Observational evidence of solar activity interaction with chlorine chemistry curbing Antarctic ozone loss

<p>We present the impact of the so-called energetic particle precipitation (EPP), part of natural solar forcing on the atmosphere, on polar stratospheric NO<sub>x</sub>, ozone, and chlorine chemistry in the Antarctic springtime, using multi-satellite observations covering the overall period of 2005–2017. We find consistent ozone increases when high solar activity occurs during years with easterly phase of the quasi biennial oscillation. These ozone enhancements are also present in total O<sub>3</sub> column observations. We find consistent decreases in springtime active chlorine following winters of elevated solar activity. Further analysis shows that this is accompanied by increase of chemically inactive chlorine reservoir species, explaining the observed ozone increase. This provides the first observational evidence supporting the previously proposed mechanism relating to EPP modulating chlorine driven ozone loss. Our findings suggest that solar activity via EPP has played an important role in modulating Antarctic ozone depletion in the last 15 years. As chlorine loading in the polar stratosphere continues to decrease in the future, this buffering mechanism will become less effective and catalytic ozone destruction by EPP produced NO<sub>x</sub> will likely become a major contributor to Antarctic ozone loss.</p>

Reformulating the bromine alpha factor and equivalent effective stratospheric chlorine (EESC): evolution of ozone destruction rates of bromine and chlorine in future climate scenarios

Future trajectories of the stratospheric trace gas background will alter the rates of bromine- and chlorine-mediated catalytic ozone destruction via changes in the partitioning of inorganic halogen reservoirs and the underlying temperature structure of the stratosphere. The current formulation of the bromine alpha factor, the ozone-destroying power of stratospheric bromine atoms relative to stratospheric chlorine atoms, is invariant with the climate state. Here, we refactor the bromine alpha factor, introducing normalization to a benchmark chemistry–climate state, and formulate Equivalent Effective Stratospheric Benchmark-normalized Chlorine (EESBnC) to reflect changes in the rates of both bromine- and chlorine-mediated ozone loss catalysis with time. We show that the ozone-processing power of the extrapolar stratosphere is significantly perturbed by future climate assumptions. Furthermore, we show that our EESBnC-based estimate of the extrapolar ozone recovery date is in closer agreement with extrapolar ozone recovery dates predicted using more sophisticated 3-D chemistry–climate models than predictions made using equivalent effective stratospheric chlorine (EESC).

Temporal Evolution of the Bromine Alpha Factor and Equivalent Effective Stratospheric Chlorine in Future Climate Scenarios

Future trajectories of the stratospheric trace gas background will alter the rates of bromine- and chlorine-mediated catalytic ozone destruction via changes in the partitioning of inorganic halogen reservoirs and the underlying temperature structure of the stratosphere. The current formulation of the bromine alpha factor, the ozone-destroying power of stratospheric bromine atoms relative to stratospheric chlorine atoms, is invariant with climate state. Here, we refactor the bromine alpha factor, introducing climate normalization to a benchmark climate state, and reformulate Equivalent Effective Stratospheric Chlorine (EESC) to reflect changes in the rates of both chlorine- and bromine-mediated ozone loss catalysis with time. We show that the ozone-processing power of the extrapolar stratosphere is significantly perturbed by future climate assumptions. Furthermore, we show that our EESC-based estimate of the extrapolar ozone-recovery date is in closer agreement with extrapolar ozone recovery dates predicted using more sophisticated 3-D chemistry-climate models than prior formulations of EESC that employ climate-invariant values of the bromine alpha factor.

Global observation of iodic acid (HIO3)

<p>Trace iodine vapours have a significant impact on atmospheric chemistry, influencing catalytic ozone destruction and the HO<sub>x</sub> / NO<sub>x</sub> cycles. Oxidized iodine species also form aerosols in coastal and polar regions (O’Dowd et al, 2002), playing a direct role in Earth’s radiation balance. It was recently shown that iodic acid (HIO<sub>3</sub>) has a significant impact on coastal new particle formation processes (Sipilä et al., 2016). However, neutral HIO<sub>3 </sub>molecules have only been measured in two sites (Sipilä et al., 2016).</p><p>In this study, a global observation of HIO<sub>3</sub> has been carried out in ten sites around the globe, including city sites, Arctic and Antarctica sites, a remote island site, a coastal site and a boreal forest site. While the existence of HIO<sub>3</sub> is unambiguously revealed in all of the sites, its concentration varies significantly among them. Dedicated laboratory experiments are required to examine the particle formation rates from iodine-containing species to be able to predict their global importance in particle formation, and further, in cloud condensation nuclei formation.</p><p> </p><p>O’Dowd, C. D. et al. Marine aerosol formation from biogenic iodine emissions. Nature <strong>417</strong>, 632–6 (2002)</p><p>Sipilä, M. et al. Molecular-scale evidence of aerosol particle formation via sequential addition of HIO<sub>3</sub>. Nature <strong>537</strong>, 532–534 (2016).</p><p> </p>

