Abstract Rapid growing emissions of dichloromethane (CH2Cl2), a chlorinated very‐short‐lived substance (Cl‐VSLS) and an ozone depleting substance (ODS), has raised concerns as this increase offset a part of the stratospheric chlorine (Cl) reduction due to decreasing long‐lived ODSs. We have combined simulations of the two most abundant Cl‐VSLSs, CH2Cl2and chloroform (CHCl3) using the NASA GEOS Chemistry Climate Model (GEOSCCM) with Asian Summer Monsoon Chemical and CLimate Impact Project aircraft observations to examine transport of Cl‐VSLSs to the stratosphere and to assess their contribution to total stratospheric Cl. With ongoing large emissions (total ∼1,500 Gg yr−1), Cl‐VSLSs add about 100 ppt Cl to the stratosphere between 2020 and 2022. The Asian Summer Monsoon plays a primary role in the troposphere‐to‐stratosphere transport of Cl‐VSLSs and delivers double the amount to the stratosphere, about 200 ppt Cl in August 2022. The overall Cl‐VSLSs impact on stratospheric chlorine (∼3.3%) and ozone (∼1 DU) remain small.
more »
« less
Measurements and Modeling of the Interhemispheric Differences of Atmospheric Chlorinated Very Short‐Lived Substances
Abstract Chlorinated very short‐lived substances (Cl‐VSLS) are ubiquitous in the troposphere and can contribute to the stratospheric chlorine budget. In this study, we present measurements of atmospheric dichloromethane (CH2Cl2), tetrachloroethene (C2Cl4), chloroform (CHCl3), and 1,2‐dichloroethane (1,2‐DCA) obtained during the National Aeronautics and Space Administration (NASA) Atmospheric Tomography (ATom) global‐scale aircraft mission (2016–2018), and use the Community Earth System Model (CESM) updated with recent chlorine chemistry to further investigate their global tropospheric distribution. The measured global average Cl‐VSLS mixing ratios, from 0.2 to 13 km altitude, were 46.6 ppt (CH2Cl2), 9.6 ppt (CHCl3), 7.8 ppt (1,2‐DCA), and 0.84 ppt (C2Cl4) measured by the NSF NCAR Trace Organic Analyzer (TOGA) during ATom. Both measurements and model show distinct hemispheric gradients with the mean measured Northern to Southern Hemisphere (NH/SH) ratio of 2 or greater for all four Cl‐VSLS. In addition, the TOGA profiles over the NH mid‐latitudes showed general enhancements in the Pacific basin compared to the Atlantic basin, with up to ∼18 ppt difference for CH2Cl2in the mid troposphere. We tagged regional source emissions of CH2Cl2and C2Cl4in the model and found that Asian emissions dominate the global distributions of these species both at the surface (950 hPa) and at high altitudes (150 hPa). Overall, our results confirm relatively high mixing ratios of Cl‐VSLS in the UTLS region and show that the CESM model does a reasonable job of simulating their global abundance but we also note the uncertainties with Cl‐VSLS emissions and active chlorine sources in the model. These findings will be used to validate future emission inventories and to investigate the fast convective transport of Cl‐VSLS to the UTLS region and their impact on stratospheric ozone.
more »
« less
- Award ID(s):
- 2032328
- PAR ID:
- 10562281
- Publisher / Repository:
- JGR - Atmospheres
- Date Published:
- Journal Name:
- Journal of Geophysical Research: Atmospheres
- Volume:
- 129
- Issue:
- 2
- ISSN:
- 2169-897X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Deep convection in the Asian summer monsoon is a significant transport process for lifting pollutants from the planetary boundary layer to the tropopause level. This process enables efficient injection into the stratosphere of reactive species such as chlorinated very short-lived substances (Cl-VSLSs) that deplete ozone. Past studies of convective transport associated with the Asian summer monsoon have focused mostly on the south Asian summer monsoon. Airborne observations reported in this work identify the East Asian summer monsoon convection as an effective transport pathway that carried record-breaking levels of ozone-depleting Cl-VSLSs (mean organic chlorine from these VSLSs ~500 ppt) to the base of the stratosphere. These unique observations show total organic chlorine from VSLSs in the lower stratosphere over the Asian monsoon tropopause to be more than twice that previously reported over the tropical tropopause. Considering the recently observed increase in Cl-VSLS emissions and the ongoing strengthening of the East Asian summer monsoon under global warming, our results highlight that a reevaluation of the contribution of Cl-VSLS injection via the Asian monsoon to the total stratospheric chlorine budget is warranted.more » « less
-
