Chlorine activation and enhanced ozone depletion induced by wildfire aerosol.

Remarkable perturbations in the stratospheric abundances of chlorine species and ozone were observed over Southern Hemisphere mid-latitudes following the 2020 Australian wildfires1,2. These changes in atmospheric chemical composition suggest that wildfire aerosols affect stratospheric chlorine and ozone depletion chemistry. Here we propose that wildfire aerosol containing a mixture of oxidized organics and sulfate3-7 increases hydrochloric acid solubility8-11 and associated heterogeneous reaction rates, activating reactive chlorine species and enhancing ozone loss rates at relatively warm stratospheric temperatures. We test our hypothesis by comparing atmospheric observations to model simulations that include the proposed mechanism. Modelled changes in 2020 hydrochloric acid, chlorine nitrate and hypochlorous acid abundances are in good agreement with observations1,2. Our results indicate that wildfire aerosol chemistry, although not accounting for the record duration of the 2020 Antarctic ozone hole, does yield an increase in its area and a 3-5% depletion of southern mid-latitude total column ozone. These findings increase concern2,12,13 that more frequent and intense wildfires could delay ozone recovery in a warming world.

Trifluoroiodomethane as a Precursor to High Global Warming Potential Climate Pollutants: Could the Transformation of Climatically Benign CF3I into Potent Greenhouse Gases Significantly Increase Refrigerant-Related Greenhouse Gas Emissions?

The transition away from the production and consumption of high global warming potential (GWP) hydrofluorocarbons (HFCs) under the 2016 Kigali Amendment to the Montreal Protocol on Substances that Deplete the Ozone Layer (Montreal Protocol) has prompted air conditioning, refrigeration, and heat pump equipment manufacturers to seek alternative refrigerants with lower direct climate impacts. Additional factors affecting alternative refrigerant choice include safety (i.e., flammability and toxicity), environmental, and thermodynamic constraints. At the same time, manufacturers are incentivized to seek refrigerants with higher energy efficiency, which saves on electricity costs and reduces indirect greenhouse gas emissions from electricity generation. The life cycle climate performance (LCCP) metric is commonly used to assess the combined direct and indirect climate impacts of refrigerant-use equipment. Here, we consider an additional impact on climate performance: the degradation of refrigerant in equipment, i.e., the direct climate impacts of high-GWP byproducts that can form as the result of adding trifluoroiodomethane (CF3I) to refrigerant blends to reduce flammability. Such a production of high-GWP gases could change the acceptability of CF3I-containing refrigerants. Further, it highlights the need to understand refrigerant degradation within equipment in calculations of the environmental acceptability of new cooling technology.

Outdoor air pollution in India is not only an urban problem.

Urban outdoor air pollution in the developing world, mostly due to particulate matter with diameters smaller than 2.5 µm (PM2.5), has been highlighted in recent years. It leads to millions of premature deaths. Outdoor air pollution has also been viewed mostly as an urban problem. We use satellite-derived demarcations to parse India's population into urban and nonurban regions, which agrees with the census data. We also use the satellite-derived surface PM2.5 levels to calculate the health impacts in the urban and nonurban regions. We show that outdoor air pollution is just as severe in nonurban regions as in the urban regions of India, with implications to monitoring, regulations, health, and policy.

Thermal Decomposition of CH3O: A Curious Case of Pressure-Dependent Tunneling Effects.

The thermal unimolecular decomposition of a methoxy radical (CH3O), a key intermediate in the combustion of methane, methanol, and other hydrocarbons, was studied using high-level coupled-cluster calculations, followed by E,J-resolved master equation analyses. The experimental results available for a wide range of temperature and pressure are in striking agreement with the calculations. In line with a previous theoretical study that used a one-dimensional master equation, the tunneling correction is found to exhibit a marked pressure dependence, being the largest at low pressure. This curious effect on the tunneling enhancement also affects the calculated kinetic isotope effect, which falls initially with pressure but is predicted to rise again at high pressures. These findings serve to reconcile a set of conflicting results regarding the importance of tunneling in this prototype unimolecular reaction and also motivate further experimental investigation. This study also exemplifies how changes in the energy redistribution due to collisions manifest in the tunneling rates.

