UV spectroscopic determination of the chlorine monoxide (ClO) ∕ chlorine peroxide (ClOOCl) thermal equilibrium constant

The thermal equilibrium constant between the chlorine monoxide radical (ClO) and its dimer, chlorine peroxide (ClOOCl), was determined as a function of temperature between 228 and 301 K in a discharge flow apparatus using broadband UV absorption spectroscopy. A third-law fit of the equilibrium values determined from the experimental data provides the expression Keq=2.16×10-27e8527±35K/T cm3 molecule−1 (1σ uncertainty). A second-law analysis of the data is in good agreement. From the slope of the van't Hoff plot in the third-law analysis, the enthalpy of formation for ClOOCl is calculated, ΔHf∘(298K)=130.0±0.6 kJ mol−1. The equilibrium constant results from this study suggest that the uncertainties in Keq recommended in the most recent (year 2015) NASA JPL Data Evaluation can be significantly reduced.

UV spectroscopic determination of the chlorine monoxide (ClO) / chlorine peroxide (ClOOCl) thermal equilibrium constant

The thermal equilibrium constant between the chlorine monoxide radical (ClO) and its dimer, chlorine peroxide (ClOOCl), was determined as a function of temperature between 228–301 K in a discharge flow apparatus using broadband UV absorption spectroscopy. A third law fit of the equilibrium values determined from the experimental data provides the expression: Keq = 2.16 × 10−27 e(8533 ± 25 K/T) cm3 molecule−1. A second law analysis of the data deviates minimally: Keq = (2.06 ± 1.27) × 10−27 e(8546 ± 123 K/T) cm3 molecule−1. From the slope of the van't Hoff plot in the third law analysis, the enthalpy of formation for ClOOCl is calculated, ∆H◦f (298 K) = 129.9 ± 0.6 kJ mol−1. The equilibrium constant results from this study suggest that the uncertainties in Keq recommended in the most recent (year 2015) NASA JPL Data Evaluation can be significantly reduced.

The Chemistry Climate Model ECHAM6.3-HAM2.3-MOZ1.0

The chemistry climate model ECHAM-HAMMOZ contains a detailed representation of tropospheric and stratospheric reactive chemistry and state-of-the-art parametrisations of aerorols using either a modal scheme (M7) or a bin scheme (SALSA). This article describes and evaluates the model version ECHAM6.3-HAM2.3-MOZ1.0 with a focus on the tropospheric gas-phase chemistry. A ten-year model simulation was performed to test the stability of the model and provide data for its evaluation. The comparison to observations concentrates on the year 2008 and includes total column observations of ozone (O₃) and carbon monoxide (CO) from Infrared Atmospheric Sounding Interferometer (IASI) and Ozone Monitoring Instrument (OMI), Microwave Limb Sounder (MLS) observations of temperature, nitric acid (HNO₃), chlorine monoxide (ClO), and O₃ for the evaluation of polar stratospheric processes, an ozone sonde climatology, surface ozone observations from the Tropospheric Ozone Assessment Report (TOAR) database, and surface CO data from the Global Atmosphere Watch network. Global budgets of ozone, hydroxide (OH), nitrogen oxides (NO_x), aerosols, clouds, and radiation are analyzed and compared to the literature. ECHAM-HAMMOZ performs well in many aspects. However, in the base simulation, lightning NO_x emissions are very low, and the impact of the heterogeneous reaction of HNO₃ on dust and seasalt aerosol is too strong. Sensitivity simulations with increased lightning NOx or modified heterogeneous chemistry deteriorate the comparison with observations and yield excessively large ozone budget terms and too much OH. We hypothesize that this is an impact of potential issues with tropical convection in the ECHAM model.

20 years of ClO measurements in the Antarctic lower stratosphere

We present 20 years (1996–2015) of austral springtime measurements of chlorine monoxide (ClO) over Antarctica from the Chlorine Oxide Experiment (ChlOE1) ground-based millimeter wave spectrometer at Scott Base, Antarctica, as well 12 years (2004–2015) of ClO measurements from the Aura Microwave Limb Sounder (MLS). From August onwards we observe a strong increase in lower stratospheric ClO, with a peak column amount usually occurring in early September. From mid-September onwards we observe a strong decrease in ClO. In order to study interannual differences, we focus on a 3-week period from 28 August to 17 September for each year and compare the average column ClO anomalies. These column ClO anomalies are shown to be highly correlated with the average ozone mass deficit for September and October of each year. We also show that anomalies in column ClO are strongly anti-correlated with 30 hPa temperature anomalies, both on a daily and an interannual timescale. Making use of this anti-correlation we calculate the linear dependence of the interannual variations in column ClO on interannual variations in temperature. By making use of this relationship, we can better estimate the underlying trend in the total chlorine (Cly = HCl + ClONO2 + HOCl + 2 × Cl2 + 2 × Cl2O2 + ClO + Cl). The resultant trends in Cly, which determine the long-term trend in ClO, are estimated to be −0.5 ± 0.2, −1.4 ± 0.9, and −0.6 ± 0.4 % year−1, for zonal MLS, Scott Base MLS (both 2004–2015), and ChlOE (1996–2015) respectively. These trends are within 1σ of trends in stratospheric Cly previously found at other latitudes. The decrease in ClO is consistent with the trend expected from regulations enacted under the Montreal Protocol.

