skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


This content will become publicly available on September 16, 2025

Title: Stratospheric Chlorine Processing After the Unprecedented Hunga Tonga Eruption
Abstract Following the Hunga Tonga–Hunga Ha'apai (HTHH) eruption in January 2022, significant reductions in stratospheric hydrochloric acid (HCl) were observed in the Southern Hemisphere mid‐latitudes during the latter half of 2022, suggesting potential chlorine activation. The objective of this study is to comprehensively understand the loss of HCl in the aftermath of HTHH. Satellite measurements and a global chemistry‐climate model are employed for the analysis. We find strong agreement of 2022 anomalies between the modeled and the measured data. The observed tracer‐tracer relations between nitrous oxide (N2O) and HCl indicate a significant role of chemical processing in the observed HCl reduction, especially during the austral winter of 2022. Further examining the roles of chlorine gas‐phase and heterogeneous chemistry, we find that heterogeneous chemistry emerges as the primary driver for the chemical loss of HCl, and the reaction between hypobromous acid (HOBr) and HCl on sulfate aerosols is the dominant loss process.  more » « less
Award ID(s):
2316980
PAR ID:
10582445
Author(s) / Creator(s):
; ; ; ; ; ;
Publisher / Repository:
American Geophysical Union
Date Published:
Journal Name:
Geophysical research letters
Volume:
51
Issue:
17
ISSN:
1944-8007
Subject(s) / Keyword(s):
atmospheric chemistry volcano
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. 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. 
    more » « less
  2. We present a comprehensive simulation of tropospheric chlorine within the GEOS-Chem global 3-D model of oxidant–aerosol–halogen atmospheric chemistry. The simulation includes explicit accounting of chloride mobilization from sea salt aerosol by acid displacement of HCl and by other heterogeneous processes. Additional small sources of tropospheric chlorine (combustion, organochlorines, transport from stratosphere) are also included. Reactive gas-phase chlorine Cl*, including Cl, ClO, Cl2, BrCl, ICl, HOCl, ClNO3, ClNO2, and minor species, is produced by the HCl+OH reaction and by heterogeneous conversion of sea salt aerosol chloride to BrCl, ClNO2, Cl2, and ICl. The model successfully simulates the observed mixing ratios of HCl in marine air (highest at northern midlatitudes) and the associated HNO3 decrease from acid displacement. It captures the high ClNO2 mixing ratios observed in continental surface air at night and attributes the chlorine to HCl volatilized from sea salt aerosol and transported inland following uptake by fine aerosol. The model successfully simulates the vertical profiles of HCl measured from aircraft, where enhancements in the continental boundary layer can again be largely explained by transport inland of the marine source. It does not reproduce the boundary layer Cl2 mixing ratios measured in the WINTER aircraft campaign (1–5 ppt in the daytime, low at night); the model is too high at night, which could be due to uncertainty in the rate of the ClNO2+Cl− reaction, but we have no explanation for the high observed Cl2 in daytime. The global mean tropospheric concentration of Cl atoms in the model is 620 cm−3 and contributes 1.0 % of the global oxidation of methane, 20 % of ethane, 14 % of propane, and 4 % of methanol. Chlorine chemistry increases global mean tropospheric BrO by 85 %, mainly through the HOBr+Cl− reaction, and decreases global burdens of tropospheric ozone by 7 % and OH by 3 % through the associated bromine radical chemistry. ClNO2 chemistry drives increases in ozone of up to 8 ppb over polluted continents in winter. 
    more » « less
  3. 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 ClONO 2 . 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. 
    more » « less
  4. Abstract Hydrogen chloride (HCl) is a key repository of chlorine in the interstellar medium. Accurate determinations of its abundance are critical to assessing the chlorine elemental abundance and constraining stellar nucleosynthesis models. To aid in modeling recent and future observations of HCl rovibrational spectra, we present cross sections and rate coefficients for collisions between HCl and molecular hydrogen. Transitions between rovibrational states of HCl are considered for temperatures ranging from 10 to 3000 K. Cross sections are computed using a full dimensional quantum close-coupling (CC) method and a reduced dimensionality coupled-states (CS) approach. The CS results, benchmarked against the CC results, are used with a recoupling approach to calculate hyperfine-resolved rate coefficients for rovibrational transitions of HCl induced by H2. The rate coefficients will allow for a better determination of the HCl abundance in the interstellar medium and an improved understanding of interstellar chlorine chemistry. We demonstrate the utility of the new rate coefficients in a nonthermodynamic equilibrium radiative transfer model applied to observations of HCl rovibrational transitions in a circumstellar shell. 
    more » « less
  5. Abstract The inorganic chlorine (Cly) and odd nitrogen (NOy) chemical families influence stratospheric O3. In January 2020 Australian wildfires injected record‐breaking amounts of smoke into the southern stratosphere. Within 1–2 months ground‐based and satellite observations showed Clyand NOywere repartitioned. By May, lower stratospheric HCl columns declined by ∼30% and ClONO2columns increased by 40%–50%. The Clyperturbations began and ended near the equinoxes, increased poleward, and peaked at the winter solstice. NO2decreased from February to April, consistent with sulfate aerosol reactions, but returned to typical values by June ‐ months before the Clyrecovery. Transport tracers show that dynamics not chemistry explains most of the observed O3decrease after April, with no significant transport earlier. Simulations assuming wildfire smoke behaves identically to sulfate aerosols couldn't reproduce observed Clychanges, suggesting they have different composition and chemistry. This undermines our ability to predict ozone in a changing climate. 
    more » « less