Measuring Photodissociation Product Quantum Yields Using Chemical Ionization Mass Spectrometry: A Case Study with Ketones.

Measurements of photolysis quantum yields are challenging because of the difficulties in measuring the first-generation photodissociation products, interference from other products or contaminants, sufficient photon fluxes and/or low absorption cross sections of the photolyte to make detectable amounts of products, and quantification of the photon flux. In the case of acetone (and other atmospherically relevant ketones) the uncertainty in the photolysis quantum yield creates uncertainty in the calculated OH radical and acyl peroxy nitrate production in the atmosphere. We present a new method for determining photodissociation product quantum yields by measuring acyl peroxy radicals (RC(O)O2) produced in the photolysis of ketones in air using chemical ionization mass spectrometry (CIMS). We show good agreement of our CIMS method with previously published quantum yields of the acyl radical from photolysis of biacetyl and methyl ethyl ketone (MEK) at 254 nm. Additionally, we highlight the capabilities of this CIMS method through the measurement of photolysis branching ratios for MEK. We suggest future applications of CIMS (in the laboratory and field) to measure RC(O)O2 and associated photolysis processes.

Trends and patterns in the contributions to cumulative radiative forcing from different regions of the world.

Different regions of the world have had different historical patterns of emissions of carbon dioxide, other greenhouse gases, and aerosols as well as different land-use changes. One can estimate the net cumulative contribution by each region to the global mean radiative forcing due to past greenhouse gas emissions, aerosol precursors, and carbon dioxide from land-use changes. Several patterns stand out from such calculations. Some regions have had a common historical pattern in which the short-term offsets between the radiative forcings from carbon dioxide and sulfate aerosols temporarily led to near-zero radiative forcing during periods of exponential emissions growth with few emission controls. This happened for North America and Europe in the mid-20th century and China in the 1990s and 2000s. However, these same periods lead to a commitment to future radiative forcing from the carbon dioxide and other greenhouse gases that stay in the atmosphere long after the aerosols. For every region, this commitment to future radiative forcing (2018-2100) from emissions already in the atmosphere is larger than the cumulative radiative forcing to date (1900-2017). This comparison again highlights how the full radiative forcing from greenhouse gases is unmasked once the aerosol emissions are reduced to improve air quality. The relative contributions from various regions to global climate forcing depends more on the time the contributions are compared (e.g., now or 2100) and future development scenarios than on whether cumulative radiative forcing, ocean heat content, or temperature is used to compare regional contributions.

Kinetics of the reactions of NO3 radical with alkanes.

The rate coefficients for the reactions of NO3 radicals with methane (CH4), ethane (C2H6), propane (C3H8), n-butane (n-C4H10), iso-butane (iso-C4H10), 2,3-dimethylbutane (C6H14), cyclopentane (C5H10) and cyclohexane (C6H12) at atmosphere pressure (1000 ± 5 hPa) and room temperature (298 ± 1.5 K) were measured using an absolute method. Careful attention was paid to the role of secondary reactions and impurities. The upper limits of rate coefficients for methane and ethane at 298 K are <4 × 10-20 and <5 × 10-19 cm3 molecule-1 s-1, respectively. The rate coefficients at 298 K for propane, n-butane, iso-butane, 2,3-dimethybutane, cyclopentane and cyclohexane are, (9.2 ± 2.9) × 10-18, (1.5 ± 0.4) × 10-17, (8.2 ± 2.2) × 10-17, (5.8 ± 2.4) × 10-16, (1.5 ± 0.6) × 10-16 and (1.3 ± 0.4) × 10-16 cm3 molecule-1 s-1, respectively. Rate coefficients for the reactions of NO3 radical with two deuterated n-butanes (butane-D10 and butane-1,1,1,4,4,4-D6) are also reported. We show that the rate coefficients for NO3 reactions correlate with the enthalpy change for the reaction, thereby suggesting that the mechanism for NO3 reactions with alkanes is through H atom abstraction. The measured rate coefficients are compared with available literature values. This study increases the number of available rate coefficients for the reactions of NO3 with alkanes and sets significantly lower upper limits for reaction of NO3 with ethane and methane. The atmospheric significance of our reported rate coefficients is briefly discussed.

