent emissions of environmentally important substances. We focus here on three hydrochlorofluorocarbons (HCFCs) that are restricted by the Montreal Protocol because of their roles in stratospheric ozone depletion. Based on measurements of archived air samples and on in situ measurements at stations of the Advanced Global Atmospheric Gases Experiment (AGAGE) network, we report global abundances, trends, and regional enhancements for HCFC-132b ([Formula: see text]), which is newly discovered in the atmosphere, and updated results for HCFC-133a ([Formula: see text]) and HCFC-31 ([Formula: see text]ClF). No purposeful end-use is known for any of these compounds. We find that HCFC-132b appeared in the atmosphere 20 y ago and that its global emissions increased to 1.1 Gg⋅y-1 by 2019. Regional top-down emission estimates for East Asia, based on high-frequency measurements for 2016-2019, account for ∼95% of the global HCFC-132b emissions and for ∼80% of the global HCFC-133a emissions of 2.3 Gg⋅y-1 during this period. Global emissions of HCFC-31 for the same period are 0.71 Gg⋅y-1 Small European emissions of HCFC-132b and HCFC-133a, found in southeastern France, ceased in early 2017 when a fluorocarbon production facility in that area closed. Although unreported emissive end-uses cannot be ruled out, all three compounds are most likely emitted as intermediate by-products in chemical production pathways. Identification of harmful emissions to the atmosphere at an early stage can guide the effective development of global and regional environmental policy.

With the successful implementation of the Montreal Protocol on Substances that Deplete the Ozone Layer, the atmospheric abundance of ozone-depleting substances continues to decrease slowly and the Antarctic ozone hole is showing signs of recovery. However, growing emissions of unregulated short-lived anthropogenic chlorocarbons are offsetting some of these gains. Here, we report an increase in emissions from China of the industrially produced chlorocarbon, dichloromethane (CH2Cl2). The emissions grew from 231 (213-245) Gg yr-1 in 2011 to 628 (599-658) Gg yr-1 in 2019, with an average annual increase of 13 (12-15) %, primarily from eastern China. The overall increase in CH2Cl2 emissions from China has the same magnitude as the global emission rise of 354 (281-427) Gg yr-1 over the same period. If global CH2Cl2 emissions remain at 2019 levels, they could lead to a delay in Antarctic ozone recovery of around 5 years compared to a scenario with no CH2Cl2 emissions.

Nitrous oxide (N2O), like carbon dioxide, is a long-lived greenhouse gas that accumulates in the atmosphere. Over the past 150 years, increasing atmospheric N2O concentrations have contributed to stratospheric ozone depletion1 and climate change2, with the current rate of increase estimated at 2 per cent per decade. Existing national inventories do not provide a full picture of N2O emissions, owing to their omission of natural sources and limitations in methodology for attributing anthropogenic sources. Here we present a global N2O inventory that incorporates both natural and anthropogenic sources and accounts for the interaction between nitrogen additions and the biochemical processes that control N2O emissions. We use bottom-up (inventory, statistical extrapolation of flux measurements, process-based land and ocean modelling) and top-down (atmospheric inversion) approaches to provide a comprehensive quantification of global N2O sources and sinks resulting from 21 natural and human sectors between 1980 and 2016. Global N2O emissions were 17.0 (minimum-maximum estimates: 12.2-23.5) teragrams of nitrogen per year (bottom-up) and 16.9 (15.9-17.7) teragrams of nitrogen per year (top-down) between 2007 and 2016. Global human-induced emissions, which are dominated by nitrogen additions to croplands, increased by 30% over the past four decades to 7.3 (4.2-11.4) teragrams of nitrogen per year. This increase was mainly responsible for the growth in the atmospheric burden. Our findings point to growing N2O emissions in emerging economies-particularly Brazil, China and India. Analysis of process-based model estimates reveals an emerging N2O-climate feedback resulting from interactions between nitrogen additions and climate change. The recent growth in N2O emissions exceeds some of the highest projected emission scenarios3,4, underscoring the urgency to mitigate N2O emissions.

