Peidong Wang

The Antarctic ozone ‘hole’ was discovered in 1985 and man-made ozone-depleting substances (ODSs) are its primary cause. Following reductions of ODSs under the Montreal Protocol, signs of ozone recovery have been reported, based largely on observations and broad yet compelling model–data comparisons. Although such approaches are highly valuable, they do not provide rigorous statistical detection of the temporal and spatial structure of Antarctic ozone recovery in the presence of internal climate variability. Here we apply pattern-based detection and attribution methods as used in climate-change studies to separate anthropogenically forced ozone responses from internal variability, relying on trend pattern information as a function of month and height. The analysis uses satellite observations together with single-model and multi-model ensemble simulations to identify and quantify the month–height Antarctic ozone recovery ‘fingerprint’. We demonstrate that the data and simulations show compelling agreement in the fingerprint pattern of the ozone response to decreasing ODSs since 2005. We also show that ODS forcing has enhanced ozone internal variability during the austral spring, influencing detection of forced responses and their time of emergence. Our results provide robust statistical and physical evidence that actions taken under the Montreal Protocol to reduce ODSs are indeed resulting in the beginning of Antarctic ozone recovery, defined as increases in ozone consistent with expected month–height patterns.

Abstract Volcanic eruptions and wildfires can impact stratospheric chemistry. We apply tracer-tracer correlations to satellite data from Atmospheric Chemistry Experiment—Fourier Transform Spectrometer and the Halogen Occultation Experiment at 68 hPa to consistently compare the chemical impact on HCl after multiple wildfires and volcanic eruptions of different magnitudes. The 2020 Australian New Year (ANY) fire displayed an order of magnitude less stratospheric aerosol extinction than the 1991 Pinatubo eruption, but showed similar large changes in mid-latitude lower stratosphere HCl. While the mid-latitude aerosol loadings from the 2015 Calbuco and 2022 Hunga volcanic eruptions were similar to the ANY fire, little impact on HCl occurred. The 2009 Australian Black Saturday fire and 2021 smoke remaining from 2020 yield small HCl changes, at the edge of the detection method. These observed contrasts across events highlight greater reactivity for smoke versus volcanic aerosols at warm temperatures.

Abstract Hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) are potent greenhouse gases regulated under the Montreal Protocol and its amendments. Emission estimates generally use constant atmospheric lifetimes accounting for loss via hydroxyl radical (OH) reactions. However, chemistry-climate models suggest OH increases after 1980, implying underestimated emissions. Further, HCFCs and HFCs are soluble in seawater and could be destroyed through in situ oceanic microbial activity. These ocean sinks are largely overlooked. Using a coupled atmosphere-ocean model, we show that increases in modeled OH imply underestimated HCFC and HFC emissions by 10% near their respective peak emissions. Our model results also suggest that oceanic processes could lead to up to an additional 10% underestimation in these halocarbon emissions in the 2020s. Ensuring global compliance to the Protocol and accurate knowledge of contributions to global warming from these gases therefore requires understanding of these processes.

Heterogeneous chlorine activation is a major driver for stratospheric ozone depletion and is understood to happen on polar stratospheric clouds (PSCs) at temperatures below about 195 K. The 2020 Australian wildfire released large amounts of organic aerosols, whose chemical properties under stratospheric conditions are virtually unknown. Here, we developed an approach to analyze the temperature dependency of atmospheric chlorine heterogeneous chemistry using satellite data. We found that such reactions can happen at temperatures even at 220 K on wildfire aerosols in 2020. Organic aerosols are present to some degree in the lower stratosphere even under background conditions. This result indicates that Cl processes on organic aerosols likely need to be considered in future stratospheric ozone simulations. The 2019 to 2020 Australian summer wildfires injected an amount of organic gases and particles into the stratosphere unprecedented in the satellite record since 2002, causing large unexpected changes in HCl and ClONO2. These fires provided a novel opportunity to evaluate heterogeneous reactions on organic aerosols in the context of stratospheric chlorine and ozone depletion chemistry. It has long been known that heterogeneous chlorine (Cl) activation occurs on the polar stratospheric clouds (PSCs; liquid and solid particles containing water, sulfuric acid, and in some cases nitric acid) that are found in the stratosphere, but these are only effective for ozone depletion chemistry at temperatures below about 195 K (i.e., largely in the polar regions during winter). Here, we develop an approach to quantitatively assess atmospheric evidence for these reactions using satellite data for both the polar (65 to 90°S) and the midlatitude (40 to 55°S) regions. We show that heterogeneous reactions apparently even happened at temperatures at 220 K during austral autumn on the organic aerosols present in 2020 in both regions, in contrast to earlier years. Further, increased variability in HCl was also found after the wildfires, suggesting diverse chemical properties among the 2020 aerosols. We also confirm the expectation based upon laboratory studies that heterogeneous Cl activation has a strong dependence upon water vapor partial pressure and hence atmospheric altitude, becoming much faster close to the tropopause. Our analysis improves the understanding of heterogeneous reactions that are important for stratospheric ozone chemistry under both background and wildfire conditions.

Manufactured CFC-11 is depleting the Antarctic ozone layer. CFC production has been strictly controlled by the Montreal Protocol, but emission estimates are very sensitive to choices of lifetimes, which are often assumed as constant over time. We employ a hierarchy of models to study the effect of the ocean on the time-dependent uptake and release of atmospheric CFC-11. The ocean is a sink for CFC-11 and significantly affects its total lifetime and hence the emission inferred from concentration data of past decades. This has not been explicitly included in international ozone assessments. We show that, as anthropogenic production ceases, ocean fluxes become more important, suggesting a need for further studies with high-resolution global models linking atmospheric chemistry and ocean processes. The ocean is a reservoir for CFC-11, a major ozone-depleting chemical. Anthropogenic production of CFC-11 dramatically decreased in the 1990s under the Montreal Protocol, which stipulated a global phase out of production by 2010. However, studies raise questions about current overall emission levels and indicate unexpected increases of CFC-11 emissions of about 10 Gg/yr after 2013 (based upon measured atmospheric concentrations and an assumed atmospheric lifetime). These findings heighten the need to understand processes that could affect the CFC-11 lifetime, including ocean fluxes. We evaluate how ocean uptake and release through 2300 affects CFC-11 lifetimes, emission estimates, and the long-term return of CFC-11 from the ocean reservoir. We show that ocean uptake yields a shorter total lifetime and larger inferred emission of atmospheric CFC-11 from 1930 to 2075 compared to estimates using only atmospheric processes. Ocean flux changes over time result in small but not completely negligible effects on the calculated unexpected emissions change (decreasing it by 0.4 ± 0.3 Gg/yr). Moreover, it is expected that the ocean will eventually become a source of CFC-11, increasing its total lifetime thereafter. Ocean outgassing should produce detectable increases in global atmospheric CFC-11 abundances by the mid-2100s, with emission of around 0.5 Gg/yr; this should not be confused with illicit production at that time. An illustrative model projection suggests that climate change is expected to make the ocean a weaker reservoir for CFC-11, advancing the detectable change in the global atmospheric mixing ratio by about 5 yr.