Atmospheric loss of nitrous oxide (N2O) is not influenced by its potential reactions with OH and NO3 radicals.

The rate coefficient for the possible reaction of OH radical with N2O was determined to be k1 < 1 × 10-17 cm3 molecule-1 s-1 between 253 and 372 K using pulsed laser photolysis to generate OH radicals and pulsed laser induced fluorescence to detect them. The rate coefficient for the reaction of NO3 radical with N2O was measured to be k2 < 5 × 10-20 cm3 molecule-1 s-1 at 298 K using a direct method that involves a large reaction chamber equipped with cavity ring down spectroscopic detection of NO3 and N2O5. Various tests were carried out ensure the accuracy of our measurements. Based on our measured upper limits, we suggest that these two reactions alter the atmospheric lifetime of N2O of ∼120 years by less than 4%.

Improving our fundamental understanding of the role of aerosol-cloud interactions in the climate system.

The effect of an increase in atmospheric aerosol concentrations on the distribution and radiative properties of Earth's clouds is the most uncertain component of the overall global radiative forcing from preindustrial time. General circulation models (GCMs) are the tool for predicting future climate, but the treatment of aerosols, clouds, and aerosol-cloud radiative effects carries large uncertainties that directly affect GCM predictions, such as climate sensitivity. Predictions are hampered by the large range of scales of interaction between various components that need to be captured. Observation systems (remote sensing, in situ) are increasingly being used to constrain predictions, but significant challenges exist, to some extent because of the large range of scales and the fact that the various measuring systems tend to address different scales. Fine-scale models represent clouds, aerosols, and aerosol-cloud interactions with high fidelity but do not include interactions with the larger scale and are therefore limited from a climatic point of view. We suggest strategies for improving estimates of aerosol-cloud relationships in climate models, for new remote sensing and in situ measurements, and for quantifying and reducing model uncertainty.

Changes in Emissions of Ozone-Depleting Substances from China Due to Implementation of the Montreal Protocol.

The ozone layer depletion and its recovery, as well as the climate influence of ozone-depleting substances (ODSs) and their substitutes that influence climate, are of interest to both the scientific community and the public. Here we report on the emissions of ODSs and their substitute from China, which is currently the largest consumer (and emitter) of these substances. We provide, for the first time, comprehensive information on ODSs and replacement hydrofluorocarbon (HFC) emissions in China starting from 1980 based on reported production and usage. We also assess the impacts (and costs) of controls on ODS consumption and emissions on the ozone layer (in terms of CFC-11-equivalent) and climate (in CO2-equivalent). In addition, we show that while China's future ODS emissions are likely to be defined as long as there is full compliance with the Montreal Protocol; its HFC emissions through 2050 are very uncertain. Our findings imply that HFC controls over the next decades that are more stringent than those under the Kigali Amendment to the Montreal Protocol would be beneficial in mitigating global climate change.

Rate Coefficient Measurements and Theoretical Analysis of the OH + ( E)-CF3CH═CHCF3 Reaction.