Abstract. We reconstruct atmospheric abundances of the potentgreenhouse gas c-C4F8 (perfluorocyclobutane, perfluorocarbonPFC-318) from measurements of in situ, archived, firn, and aircraft airsamples with precisions of ∼1 %–2 % reported on the SIO-14gravimetric calibration scale. Combined with inverse methods, we found near-zero atmospheric abundances from the early 1900s to the early 1960s, afterwhich they rose sharply, reaching 1.66 ppt (parts per trillion dry-air molefraction) in 2017. Global c-C4F8 emissions rose from near zero inthe 1960s to 1.2±0.1 (1σ) Gg yr−1 in the late 1970s tolate 1980s, then declined to 0.77±0.03 Gg yr−1 in the mid-1990sto 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 thaninventory-based emission estimates. Estimated emissions from eastern Asiarose 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 estimateemissions of 0.14 Gg yr−1 from northern and central India in 2016 andfind evidence for significant emissions from Russia. In contrast, recentemissions from northwestern Europe and Australia are estimated to be small(≤1 % each). We suggest that emissions from China, India, and Russiaare likely related to production of polytetrafluoroethylene (PTFE,“Teflon”) and other fluoropolymers and fluorochemicals that are based onthe pyrolysis of hydrochlorofluorocarbon HCFC-22 (CHClF2) in whichc-C4F8 is a known by-product. The semiconductor sector, wherec-C4F8 is used, is estimated to be a small source, at least inSouth Korea, Japan, Taiwan, and Europe. Without an obvious correlation withpopulation density, incineration of waste-containing fluoropolymers isprobably a minor source, and we find no evidence of emissions fromelectrolytic production of aluminum in Australia. While many possibleemissive uses of c-C4F8 are known and though we cannotcategorically exclude unknown sources, the start of significant emissionsmay well be related to the advent of commercial PTFE production in 1947.Process controls or abatement to reduce the c-C4F8 by-product wereprobably not in place in the early decades, explaining the increase inemissions in the 1960s and 1970s. With the advent of by-product reportingrequirements 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 usein the semiconductor industry where it can be easily abated, it isconceivable that emissions in developed countries were stabilized and thenreduced, explaining the observed emission reduction in the 1980s and 1990s.Concurrently, production of PTFE in China began to increase rapidly. Withoutemission reduction requirements, it is plausible that global emissions todayare dominated by China and other developing countries. We predict thatc-C4F8 emissions will continue to rise and that c-C4F8will become the second most important emitted PFC in terms ofCO2-equivalent emissions within a year or two. The 2017 radiativeforcing of c-C4F8 (0.52 mW m−2) is small but emissions ofc-C4F8 and other PFCs, due to their very long atmosphericlifetimes, essentially permanently alter Earth's radiative budget and shouldbe reduced. Significant emissions inferred outside of the investigatedregions clearly show that observational capabilities and reportingrequirements need to be improved to understand global and country-scaleemissions of PFCs and other synthetic greenhouse gases and ozone-depletingsubstances.

The detection of meteorological, chemical, or other signals in modeled or observed air quality data - such as an estimate of a temporal trend in surface ozone data, or an estimate of the mean ozone of a particular region during a particular season - is a critical component of modern atmospheric chemistry. However, the magnitude of a surface air quality signal is generally small compared to the magnitude of the underlying chemical, meteorological, and climatological variabilities (and their interactions) that exist both in space and in time, and which include variability in emissions and surface processes. This can present difficulties for both policymakers and researchers as they attempt to identify the influence or signal of climate trends (e.g., any pauses in warming trends), the impact of enacted emission reductions policies (e.g., United States NOx State Implementation Plans), or an estimate of the mean state of highly variable data (e.g., summertime ozone over the northeastern United States). Here we examine the scale dependence of the variability of simulated and observed surface ozone data within the United States and the likelihood that a particular choice of temporal or spatial averaging scales produce a misleading estimate of a particular ozone signal. Our main objective is to develop strategies that reduce the likelihood of overconfidence in simulated ozone estimates. We find that while increasing the extent of both temporal and spatial averaging can enhance signal detection capabilities by reducing the noise from variability, a strategic combination of particular temporal and spatial averaging scales can maximize signal detection capabilities over much of the continental US. For signals that are large compared to the meteorological variability (e.g., strong emissions reductions), shorter averaging periods and smaller spatial averaging regions may be sufficient, but for many signals that are smaller than or comparable in magnitude to the underlying meteorological variability, we recommend temporal averaging of 10-15 years combined with some level of spatial averaging (up to several hundred kilometers). If this level of averaging is not practical (e.g., the signal being examined is at a local scale), we recommend some exploration of the spatial and temporal variability to provide context and confidence in the robustness of the result. These results are consistent between simulated and observed data, as well as within a single model with different sets of parameters. The strategies selected in this study are not limited to surface ozone data and could potentially maximize signal detection capabilities within a broad array of climate and chemical observations or model output.

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.

