Unexpected nascent atmospheric emissions of three ozone-depleting hydrochlorofluorocarbons.

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.

Recent Trends in Stratospheric Chlorine From Very Short-Lived Substances.

Very short-lived substances (VSLS), including dichloromethane (CH2Cl2), chloroform (CHCl3), perchloroethylene (C2Cl4), and 1,2-dichloroethane (C2H4Cl2), are a stratospheric chlorine source and therefore contribute to ozone depletion. We quantify stratospheric chlorine trends from these VSLS (VSLCltot) using a chemical transport model and atmospheric measurements, including novel high-altitude aircraft data from the NASA VIRGAS (2015) and POSIDON (2016) missions. We estimate VSLCltot increased from 69 (±14) parts per trillion (ppt) Cl in 2000 to 111 (±22) ppt Cl in 2017, with >80% delivered to the stratosphere through source gas injection, and the remainder from product gases. The modeled evolution of chlorine source gas injection agrees well with historical aircraft data, which corroborate reported surface CH2Cl2 increases since the mid-2000s. The relative contribution of VSLS to total stratospheric chlorine increased from ~2% in 2000 to ~3.4% in 2017, reflecting both VSLS growth and decreases in long-lived halocarbons. We derive a mean VSLCltot growth rate of 3.8 (±0.3) ppt Cl/year between 2004 and 2017, though year-to-year growth rates are variable and were small or negative in the period 2015-2017. Whether this is a transient effect, or longer-term stabilization, requires monitoring. In the upper stratosphere, the modeled rate of HCl decline (2004-2017) is -5.2% per decade with VSLS included, in good agreement to ACE satellite data (-4.8% per decade), and 15% slower than a model simulation without VSLS. Thus, VSLS have offset a portion of stratospheric chlorine reductions since the mid-2000s.