A mechanism for biologically induced iodine emissions from sea ice

Ground- and satellite-based measurements have reported high concentrations of iodine monoxide (IO) in coastal Antarctica. The sources of such a large iodine burden in the coastal Antarctic atmosphere remain unknown. We propose a mechanism for iodine release from sea ice based on the premise that micro-algae are the primary source of iodine emissions in this environment. The emissions are triggered by the biological production of iodide (I−) and hypoiodous acid (HOI) from micro-algae (contained within and underneath sea ice) and their diffusion through sea-ice brine channels, ultimately accumulating in a thin brine layer (BL) on the surface of sea ice. Prior to reaching the BL, the diffusion timescale of iodine within sea ice is depth-dependent. The BL is also a vital component of the proposed mechanism as it enhances the chemical kinetics of iodine-related reactions, which allows for the efficient release of iodine to the polar boundary layer. We suggest that iodine is released to the atmosphere via three possible pathways: (1) emitted from the BL and then transported throughout snow atop sea ice, from where it is released to the atmosphere; (2) released directly from the BL to the atmosphere in regions of sea ice that are not covered with snowpack; or (3) emitted to the atmosphere directly through fractures in the sea-ice pack. To investigate the proposed biology–ice–atmosphere coupling at coastal Antarctica we use a multiphase model that incorporates the transport of iodine species, via diffusion, at variable depths, within brine channels of sea ice. Model simulations were conducted to interpret observations of elevated springtime IO in the coastal Antarctic, around the Weddell Sea. While a lack of experimental and observational data adds uncertainty to the model predictions, the results nevertheless show that the levels of inorganic iodine (i.e. I2, IBr, ICl) released from sea ice through this mechanism could account for the observed IO concentrations during this timeframe. The model results also indicate that iodine may trigger the catalytic release of bromine from sea ice through phase equilibration of IBr. Considering the extent of sea ice around the Antarctic continent, we suggest that the resulting high levels of iodine may have widespread impacts on catalytic ozone destruction and aerosol formation in the Antarctic lower troposphere.

The chemistry of daytime sprite streamers – a model study

The chemical processes in daytime sprite streamers in the altitude range of 30–54 km are investigated by means of a detailed ion–neutral chemistry model (without consideration of transport). The focus lies on nitrogen, hydrogen and oxygen species, and in particular on ozone perturbations. Initial effects of the breakdown electric fields at the tip of sprite streamers include a short-term loss of ozone due to ion–chemical reactions, a production of nitrogen radicals, and a liberation of atomic oxygen. The latter leads to a formation of ozone. In terms of relative ozone change, this effect decreases with altitude. The model results indicate that the subsequent ozone perturbations due to daytime sprites streamers differ considerably from the ones of night-time events. For night-time conditions, reactive nitrogen produced at the streamer heads is rapidly converted into significantly less reactive NO2, and there is basically no ozone depletion. The situation is different for daytime conditions where NOx causes catalytic ozone destruction. As a consequence, there is significant ozone loss in sprite streamers in the daytime atmosphere, in particular at higher altitudes. At an altitude of 54 km, ozone in the streamer column has decreased by about 15% fifteen minutes after the sprite event.

The chemistry of daytime sprite streamers – a model study

The chemical processes in daytime sprite streamers in the altitude range of 30–54 km are investigated by means of a detailed ion-neutral chemistry model (without consideration of transport). The model results indicate that ozone perturbations due to daytime sprites streamers differ considerably from the ones of nighttime events. Due to liberation of atomic oxygen there is an initial increase of ozone. In terms of relative ozone change, this effect decreases with altitude. While for nighttime conditions, reactive nitrogen produced during the electric breakdown is converted into less reactive NO2, in the sunlit atmosphere NOx causes catalytic ozone destruction. As a consequence, there is significant ozone loss in sprite streamers in the daytime atmosphere, in particular at higher altitudes. At an altitude of 54 km, ozone in the streamer column has decreased by about 15% fifteen minutes after the breakdown event.

