Quantifying contributions of chlorofluorocarbon banks to emissions and impacts on the ozone layer and climate

Chlorofluorocarbon (CFC) banks from uses such as air conditioners or foams can be emitted after global production stops. Recent reports of unexpected emissions of CFC-11 raise the need to better quantify releases from these banks, and associated impacts on ozone depletion and climate change. Here we develop a Bayesian probabilistic model for CFC-11, 12, and 113 banks and their emissions, incorporating the broadest range of constraints to date. We find that bank sizes of CFC-11 and CFC-12 are larger than recent international scientific assessments suggested, and can account for much of current estimated CFC-11 and 12 emissions (with the exception of increased CFC-11 emissions after 2012). Left unrecovered, these CFC banks could delay Antarctic ozone hole recovery by about six years and contribute 9 billion metric tonnes of equivalent CO2 emission. Derived CFC-113 emissions are subject to uncertainty, but are much larger than expected, raising questions about its sources

Modelling marine emissions and atmospheric distributions of halocarbons and dimethyl sulfide: The influence of prescribed water concentration vs. prescribed emissions

Marine-produced short-lived trace gases such as dibromomethane (CH$_{2}$Br$_{2}$), bromoform (CHBr$_{3}$), methyliodide (CH$_{3}$I) and dimethyl sulfide (DMS) significantly impact tropospheric and stratospheric chemistry. Describing their marine emissions in atmospheric chemistry models as accurately as possible is necessary to quantify their impact on ozone depletion and Earth’s radiative budget. So far, marine emissions of trace gases have mainly been prescribed from emission climatologies, thus lacking the interaction between the actual state of the atmosphere and the ocean. Here we present simulations with the chemistry climate model EMAC (ECHAM5/MESSy Atmospheric Chemistry) with online calculation of emissions based on surface water concentrations, in contrast to directly prescribed emissions. Considering the actual state of the model atmosphere results in a concentration gradient consistent with model realtime conditions at the ocean surface and in the atmosphere, which determine the direction and magnitude of the computed flux. This method has a number of conceptual and practical benefits, as the modelled emission can respond consistently to changes in sea surface temperature, surface wind speed, sea ice cover and especially atmospheric mixing ratio. This online calculation could enhance, dampen or even invert the fluxes (i.e. deposition instead of emissions) of very short-lived substances (VSLS). We show that differences between prescribing emissions and prescribing concentrations (-28%for CH$_{2}$Br$_{2}$ to +11%for CHBr$_{3}$) result mainly from consideration of the actual, time-varying state of the atmosphere. The absolute magnitude of the differences depends mainly on the surface ocean saturation of each particular gas. Comparison to observations from aircraft, ships and ground stations reveals that computing the air–sea flux interactively leads in most of the cases to more accurate atmospheric mixing ratios in the model compared to the computation from prescribed emissions. Calculating emissions online also enables effective testing of different air–sea transfer velocity (k) parameterizations, which was performed here for eight different parameterizations. The testing of these different k values is of special interest for DMS, as recently published parameterizations derived by direct flux measurements using eddy covariance measurements suggest decreasing k values at high wind speeds or a linear relationship with wind speed. Implementing these parameterizations reduces discrepancies in modelled DMS atmospheric mixing ratios and observations by a factor of 1.5 compared to parameterizations with a quadratic or cubic relationship to wind speed

Report on unexpected emissions of CFC-11

peer reviewedEXECUTIVE SUMMARY Global CFC-11 emissions were expected to decrease steadily after 2010 because of the full phaseout of production and consumption. Surprisingly, however, CFC-11 emissions began to increase in 2013 and were high from 2014 to 2018. After the publication of this emission increase in 2018, emissions were substantially lower in 2019. A large fraction of the emission increase was attributed to Eastern China based on regional emission estimates. These regional emissions also declined substantially from 2017 to 2019. The increase in global CFC-11 emissions was not a result of increased bank releases. The amounts of CFC-11 in banks and the release rates from the banks remain highly uncertain. The increases in emissions observed to date are small enough not to have a major impact on CFC-11 atmospheric abundances, so they will not have a major impact on the expected stratospheric ozone recovery. However, the increases in banks and how they might augment future emissions have large uncertainties

Deriving Global OH Abundance and Atmospheric Lifetimes for Long-Lived Gases: A Search for CH 3 CCl 3 Alternatives

An accurate estimate of global hydroxyl radical (OH) abundance is important for projections of air quality, climate, and stratospheric ozone recovery. As the atmospheric mixing ratios of methyl chloroform (CH₃CCl₃) (MCF), the commonly used OH reference gas, approaches zero, it is important to find alternative approaches to infer atmospheric OH abundance and variability. The lack of global bottom‐up emission inventories is the primary obstacle in choosing a MCF alternative. We illustrate that global emissions of long‐lived trace gases can be inferred from their observed mixing ratio differences between the Northern Hemisphere (NH) and Southern Hemisphere (SH), given realistic estimates of their NH‐SH exchange time, the emission partitioning between the two hemispheres, and the NH versus SH OH abundance ratio. Using the observed long‐term trend and emissions derived from the measured hemispheric gradient, the combination of HFC‐32 (CH₂F₂), HFC‐134a (CH₂FCF₃, HFC‐152a (CH₃CHF₂), and HCFC‐22 (CHClF₂), instead of a single gas, will be useful as a MCF alternative to infer global and hemispheric OH abundance and trace gas lifetimes. The primary assumption on which this multispecies approach relies is that the OH lifetimes can be estimated by scaling the thermal reaction rates of a reference gas at 272 K on global and hemispheric scales. Thus, the derived hemispheric and global OH estimates are forced to reconcile the observed trends and gradient for all four compounds simultaneously. However, currently, observations of these gases from the surface networks do not provide more accurate OH abundance estimate than that from MCF

