Assessing and improving cloud-height-based parameterisations of global lightning flash rate, and their impact on lightning-produced NO_<i>x</i> and tropospheric composition in a chemistry–climate model

Although lightning-generated oxides of nitrogen (LNOx) account for only approximately 10 % of the global NOx source, they have a disproportionately large impact on tropospheric photochemistry due to the conducive conditions in the tropical upper troposphere where lightning is mostly discharged. In most global composition models, lightning flash rates used to calculate LNOx are expressed in terms of convective cloud-top height via the Price and Rind (1992) (PR92) parameterisations for land and ocean, where the oceanic parameterisation is known to greatly underestimate flash rates. We conduct a critical assessment of flash-rate parameterisations that are based on cloud-top height and validate them within the Australian Community Climate and Earth System Simulator – United Kingdom Chemistry and Aerosol (ACCESS-UKCA) global chemistry–climate model using the Lightning Imaging Sensor and Optical Transient Detector (LIS/OTD) satellite data. While the PR92 parameterisation for land yields satisfactory predictions, the oceanic parameterisation, as expected, underestimates the observed flash-rate density severely, yielding a global average over the ocean of 0.33 flashes s−1 compared to the observed 9.16 flashes s−1 and leading to LNOx being underestimated proportionally. We formulate new flash-rate parameterisations following Boccippio's (2002) scaling relationships between thunderstorm electrical generator power and storm geometry coupled with available data. The new parameterisation for land performs very similarly to the corresponding PR92 one, as would be expected, whereas the new oceanic parameterisation simulates the flash-rate observations much more accurately, giving a global average over the ocean of 8.84 flashes s−1. The use of the improved flash-rate parameterisations in ACCESS-UKCA changes the modelled tropospheric composition – global LNOx increases from 4.8 to 6.6 Tg N yr−1; the ozone (O3) burden increases by 8.5 %; there is an increase in the mid- to upper-tropospheric NOx by as much as 40 pptv, a 13 % increase in the global hydroxyl radical (OH), a decrease in the methane lifetime by 6.7 %, and a decrease in the lower-tropospheric carbon monoxide (CO) by 3 %–7 %. Compared to observations, the modelled tropospheric NOx and ozone in the Southern Hemisphere and over the ocean are improved by this new flash-rate parameterisation.

Marine iodine emissions in a changing world

Iodine is a critical trace element involved in many diverse and important processes in the Earth system. The importance of iodine for human health has been known for over a century, with low iodine in the diet being linked to goitre, cretinism and neonatal death. Research over the last few decades has shown that iodine has significant impacts on tropospheric photochemistry, ultimately impacting climate by reducing the radiative forcing of ozone (O 3 ) and air quality by reducing extreme O 3 concentrations in polluted regions. Iodine is naturally present in the ocean, predominantly as aqueous iodide and iodate. The rapid reaction of sea-surface iodide with O 3 is believed to be the largest single source of gaseous iodine to the atmosphere. Due to increased anthropogenic O 3 , this release of iodine is believed to have increased dramatically over the twentieth century, by as much as a factor of 3. Uncertainties in the marine iodine distribution and global cycle are, however, major constraints in the effective prediction of how the emissions of iodine and its biogeochemical cycle may change in the future or have changed in the past. Here, we present a synthesis of recent results by our team and others which bring a fresh perspective to understanding the global iodine biogeochemical cycle. In particular, we suggest that future climate-induced oceanographic changes could result in a significant change in aqueous iodide concentrations in the surface ocean, with implications for atmospheric air quality and climate.

Assessing and improving cloud-height based parameterisations of global lightning flash rate, and their impact on lightning-produced NO_x and tropospheric composition

Although lightning-generated oxides of nitrogen (LNOx) account for only approximately 10 % of the global NOx source, it has a disproportionately large impact on tropospheric photochemistry due to the conducive conditions in the tropical upper troposphere where lightning is mostly discharged. In most global composition models, lightning flash rates used to calculate LNOx are expressed in terms of convective cloud-top height via the Price and Rind (1992) (PR92) parameterisations for land and ocean. We conduct a critical assessment of flash-rate parameterisations that are based on cloud-top height and validate them within the ACCESS-UKCA global chemistry-climate model using the LIS/OTD satellite data. While the PR92 parameterisation for land yields satisfactory predictions, the oceanic parameterisation underestimates the observed flash-rate density severely, yielding a global average of 0.33 flashes/s compared to the observed 9.16 flashes/s over the ocean and leading to LNOx being underestimated proportionally. We formulate new/alternative flash-rate parameterisations following Boccippio’s (2002) scaling relationships between thunderstorm electrical generator power and storm geometry coupled with available data. While the new parameterisation for land performs very similar to the corresponding PR92 one as would be expected, the new oceanic parameterisation simulates the flash-rate observations more accurately, giving a global average of 8.84 flashes/s. The use of the improved flash-rate parameterisations in ACCESS-UKCA changes the modelled tropospheric composition—global LNOx increases from 4.8 to 6.6 Tg N/yr; the ozone (O3) burden increases by 8.5 %; there is an increase in the mid- to upper-tropospheric NOx by as much as 40 ppt; a 13 % increase in the global hydroxyl (OH); a decrease in the methane lifetime by 6.7 %; and a decrease in the lower tropospheric carbon monoxide (CO) by 3–7 %. Overall, the modelled tropospheric NOx and ozone are improved compared to observations, particularly in the Southern Hemisphere and over the ocean.

i_NRACM: Incorporating ¹⁵N into the Regional Atmospheric Chemistry Mechanism (RACM) for assessing the role photochemistry plays in controlling the isotopic composition of NO_x, NO_y, and atmospheric nitrate.