Molecular hydrogen (H2 ) is an atmospheric trace gas with a large microbe-mediated soil sink, yet cycling of this compound throughout ecosystems is poorly understood. Measurements of the sources and sinks of H2 in various ecosystems are sparse, resulting in large uncertainties in the global H2 budget. Constraining the H2 cycle is critical to understanding its role in atmospheric chemistry and climate. We measured H2 fluxes at high frequency in a temperate mixed deciduous forest for 15 months using a tower-based flux-gradient approach to determine both the soil-atmosphere and the net ecosystem flux of H2 . We found that Harvard Forest is a net H2 sink (-1.4 ± 1.1 kg H2  ha-1 ) with soils as the dominant H2 sink (-2.0 ± 1.0 kg H2  ha-1 ) and aboveground canopy emissions as the dominant H2 source (+0.6 ± 0.8 kg H2  ha-1 ). Aboveground emissions of H2 were an unexpected and substantial component of the ecosystem H2 flux, reducing net ecosystem uptake by 30% of that calculated from soil uptake alone. Soil uptake was highly seasonal (July maximum, February minimum), positively correlated with soil temperature and negatively correlated with environmental variables relevant to diffusion into soils (i.e., soil moisture, snow depth, snow density). Soil microbial H2 uptake was correlated with rhizosphere respiration rates (r = 0.8, P

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.

HCFC-22 (CHClF2) and HFC-134a (CH2FCF3) are two major gases currently used worldwide in domestic and commercial refrigeration and air conditioning. HCFC-22 contributes to stratospheric ozone depletion, and both species are potent greenhouse gases. In this work, we study in situ observations of HCFC-22 and HFC-134a taken from research aircraft over the Pacific Ocean in a 3-y span [HIaper-Pole-to-Pole Observations (HIPPO) 2009-2011] and combine these data with long-term ground observations from global surface sites [National Oceanic and Atmospheric Administration (NOAA) and Advanced Global Atmospheric Gases Experiment (AGAGE) networks]. We find the global annual emissions of HCFC-22 and HFC-134a have increased substantially over the past two decades. Emissions of HFC-134a are consistently higher compared with the United Nations Framework Convention on Climate Change (UNFCCC) inventory since 2000, by 60% more in recent years (2009-2012). Apart from these decadal emission constraints, we also quantify recent seasonal emission patterns showing that summertime emissions of HCFC-22 and HFC-134a are two to three times higher than wintertime emissions. This unforeseen large seasonal variation indicates that unaccounted mechanisms controlling refrigerant gas emissions are missing in the existing inventory estimates. Possible mechanisms enhancing refrigerant losses in summer are (i) higher vapor pressure in the sealed compartment of the system at summer high temperatures and (ii) more frequent use and service of refrigerators and air conditioners in summer months. Our results suggest that engineering (e.g., better temperature/vibration-resistant system sealing and new system design of more compact/efficient components) and regulatory (e.g., reinforcing system service regulations) steps to improve containment of these gases from working devices could effectively reduce their release to the atmosphere.

Methane is an important greenhouse gas, responsible for about 20% of the warming induced by long-lived greenhouse gases since pre-industrial times. By reacting with hydroxyl radicals, methane reduces the oxidizing capacity of the atmosphere and generates ozone in the troposphere. Although most sources and sinks of methane have been identified, their relative contributions to atmospheric methane levels are highly uncertain. As such, the factors responsible for the observed stabilization of atmospheric methane levels in the early 2000s, and the renewed rise after 2006, remain unclear. Here, we construct decadal budgets for methane sources and sinks between 1980 and 2010, using a combination of atmospheric measurements and results from chemical transport models, ecosystem models, climate chemistry models and inventories of anthropogenic emissions. The resultant budgets suggest that data-driven approaches and ecosystem models overestimate total natural emissions. We build three contrasting emission scenarios-which differ in fossil fuel and microbial emissions-to explain the decadal variability in atmospheric methane levels detected, here and in previous studies, since 1985. Although uncertainties in emission trends do not allow definitive conclusions to be drawn, we show that the observed stabilization of methane levels between 1999 and 2006 can potentially be explained by decreasing-to-stable fossil fuel emissions, combined with stable-to-increasing microbial emissions. We show that a rise in natural wetland emissions and fossil fuel emissions probably accounts for the renewed increase in global methane levels after 2006, although the relative contribution of these two sources remains uncertain. © 2013 Macmillan Publishers Limited.

The diurnal-to-monthly behavior of the fluxes of OCS, H2S, and CS2 from a mixed-Spartina grass-covered site in a Wallops Island salt water marsh was determined through a series of experiments in August and September, 1982. Absolute flux values were determined for OCS and H2S, while only relative values were determined for CS2. The rates of emission of OCS and H2S were observed to vary diurnally and to be strongly influenced by tides. The time-averaged flux values show that such mixed-Spartina stands are insignificant (≪ 1%) global sources of H2S or CS2 and insignificant contributors to the global OCS cycle (< 1%). These results demonstrate that some marsh regions play a minor role in the global sulfur budget and, consequently, that the inclusion of such areas in extrapolations of measurements of more productive regions could lead to an overestimate of the role of salt water marshes in the global sulfur budget. © 1986 D. Reidel Publishing Company.