Rate coefficients, k, for the gas-phase reaction of the OH radical with ( E)-CF3CH═CHCF3 (( E)-1,1,1,4,4,4-hexafluoro-2-butene, HFO-1336mzz(E)) were measured over a range of temperatures (211-374 K) and bath gas pressures (20-300 Torr; He, N2) using a pulsed laser photolysis-laser-induced fluorescence (PLP-LIF) technique. k1( T) was independent of pressure over this range of conditions with k1(296 K) = (1.31 ± 0.15) × 10-13 cm3 molecule-1 s-1 and k1( T) = (6.94 ± 0.80) × 10-13exp[-(496 ± 10)/ T] cm3 molecule-1 s-1, where the uncertainties are 2σ, and the pre-exponential term includes estimated systematic error. Rate coefficients for the OD reaction were also determined over a range of temperatures (262-374 K) at 100 Torr (He). The OD rate coefficients were ∼15% greater than the OH values and showed similar temperature dependent behavior with k2( T) = (7.52 ± 0.44) × 10-13exp[-(476 ± 20)/ T] and k2(296 K) = (1.53 ± 0.15) × 10-13 cm3 molecule-1 s-1. The rate coefficients for reaction 1 were also measured using a relative rate technique between 296 and 375 K with k1(296 K) measured to be (1.22 ± 0.1) × 10-13 cm3 molecule-1 s-1, in agreement with the PLP-LIF results. In addition, the 296 K rate coefficient for the O3 + ( E)-CF3CH═CHCF3 reaction was determined to be <5.2 × 10-22 cm3 molecule-1 s-1. A theoretical computational analysis is presented to interpret the observed positive temperature dependence for the addition reaction and the significant decrease in OH reactivity compared to the ( Z)-CF3CH═CHCF3 stereoisomer reaction. The estimated atmospheric lifetime of ( E)-CF3CH═CHCF3, due to loss by reaction with OH, is estimated to be ∼90 days, while the actual lifetime will depend on the location and season of its emission. Infrared absorption spectra of ( E)-CF3CH═CHCF3 were measured and used to estimate the 100 year time horizon global warming potentials (GWP) of 32 (atmospherically well-mixed) and 14 (lifetime-adjusted).

Kinetics of the Reactions of NO3 Radical with Methacrylate Esters.

Two different experimental methods (relative rate and absolute rate methods) were used to measure the rate coefficients for the reactions of NO3 radical with six methacrylate esters: methyl methacrylate (MMA, k1), ethyl methacrylate (EMA, k2), propyl methacrylate (PMA, k3), isopropyl methacrylate (IPMA, k4), butyl methacrylate (BMA, k5), and isobutyl methacrylate (IBMA, k6). In the relative rate method, the loss of the esters relative to that of a reference compound was followed in a 7300 L Teflon-walled chamber at 298 ± 2 K and 1000 ± 5 hpa. In the absolute method, the temporal profiles of NO3 and N2O5 were followed by using a dual channel cavity ring-down spectrometer in the presence of an excess of ester in the 7300 L chamber. The rate coefficients from these two methods (weighted averages) in the units of 10-15 cm3 molecule-1 s-1 at 298 K are k1 = 2.98 ± 0.35, k2 = 4.67 ± 0.49, k3 = 5.23 ± 0.60, k4 = 7.91 ± 1.00, k5 = 5.91 ± 0.58, and k6 = 6.24 ± 0.66. The quoted uncertainties are at the 2σ level and include estimated systematic errors. Unweighted averages are also reported. In addition, the rate coefficient k7 for the reaction of NO3 radical with deuterated methyl methacrylate (MMA-d8) was measured by using the relative rate method to be essentially the same as k1. The trends in the measured rate coefficient with the length and nature of the alkyl group, along with the equivalence of k1 and k7, strongly suggest that the reaction of NO3 with the methacrylate esters proceeds via addition to the double bond on the methacrylate group. The present results are compared with those from previous studies. Using the measured values of the rate coefficients, along with those for reactions of these esters with OH, O3, and chlorine atoms, we calculated the atmospheric lifetimes of methacrylate esters. We suggest that NO3 radicals do contribute to the atmospheric loss of these unsaturated esters, but to a lesser extent than their reactions with OH and O3.