Persistence of upper stratospheric wintertime tracer variability into the Arctic spring and summer

Using data from the Aeronomy of Ice in the Mesosphere (AIM) and Aura satellites, we have categorized the interannual variability of winter- and springtime upper stratospheric methane (CH4). We further show the effects of this variability on the chemistry of the upper stratosphere throughout the following summer. Years with strong wintertime mesospheric descent followed by dynamically quiet springs, such as 2009, lead to the lowest summertime CH4. Years with relatively weak wintertime descent, but strong springtime planetary wave activity, such as 2011, have the highest summertime CH4. By sampling the Aura Microwave Limb Sounder (MLS) according to the occultation pattern of the AIM Solar Occultation for Ice Experiment (SOFIE), we show that summertime upper stratospheric chlorine monoxide (ClO) almost perfectly anticorrelates with the CH4. This is consistent with the reaction of atomic chlorine with CH4 to form the reservoir species, hydrochloric acid (HCl). The summertime ClO for years with strong, uninterrupted mesospheric descent is about 50 % greater than in years with strong horizontal transport and mixing of high CH4 air from lower latitudes. Small, but persistent effects on ozone are also seen such that between 1 and 2 hPa, ozone is about 4–5 % higher in summer for the years with the highest CH4 relative to the lowest. This is consistent with the role of the chlorine catalytic cycle on ozone. These dependencies may offer a means to monitor dynamical effects on the high-latitude upper stratosphere using summertime ClO measurements as a proxy. Additionally, these chlorine-controlled ozone decreases, which are seen to maximize after years with strong uninterrupted wintertime descent, represent a new mechanism by which mesospheric descent can affect polar ozone. Finally, given that the effects on ozone appear to persist much of the rest of the year, the consideration of winter/spring dynamical variability may also be relevant in studies of ozone trends.

20 Years of ClO Measurements in the Antarctic Lower Stratosphere

We present 20 years of springtime measurements of ClO over Antarctica from the Chlorine monOxide Experiment (ChlOE1) ground-based millimeter wave spectrometer at Scott Base, Antarctica, as well 12 years of ClO measurements from the Aura Microwave Limb Sounder (MLS). From August onwards we observe a strong increase in lower stratospheric ClO, with a peak column amount usually occurring in early September. From mid-September onwards we observe a strong decrease in ClO. In order to study interannual differences we focus on a 3-week period from August 28 to September 17 for each year, and compare the average column ClO anomalies. These column ClO anomalies are shown to be highly correlated with the average ozone mass deficit for September and October of each year. We also show that anomalies in column ClO are anti-correlated with 30 hPa temperature anomalies, both on a daily and an interannual timescale. We calculate the dependence of interannual variations in column ClO on interannual variations in temperature. By making use of this relationship we can better estimate the underlying trend in the Cly which provides the reservoir for the ClO. The resultant trends for zonal MLS, Scott Base MLS (both 2004–2015), and ChlOE (1996–2015) were 0.5 ± 0.2 %/yr, −1.4 ± 0.9 %/yr, and −0.6 ± 0.4 %/yr, respectively. These trends are within 1σ of trends in stratospheric Cly previously found at other latitudes. This decrease in ClO is the result of changes in anthropogenic CFC emissions due to actions taken under the Montreal Protocol.

Polar processing in a split vortex: Arctic ozone loss in early winter 2012/2013

A sudden stratospheric warming (SSW) in early January 2013 caused the Arctic polar vortex to split and temperatures to rapidly rise above the threshold for chlorine activation. However, ozone in the lower stratospheric polar vortex from late December 2012 through early February 2013 reached the lowest values on record for that time of year. Analysis of Aura Microwave Limb Sounder (MLS) trace gas measurements and Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) polar stratospheric cloud (PSC) data shows that exceptional chemical ozone loss early in the 2012/13 Arctic winter resulted from a unique combination of meteorological conditions associated with the early-January 2013 SSW: unusually low temperatures in December 2012, offspring vortices within which air remained well isolated for nearly 1 month after the vortex split, and greater-than-usual vortex sunlight exposure throughout December 2012 and January 2013. Conditions in the two offspring vortices differed substantially, with the one overlying Canada having lower temperatures, lower nitric acid (HNO3), lower hydrogen chloride, more sunlight exposure/higher ClO in late January, and a later onset of chlorine deactivation than the one overlying Siberia. MLS HNO3 and CALIPSO data indicate that PSC activity in December 2012 was more extensive and persistent than at that time in any other Arctic winter in the past decade. Chlorine monoxide (ClO, measured by MLS) rose earlier than previously observed and was the largest on record through mid-January 2013. Enhanced vortex ClO persisted until mid-February despite the cessation of PSC activity when the SSW started. Vortex HNO3 remained depressed after PSCs had disappeared; passive transport calculations indicate vortex-averaged denitrification of about 4 parts per billion by volume. The estimated vortex-averaged chemical ozone loss, ~ 0.7–0.8 parts per million by volume near 500 K (~21 km), was the largest December/January loss in the MLS record from 2004/05 to 2014/15.