The state of the Martian climate

60°N was +2.0°C, relative to the 1981–2010 average value (Fig. 5.1). This marks a new high for the record. The average annual surface air temperature (SAT) anomaly for 2016 for land stations north of starting in 1900, and is a significant increase over the previous highest value of +1.2°C, which was observed in 2007, 2011, and 2015. Average global annual temperatures also showed record values in 2015 and 2016. Currently, the Arctic is warming at more than twice the rate of lower latitudes

Small Interannual Variability of Global Atmospheric Hydroxyl

The oxidizing capacity of the global atmosphere is largely determined by hydroxyl (OH) radicals and is diagnosed by analyzing methyl chloroform (CH3CCl3) measurements. Previously, large year-to-year changes in global mean OH concentrations have been inferred from such measurements, suggesting that the atmospheric oxidizing capacity is sensitive to perturbations by widespread air pollution and natural influences. We show how the interannual variability in OH has been more precisely estimated from CH3CCl3 measurements since 1998, when atmospheric gradients of CH3CCl3 had diminished as a result of the Montreal Protocol. We infer a small interannual OH variability as a result, indicating that global OH is generally well buffered against perturbations. This small variability is consistent with measurements of methane and other trace gases oxidized primarily by OH, as well as global photochemical model calculations

Growth rate‐dependent synthesis of halomethanes in marine heterotrophic bacteria and its implications for the ozone layer recovery

Halomethanes (e.g., CH3Cl, CH3Br, CH3I and CHBr3) are ozone-depleting compounds that, in contrast to the human-made chlorofluorocarbons, marine organisms synthesize naturally. Therefore, their production cannot be totally controlled by human action. However, identifying all their natural sources and understanding their synthesis regulation can help to predict their production rates and their impact on the future recovery of the Earth's ozone layer. Here we show that the synthesis of mono-halogenated halocarbons CH3Cl, CH3Br, and CH3I is a generalized process in representatives of the major marine heterotrophic bacteria groups. Furthermore, halomethane production was growth rate dependent in all the strains we studied, implying uniform synthesis regulation patterns among bacterioplankton. Using these experimental observations and in situ halomethane concentrations, we further evaluated the potential production rates associated with higher bacterial growth rates in response to global warming in a coastal environment within the Southern California Bight. Our estimates show that a 3°C temperature rise would translate into a 35%–84% increase in halomethane production rate by 2100. Overall, these data suggest that marine heterotrophic bacteria are significant producers of these climate-relevant gases and that their contribution to the atmospheric halogen budget could increase in the future, impacting the ozone layer recovery.This work was funded by the National Science Foundation project, Division of Ocean Sciences, OCE: 1559276.Peer reviewe

Toward a better understanding and quantification of methane emissions from shale gas development

The identification and quantification of methane emissions from natural gas production has become increasingly important owing to the increase in the natural gas component of the energy sector. An instrumented aircraft platform was used to identify large sources of methane and quantify emission rates in southwestern PA in June 2012. A large regional flux, 2.0-14 g CH4 s-1 km-2, was quantified for a ?2,800-km2 area, which did not differ statistically from a bottom-up inventory, 2.3-4.6 g CH4 s-1 km-2. Large emissions averaging 34 g CH 4/s per well were observed from seven well pads determined to be in the drilling phase, 2 to 3 orders of magnitude greater than US Environmental Protection Agency estimates for this operational phase. The emissions from these well pads, representing ?1% of the total number of wells, account for 4-30% of the observed regional flux. More work is needed to determine all of the sources of methane emissions from natural gas production, to ascertain why these emissions occur and to evaluate their climate and atmospheric chemistry impacts.Funding was provided by the David R. Atkinson Center for a Sustainable Future at Cornell University

Observational evidence for interhemispheric hydroxyl-radical parity

The hydroxyl radical (OH) is a key oxidant involved in the removal of air pollutants and greenhouse gases from the atmosphere1, 2, 3. The ratio of Northern Hemispheric to Southern Hemispheric (NH/SH) OH concentration is important for our understanding of emission estimates of atmospheric species such as nitrogen oxides and methane4, 5, 6. It remains poorly constrained, however, with a range of estimates from 0.85 to 1.4 (refs 4, 7,8,9,10). Here we determine the NH/SH ratio of OH with the help of methyl chloroform data (a proxy for OH concentrations) and an atmospheric transport model that accurately describes interhemispheric transport and modelled emissions. We find that for the years 2004–2011 the model predicts an annual mean NH–SH gradient of methyl chloroform that is a tight linear function of the modelled NH/SH ratio in annual mean OH. We estimate a NH/SH OH ratio of 0.97 ± 0.12 during this time period by optimizing global total emissions and mean OH abundance to fit methyl chloroform data from two surface-measurement networks and aircraft campaigns11, 12, 13. Our findings suggest that top-down emission estimates of reactive species such as nitrogen oxides in key emitting countries in the NH that are based on a NH/SH OH ratio larger than 1 may be overestimated