Hydrofluorocarbon (HFC) Emissions in China: An Inventory for 2005-2013 and Projections to 2050.

Many hydrofluorocarbons (HFCs) that are widely used as substitutes for ozone-depleting substances (now regulated under the Montreal Protocol) are very potent greenhouse gases (GHGs). China's past and future HFC emissions are of great interest because China has emerged as a major producer and consumer of HFCs. Here, we present for the first time a comprehensive inventory estimate of China's HFC emissions during 2005-2013. Results show a rapid increase in HFC production, consumption, and emissions in China during the period and that the emissions of HFC with a relatively high global warming potential (GWP) grew faster than those with a relatively low GWP. The proportions of China's historical HFC CO2-equivalent emissions to China's CO2 emissions or global HFC CO2-equivalent emissions increased rapidly during 2005-2013. Using the "business-as-usual" (BAU) scenario, in which HFCs are used to replace a significant fraction of hydrochlorofluorocarbons (HCFCs) in China (to date, there are no regulations on HFC uses in China), emissions of HFCs are projected to be significant components of China's and global future GHG emissions. However, potentials do exist for minimizing China's HFC emissions (for example, if regulations on HFC uses are established in China). Our findings on China's historical and projected HFC emission trajectories could also apply to other developing countries, with important implications for mitigating global GHG emissions.

A post-Kyoto partner: considering the stratospheric ozone regime as a tool to manage nitrous oxide.

Nitrous oxide (N2O) is the largest known remaining anthropogenic threat to the stratospheric ozone layer. However, it is currently only regulated under the 1997 Kyoto Protocol because of its simultaneous ability to warm the climate. The threat N2O poses to the stratospheric ozone layer, coupled with the uncertain future of the international climate regime, motivates our exploration of issues that could be relevant to the Parties to the ozone regime (the 1985 Vienna Convention and its 1987 Montreal Protocol) should they decide to take measures to manage N2O in the future. There are clear legal avenues to regulate N2O under the ozone regime as well as several ways to share authority with the existing and future international climate treaties. N2O mitigation strategies exist to address the most significant anthropogenic sources, including agriculture, where behavioral practices and new technologies could contribute significantly to reducing emissions. Existing policies managing N2O and other forms of reactive nitrogen could be harnessed and built on by the ozone regime to implement N2O controls. There are several challenges and potential cobenefits to N2O control which we discuss here: food security, equity, and implications of the nitrogen cascade. The possible inclusion of N2O in the ozone regime need not be viewed as a sign of failure of the United Nations Framework Convention on Climate Change to adequately deal with climate change. Rather, it could represent an additional valuable tool in sustainable development diplomacy.

Temperature dependence of the Cl atom reaction with deuterated methanes.

