Modelling the growth of atmospheric nitrous oxide using a global hierarchical inversion

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.</p

Modelling the growth of atmospheric nitrous oxide using a global hierarchical inversion

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.</p

Global emissions of perfluorocyclobutane (PFC-318, c-C4F8) resulting from the use of hydrochlorofluorocarbon-22 (HCFC-22) feedstock to produce polytetrafluoroethylene (PTFE) and related fluorochemicals

Abstract. Emissions of the potent greenhouse gas perfluorocyclobutane (c-C4F8, PFC-318, octafluorocyclobutane) into the global atmosphere inferred from atmospheric measurements have been increasing sharply since the early 2000s. We find that these inferred emissions are highly correlated with the production of hydrochlorofluorocarbon-22 (HCFC-22, CHClF2) for feedstock (FS) uses, because almost all HCFC-22 FS is pyrolyzed to produce (poly)tetrafluoroethylene ((P)TFE) and hexafluoropropylene (HFP), a process in which c-C4F8 is a known by-product, causing a significant fraction of global c-C4F8 emissions. We find a global emission factor of ∼0.003 kg c-C4F8 per kilogram of HCFC-22 FS pyrolyzed. Mitigation of these c-C4F8 emissions, e.g., through process optimization, abatement, or different manufacturing processes, such as refined methods of electrochemical fluorination and waste recycling, could reduce the climate impact of this industry. While it has been shown that c-C4F8 emissions from developing countries dominate global emissions, more atmospheric measurements and/or detailed process statistics are needed to quantify c-C4F8 emissions at country to facility levels

Global trends and European emissions of tetrafluoromethane (CF4), hexafluoroethane (C2F6) and octafluoropropane (C3F8)

Perfluorocarbons (PFCs) are amongst the most potent greenhouse gases listed under the United Nations Framework Convention on Climate Change (UNFCCC). With atmospheric lifetimes on the order of thousands to tens of thousands of years, PFC emissions represent a permanent alteration to the global atmosphere on human timescales. While the industries responsible for the vast majority of these emissions-aluminium smelting and semi-conductor manufacturing-have made efficiency improvements and introduced abatement measures, the global mean mole fractions of three PFCs, namely tetrafluoromethane (CF4, PFC-14), hexafluoroethane (C2F6, PFC-116) and octafluoropropane (C3F8, PFC-218), continue to grow. In this study, we update baseline growth rates using in situ high-frequency measurements from the Advanced Global Atmospheric Gases Experiment (AGAGE) and, using data from four European stations, estimate PFC emissions for northwest Europe. The global growth rate of CF4 decreased from 1.3 ppt yr-1 in 1979 to 0.6 ppt yr-1 around 2010 followed by a renewed steady increase to 0.9 ppt yr-1 in 2019. For C2F6, the growth rate grew to a maximum of 0.125 ppt yr-1 around 1999, followed by a decline to a minimum of 0.075 ppt yr-1 in 2009, followed by weak growth thereafter. The C3F8 growth rate was around 0.007 ppt yr-1 until the early 1990s and then quickly grew to a maximum of 0.03 ppt yr-1 in 2003-2004. Following a period of decline until 2012 to 0.015 ppt yr-1, the growth rate slowly increased again to ∼ 0.017 ppt yr-1 in 2019. We used an inverse modelling framework to infer PFC emissions for northwest Europe. No statistically significant trend in regional emissions was observed for any of the PFCs assessed. For CF4, European emissions in early years were linked predominantly to the aluminium industry. However, we link large emissions in recent years to a chemical manufacturer in northwest Italy. Emissions of C2F6 are linked to a range of sources, including a semi-conductor manufacturer in Ireland and a cluster of smelters in Germany's Ruhr valley. In contrast, northwest European emissions of C3F8 are dominated by a single source in northwest England, raising the possibility of using emissions from this site for a tracer release experiment

Atmospheric abundance and global emissions of perfluorocarbons CF4, C2F6 and C3F8 since 1800 inferred from ice core, firn, air archive and in situ measurements