Abstract. The chemical compound 1,2-dichloroethane (DCE), or ethylene dichloride, is an industrial very short-lived substance (VSLS) whose major use is as a feedstock in the production chain of polyvinyl chloride (PVC). Like other chlorinated VSLSs, transport of DCE (and/or its atmospheric oxidation products) to the stratosphere could contribute to ozone depletion there. However, despite annual production volumes greatly exceeding those of more prominent VSLSs (e.g. dichloromethane), global DCE observations are sparse; thus, the magnitude and distribution of DCE emissions and trends in its atmospheric abundance are poorly known. In this study, we performed an exploratory analysis of the global DCE budget between 2002 and 2020. Combining bottom-up data on annual production and assumptions around fugitive losses during production and feedstock use, we assessed the DCE source strength required to reproduce atmospheric DCE observations. We show that the TOMCAT/SLIMCAT 3-D chemical transport model (CTM) reproduces DCE measurements from various aircraft missions well, including HIPPO (2009–2011), ATom (2016–2018), and KORUS-AQ (2016), along with surface measurements from Southeast Asia, when assuming a regionally varying production emission factor in the range of 0.5 %–1.5 %. Our findings imply substantial fugitive losses of DCE and/or substantial emissive applications (e.g. solvent use) that are poorly reported. We estimate that DCE's global source increased by ∼ 45 % between 2002 (349 ± 61 Gg yr−1) and 2020 (505 ± 90 Gg yr−1), with its contribution to stratospheric chlorine increasing from 8.2 (± 1.5) to ∼ 12.9 (± 2.4) ppt Cl (where ppt denotes parts per trillion) over this period. DCE's relatively short overall tropospheric lifetime (∼ 83 d) limits, although does not preclude, its transport to the stratosphere, and we show that its impact on ozone is small at present. Annually averaged, DCE is estimated to have decreased ozone in the lower stratosphere by up to several parts per billion (< 1 %) in 2020, although a larger effect in the springtime Southern Hemisphere polar lower stratosphere is apparent (decreases of up to ∼ 1.3 %). Given strong potential for growth in DCE production tied to demand for PVC, ongoing measurements would be of benefit to monitor potential future increases in its atmospheric abundance and its contribution to ozone depletion.more » « less
-
Abstract. We present an updated mechanism for tropospheric halogen (Cl + Br + I) chemistry in the GEOS-Chem global atmospheric chemical transportmodel and apply it to investigate halogen radical cycling and implications for tropospheric oxidants. Improved representation of HOBr heterogeneouschemistry and its pH dependence in our simulation leads to less efficient recycling and mobilization of bromine radicals and enables the model toinclude mechanistic sea salt aerosol debromination without generating excessive BrO. The resulting global mean tropospheric BrO mixingratio is 0.19 ppt (parts per trillion), lower than previous versions of GEOS-Chem. Model BrO shows variable consistency and biases in comparison tosurface and aircraft observations in marine air, which are often near or below the detection limit. The model underestimates the daytimemeasurements of Cl2 and BrCl from the ATom aircraft campaign over the Pacific and Atlantic, which if correct would imply a very largemissing primary source of chlorine radicals. Model IO is highest in the marine boundary layer and uniform in the free troposphere, with a globalmean tropospheric mixing ratio of 0.08 ppt, and shows consistency with surface and aircraft observations. The modeled global meantropospheric concentration of Cl atoms is 630 cm−3, contributing 0.8 % of the global oxidation of methane, 14 % of ethane,8 % of propane, and 7 % of higher alkanes. Halogen chemistry decreases the global tropospheric burden of ozone by 11 %,NOx by 6 %, and OH by 4 %. Most of the ozone decrease is driven by iodine-catalyzed loss. The resulting GEOS-Chem ozonesimulation is unbiased in the Southern Hemisphere but too low in the Northern Hemisphere.more » « less
-
The present study investigates dynamical coupling between the equatorial stratospheric Quasi31 biennial oscillation (QBO) and the boreal winter surface climate of the Northern Hemisphere mid and high latitudes using 42 years data (1979–2020). For neutral El Niño Southern Oscillation (ENSO) periods, QBO westerlies (W) at 70 hPa favor high sea level pressure in the polar region, colder conditions and deeper snow over Eurasia and North America, and the opposite effects for QBO easterlies (E). When QBO anomalies arrive in the upper troposphere and lower stratosphere (UTLS), it is observed that planetary wave activity is enhanced in the extratropical UTLS during QBO W and diminished during QBO E. This QBO teleconnection pathway along the UTLS to the high latitude surface is independent of the “stratospheric pathway” (Holton-Tan mechanism). Diagnosis of this pathway can help to improve understanding of internal sub-seasonal to seasonal variations, and long-range forecasting over Eurasia and North America.more » « less