Kinetic isotope effect (KIE) and reaction rate coefficients, k1-k4, for the gas-phase reaction of Cl atoms with (12)CH3D (k1), (12)CH2D2 (k2), (12)CHD3 (k3), and (12)CD4 (k4) over the temperature range 223-343 K in 630 Torr of synthetic air are reported. Rate coefficients were measured using a relative rate technique with (12)CH4 as the primary reference compound. Fourier transform infrared spectroscopy was used to monitor the methane isotopologue loss. The obtained KIE values were (12)CH3D: KIE1(T) = (1.227 ± 0.004) exp((43 ± 5)/T); (12)CH2D2: KIE2(T) = (1.14 ± 0.20) exp((191 ± 60)/T); (12)CHD3: KIE3(T) = (1.73 ± 0.34) exp((229 ± 60)/T); and (12)CD4: KIE4(T) = (1.01 ± 0.3) exp((724 ± 19)/T), where KIEx(T) = kCl+(12)CH4(T)/kx(T). The quoted uncertainties are at the 2σ (95% confidence) level and represent the precision of our data. The following Arrhenius expressions and 295 K rate coefficient values (in units of cm(3) molecule(-1) s(-1)) were derived from the above KIE using a rate coefficient of 7.3 × 10(-12) exp(-1280/T) cm(3) molecule(-1) s(-1) for the reaction of Cl with (12)CH4: k1(T) = (5.95 ± 0.70) × 10(-12) exp(-(1323 ± 50)/T), k1(295 K) = (6.7 ± 0.8) × 10(-14); k2(T) = (6.4 ± 1.3) × 10(-12) exp(-(1471 ± 60)/T), k2(295 K) = (4.4 ± 0.9) × 10(-14); k3(T) = (4.2 ± 1.0) × 10(-12) exp(-(1509 ± 60)/T), k3(295 K) = (2.53 ± 0.6) × 10(-14); and k4(T) = (7.13 ± 2.3) × 10(-12) exp(-(2000 ± 120)/T), k4(295 K) = (0.81 ± 0.26) × 10(-14). The reported uncertainties in the pre-exponential factors are 2σ and include estimated systematic errors in our measurements and the uncertainty in the reference reaction rate coefficient. The results from this study are compared with previously reported room-temperature rate coefficients for each of the deuterated methanes as well as the available temperature dependent data for the Cl atom reactions with CH3D and CD4. A two-dimensional atmospheric chemistry model was used to examine the implications of the present results to the atmospheric lifetime and vertical variation in the loss of the deuterated methane isotopologues. The relative contributions of the reactions of OH, Cl, and O((1)D) to the loss of the isotopologues in the stratosphere were also examined. The results of the calculations are described and discussed.

Air quality implications of the Deepwater Horizon oil spill.

During the Deepwater Horizon (DWH) oil spill, a wide range of gas and aerosol species were measured from an aircraft around, downwind, and away from the DWH site. Additional hydrocarbon measurements were made from ships in the vicinity. Aerosol particles of respirable sizes were on occasions a significant air quality issue for populated areas along the Gulf Coast. Yields of organic aerosol particles and emission factors for other atmospheric pollutants were derived for the sources from the spill, recovery, and cleanup efforts. Evaporation and subsequent secondary chemistry produced organic particulate matter with a mass yield of 8 ± 4% of the oil mixture reaching the water surface. Approximately 4% by mass of oil burned on the surface was emitted as soot particles. These yields can be used to estimate the effects on air quality for similar events as well as for this spill at other times without these data. Whereas emission of soot from burning surface oil was large during the episodic burns, the mass flux of secondary organic aerosol to the atmosphere was substantially larger overall. We use a regional air quality model to show that some observed enhancements in organic aerosol concentration along the Gulf Coast were likely due to the DWH spill. In the presence of evaporating hydrocarbons from the oil, NO(x) emissions from the recovery and cleanup operations produced ozone.

Uptake of HNO3 on aviation kerosene and aircraft engine soot: influences of H2O or/and H2SO4.

The uptake of HNO3 on aviation kerosene soot (TC-1 soot) was studied in the absence and presence of water vapor at 295 and 243 K. The influence of H2SO4 coating of the TC-1 soot surface on HNO3 uptake was also investigated. Only reversible uptake of HNO3 was observed. HONO and NO2, potential products of reactive uptake of HNO3, were not observed under any conditions studied here. The uptake of nitric acid increased slightly with relative humidity (RH). Coating of the TC-1 soot surface with sulfuric acid decreased the uptake of HNO3 and did not lead to displacement of H2SO4 from the soot surface. A limited set of measurements was carried out on soot generated by aircraft engine combustor (E-soot) with results similar to those on TC-1 soot. The influence of water on HNO3 uptake on E-soot appeared to be more pronounced than on TC-1 soot. Our results suggest that HNO3 loss in the upper troposphere due to soot is not significant except perhaps in aircraft exhaust plumes. Our results also suggest that HNO3 is not converted to either NO2 or HONO upon its uptake on soot in the atmosphere.