Perfluorocarbons (PFCs) are very potent and long-lived greenhouse gases in the atmosphere, released predominantly during aluminium production and semiconductor manufacture. They have been targeted for emission controls under the United Nations Framework Convention on Climate Change. Here we present the first continuous records of the atmospheric abundance of CF4 (PFC-14), C2F6 (PFC-116) and C3F8 (PFC-218) from 1800 to 2014. The records are derived from high-precision measurements of PFCs in air extracted from polar firn or ice at six sites (DE08, DE08-2, DSSW20K, EDML, NEEM and South Pole) and air archive tanks and atmospheric air sampled from both hemispheres. We take account of the age characteristics of the firn and ice core air samples and demonstrate excellent consistency between the ice core, firn and atmospheric measurements. We present an inversion for global emissions from 1900 to 2014. We also formulate the inversion to directly infer emission factors for PFC emissions due to aluminium production prior to the 1980s. We show that 19th century atmospheric levels, before significant anthropogenic influence, were stable at 34.1 ± 0.3 ppt for CF4 and below detection limits of 0.002 and 0.01 ppt for C2F6 and C3F8, respectively. We find a significant peak in CF4 and C2F6 emissions around 1940, most likely due to the high demand for aluminium during World War II, for example for construction of aircraft, but these emissions were nevertheless much lower than in recent years. The PFC emission factors for aluminium production in the early 20th century were significantly higher than today but have decreased since then due to improvements and better control of the smelting process. Mitigation efforts have led to decreases in emissions from peaks in 1980 (CF4) or early-to-mid-2000s (C2F6 and C3F8) despite the continued increase in global aluminium production; however, these decreases in emissions appear to have recently halted. We see a temporary reduction of around 15 % in CF4 emissions in 2009, presumably associated with the impact of the global financial crisis on aluminium and semiconductor production

Evidence of a recent decline in UK emissions of hydrofluorocarbons determined by the InTEM inverse model and atmospheric measurements

National greenhouse gas inventories (GHGIs) are submitted annually to the United Nations Framework Convention on Climate Change (UNFCCC). They are estimated in compliance with Intergovernmental Panel on Climate Change (IPCC) methodological guidance using activity data, emission factors and facility-level measurements. For some sources, the outputs from these calculations are very uncertain. Inverse modelling techniques that use high-quality, long-term measurements of atmospheric gases have been developed to provide independent verification of national GHGIs. This is considered good practice by the IPCC as it helps national inventory compilers to verify reported emissions and to reduce emission uncertainty. Emission estimates from the InTEM (Inversion Technique for Emission Modelling) model are presented for the UK for the hydrofluorocarbons (HFCs) reported to the UNFCCC (HFC-125, HFC-134a, HFC-143a, HFC-152a, HFC-23, HFC-32, HFC-227ea, HFC-245fa, HFC-43-10mee and HFC-365mfc). These HFCs have high global warming potentials (GWPs), and the global background mole fractions of all but two are increasing, thus highlighting their relevance to the climate and a need for increasing the accuracy of emission estimation for regulatory purposes. This study presents evidence that the long-term annual increase in growth of HFC-134a has stopped and is now decreasing. For HFC-32 there is an early indication, its rapid global growth period has ended, and there is evidence that the annual increase in global growth for HFC-125 has slowed from 2018. The inverse modelling results indicate that the UK implementation of European Union regulation of HFC emissions has been successful in initiating a decline in UK emissions from 2018. Comparison of the total InTEM UK HFC emissions in 2020 with the average from 2009-2012 shows a drop of 35ĝ€¯%, indicating progress toward the target of a 79ĝ€¯% decrease in sales by 2030. The total InTEM HFC emission estimates (2008-2018) are on average 73 (62-83)ĝ€¯% of, or 4.3 (2.7-5.9)ĝ€¯Tgĝ€¯CO2-eqĝ€¯yr-1 lower than, the total HFC emission estimates from the UK GHGI. There are also significant discrepancies between the two estimates for the individual HFCs.</p

Using ice core measurements from Taylor Glacier, Antarctica, to calibrate in situ cosmogenic 14 C production rates by muons