Reconciliation of essential process parameters for an enhanced predictability of Arctic stratospheric ozone loss and its climate interactions (RECONCILE): activities and results

The international research project RECONCILE has addressed central questions regarding polar ozone depletion, with the objective to quantify some of the most relevant yet still uncertain physical and chemical processes and thereby improve prognostic modelling capabilities to realistically predict the response of the ozone layer to climate change. This overview paper outlines the scope and the general approach of RECONCILE, and it provides a summary of observations and modelling in 2010 and 2011 that have generated an in many respects unprecedented dataset to study processes in the Arctic winter stratosphere. Principally, it summarises important outcomes of RECONCILE including (i) better constraints and enhanced consistency on the set of parameters governing catalytic ozone destruction cycles, (ii) a better understanding of the role of cold binary aerosols in heterogeneous chlorine activation, (iii) an improved scheme of polar stratospheric cloud (PSC) processes that includes heterogeneous nucleation of nitric acid trihydrate (NAT) and ice on non-volatile background aerosol leading to better model parameterisations with respect to denitrification, and (iv) long transient simulations with a chemistry-climate model (CCM) updated based on the results of RECONCILE that better reproduce past ozone trends in Antarctica and are deemed to produce more reliable predictions of future ozone trends. The process studies and the global simulations conducted in RECONCILE show that in the Arctic, ozone depletion uncertainties in the chemical and microphysical processes are now clearly smaller than the sensitivity to dynamic variability.

Mesosphere-to-stratosphere descent of odd nitrogen in February–March 2009 after sudden stratospheric warming

We use the 3-D FinROSE chemistry transport model (CTM) and Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) observations to study connections between atmospheric dynamics and middle atmospheric NOx (NOx = NO + NO2) distribution. Two cases are considered in the northern polar regions: (1) descent of mesospheric NOx in February–March 2009 after a major sudden stratospheric warming (SSW) and, for comparison, (2) early 2007 when no NOx descent occurred. The model uses the European Centre for Medium-Range Weather Forecasts (ECMWF) operational data for winds and temperature, and we force NOx at the model upper altitude boundary (80 km) with ACE-FTS observations. We then compare the model results with ACE-FTS observations at lower altitudes. For the periods studied, geomagnetic indices are low, which indicates absence of local NOx production by particle precipitation. This gives us a good opportunity to study effects of atmospheric transport on polar NOx. The model results show no NOx descent in 2007, in agreement with ACE-FTS. In contrast, a large amount of NOx descends in February–March 2009 from the upper to lower mesosphere at latitudes larger than 60° N, i.e. inside the polar vortex. Both observations and model results suggest NOx increases of 150–200 ppb (i.e. by factor of 50) at 65 km due to the descent. However, the model underestimates the amount of NOx around 55 km by 40–60 ppb. According to the model results, chemical loss of NOx is insignificant during the descent period, i.e. polar NOx is mainly controlled by dynamics. The descent is terminated and the polar NOx amounts return to pre-descent levels in mid-March, when the polar vortex breaks. The break-up prevents the descending NOx from reaching the upper stratosphere, where it could participate in catalytic ozone destruction. Both ACE-FTS observations and FinROSE show a decrease of ozone of 20–30 % at 30–50 km from mid-February to mid-March. In the model, these ozone changes are not related to the descent but are due to solar activation of halogen and NOx chemistry.

A mechanism for biologically-induced iodine emissions from sea-ice

Only recently, ground- and satellite-based measurements have reported high concentrations of IO in coastal Antarctica. The sources of such a large iodine burden in the Antarctic atmosphere remain unknown. We propose a novel mechanism for iodine release from sea-ice surfaces. The release is triggered by the biological production of iodide (I-) and hypoiodous acid (HOI) from marine algae, contained within and underneath sea-ice, and their diffusion through sea-ice brine channels to accumulate in the quasi-liquid layer on the surface of sea-ice. A multiphase chemical model of polar atmospheric chemistry has been developed to investigate the biology-ice-atmosphere coupling in the polar environment. Model simulations were conducted to interpret recent observations of elevated IO in the coastal Antarctic springtime. The results show that the levels of inorganic iodine (i.e. I2, IBr, ICl) released from sea-ice through this mechanism account for the observed IO concentrations in the Antarctic springtime environment. The model results also indicate that iodine may trigger the catalytic release of bromine from sea-ice through phase equilibration of IBr. Considering the extent of sea-ice around the Antarctic continent, we suggest that the resulting high levels of iodine may have widespread impact on catalytic ozone destruction and aerosol formation in the Antarctic lower troposphere.