Cosmic rays entering the Earth’s atmosphere produce showers of secondary particles such as protons, neutrons, and muons. The interaction of these particles with oxygen-16 (16O) in minerals such as ice and quartz can produce carbon-14 (14C). In glacial ice, 14C is also incorporated through trapping of 14C-containing atmospheric gases (14CO2, 14CO, and 14CH4). Understanding the production rates of in situ cosmogenic 14C is important to deconvolve the in situ cosmogenic and atmospheric 14C signals in ice, both of which contain valuable paleoenvironmental information. Unfortunately, the in situ 14C production rates by muons (which are the dominant production mechanism at depths of > 6m solid ice equivalent) are uncertain. In this study, we use measurements of in situ 14C in ancient ice (> 50 ka) from the Taylor Glacier, an ablation site in Antarctica, in combination with a 2D ice flow model to better constrain the compound-specific rates of 14C production by muons and the partitioning of in situ 14C between CO2, CO, and CH4. Our measurements show that 33.7% (11.4%; 95% confidence interval) of the produced cosmogenic 14C forms 14CO and 66.1% (11.5%; 95% confidence interval) of the produced cosmogenic 14C forms 14CO2. 14CH4 represents a very small fraction (< 0.3%) of the total. Assuming that the majority of in situ muogenic 14C in ice forms 14CO2, 14CO, and 14CH4, we also calculated muogenic 14C production rates that are lower by factors of 5.7 (3.6–13.9; 95% confidence interval) and 3.7 (2.0–11.9; 95% confidence interval) for negative muon capture and fast muon interactions, respectively, when compared to values determined in quartz from laboratory studies (Heisinger et al., 2002a, b) and in a natural setting (Lupker et al., 2015). This apparent discrepancy in muogenic 14C production rates in ice and quartz currently lacks a good explanation and requires further investigation

The increasing atmospheric burden of the greenhouse gas sulfur hexafluoride (SF&lt;sub&gt;6&lt;/sub&gt;)

We report a 40-year history of SF6 atmospheric mole fractions measured at the Advanced Global Atmospheric Gases Experiment (AGAGE) monitoring sites, combined with archived air samples, to determine emission estimates from 1978 to 2018. Previously we reported a global emission rate of 7.3±0.6 Gg yr-1 in 2008 and over the past decade emissions have continued to increase by about 24% to 9.04±0.35 Gg yr-1 in 2018. We show that changing patterns in SF6 consumption from developed (Kyoto Protocol Annex-1) to developing countries (non-Annex-1) and the rapid global expansion of the electric power industry, mainly in Asia, have increased the demand for SF6-insulated switchgear, circuit breakers, and transformers. The large bank of SF6 sequestered in this electrical equipment provides a substantial source of emissions from maintenance, replacement, and continuous leakage. Other emissive sources of SF6 occur from the magnesium, aluminium, and electronics industries as well as more minor industrial applications. More recently, reported emissions, including those from electrical equipment and metal industries, primarily in the Annex-1 countries, have declined steadily through substitution of alternative blanketing gases and technological improvements in less emissive equipment and more efficient industrial practices. Nevertheless, there are still demands for SF6 in Annex-1 countries due to economic growth, as well as continuing emissions from older equipment and additional emissions from newly installed SF6-insulated electrical equipment, although at low emission rates. In addition, in the non-Annex-1 countries, SF6 emissions have increased due to an expansion in the growth of the electrical power, metal, and electronics industries to support their continuing development. There is an annual difference of 2.5-5 Gg yr-1 (1990-2018) between our modelled top-down emissions and the UNFCCC-reported bottom-up emissions (United Nations Framework Convention on Climate Change), which we attempt to reconcile through analysis of the potential contribution of emissions from the various industrial applications which use SF6. We also investigate regional emissions in East Asia (China, S. Korea) and western Europe and their respective contributions to the global atmospheric SF6 inventory. On an average annual basis, our estimated emissions from the whole of China are approximately 10 times greater than emissions from western Europe. In 2018, our modelled Chinese and western European emissions accounted for ∼36% and 3.1 %, respectively, of our global SF6 emissions estimate.NASA (Grant NAG5-12669, NNX07AE89G and NNX11AF17G)NOAA (Contract RA-133R-15-CN-0008