Nitrogen oxides, classified as NOx (nitric oxide (NO) + nitrogen dioxide (NO2)) and NOy (NOx + NO3, N2O5 HNO3, + HNO4 + HONO + Peroxyacetyl nitrate (PAN) + organic nitrates + any oxidized N compound), are important trace gases in the troposphere, which play an important role in the formation of ozone, particulate matter (PM), and secondary organic aerosols (SOA). Among many uncertainties in movement of atmospheric N compounds, nowadays understanding of NOy cycling is limited by NOx emission budget, unresolved issues within the heterogeneous uptake coefficients of N2O5, the formation of organic nitrates in urban forests, etc. A photochemical mechanism used to simulate tropospheric photochemistry was altered to include 15N compounds and reactions as a means to simulate δ15N values in NOy compounds. The 16 N compounds and 96 reactions involving N used in Regional Atmospheric Chemistry Mechanism (RACM) were replicated using 15N in a new mechanism called iNRACM. The 192 N reactions in iNRACM were tested to see if isotope effects were relevant with respect to significantly changing the δ15N values (±1 ‰) of NOx, HONO, and/or HNO3. The isotope fractionation factors (α) for relevant reactions were assigned based on recent experimental or calculated values. Each relevant reaction in the iNRACM mechanism was tested individually and in concert in order to assess the controlling reactions. The final mechanism was tested by running simulations under different conditions that are typical of pristine, rural, urban, and highly polluted environments. The results of these simulations predicted several interesting δ15N variations.

Influences of oceanic ozone deposition on tropospheric photochemistry

The deposition of ozone to seawater is an important ozone sink. Despite constituting as much as a third of the total ozone deposition, it receives significantly less attention than the deposition to terrestrial ecosystems. Models have typically calculated the deposition rate based on a resistance-in-series model with a uniform waterside resistance. This leads to models having an essentially uniform deposition velocity of approximately 0.05 cm s−1 to seawater, which is significantly higher than the limited observational dataset. Following from Luhar et al. (2018) we include a representation of the oceanic deposition of ozone in the GEOS-Chem model of atmospheric chemistry and transport based on its reaction with sea-surface iodide. The updated scheme halves the calculated annual area-weighted mean deposition velocity to water from 0.0464 cm s−1 (25th and 75th percentiles of 0.0461 cm s−1 and 0.0471 cm s−1 respectively) to 0.0231 cm s−1 (25th and 75th percentiles of 0.0121 cm s−1 and 0.0303 cm s−1 respectively). The calculated ozone deposition velocity varies from 0.009 cm s−1 in polar waters to 0.040 cm s−1 at the tropics. This improves comparisons to observations. The variability is driven mainly by the temperature-dependent rate constant for the reaction between iodide and ozone, the temperature dependence of the solubility, and variations in the ocean iodide concentration. The calculated annual deposition flux of ozone to the ocean is reduced from 222 to 122 Tg yr−1, and overall deposition of ozone to all surface types reduces from 862 to 758 Tg yr−1. Tropospheric ozone burdens and global mean OH increase from 324 to 328 Tg, and from 1.17×106 to 1.18×106 molec.cm-3, respectively. A total of 34 % of surface grid boxes experience a 10 % or greater increase in ozone concentration. Comparisons between observations of surface ozone and the model are improved with the new parameterization notably around the Southern Ocean. Process-level representation of oceanic deposition of ozone thus appears essential for representing the concentration of surface ozone over the planet.

Detectability assessment of a satellite sensor for lower tropospheric ozone responses to its precursors emission changes in East Asian summer

Satellite sensors are powerful tools to monitor the spatiotemporal variations of air pollutants in large scales, but it has been challenging to detect surface O3 due to the presence of abundant stratospheric and upper tropospheric O3. East Asia is one of the most polluted regions in the world, but anthropogenic emissions such as NOx and SO2 began to decrease in 2010s. This trend was well observed by satellites, but the spatiotemporal impacts of these emission trends on O3 have not been well understood. Recent advancement in a retrieval method for the Ozone Monitoring Instrument (OMI) sensor enabled detection of lower tropospheric O3 and its legitimacy has been validated. In this study, we investigated the statistical significance for the OMI sensor to detect the lower tropospheric O3 responses to the future emission reduction of the O3 precursor gases over East Asia in summer, by utilizing a regional chemistry model. The emission reduction of 10, 25, 50, and 90% resulted in 4.4, 11, 23, and 53% decrease of the areal and monthly mean daytime simulated satellite-detectable O3 (ΔO3), respectively. The fractions of significant areas are 55, 84, 93, and 96% at a one-sided 95% confidence interval. Because of the recent advancement of satellite sensor technologies (e.g., TROPOMI), study on tropospheric photochemistry will be rapidly advanced in the near future. The current study proved the usefulness of such satellite analyses on the lower tropospheric O3 and its perturbations due to the precursor gas emission controls.

Influences of oceanic ozone deposition on tropospheric photochemistry

The deposition of ozone to seawater is an important ozone sink. Despite constituting as much as a third of the total ozone deposition, it receives significantly less attention than the deposition to terrestrial ecosystems. Models have typically calculated the deposition rate based on a resistance-in-series model with a uniform waterside resistance. This leads to models having an essentially uniform deposition velocity of approximately 0.05 cm s−1 to seawater, which is significantly higher than the limited observational dataset. Following from Luhar et al. (2018) we include a representation of the oceanic deposition of ozone into the GEOS-Chem model of atmospheric chemistry and transport based on its reaction with sea-surface iodide. The updated scheme halves the calculated annual area-weighted mean deposition velocity to water from 0.0464 cm s−1 (25th and 75th percentiles of 0.0461 cm s−1 and 0.0471 cm s−1 respectively), to 0.0231 cm s−1 (25th and 75th percentiles of 0.0121 cm s−1 and 0.0303 cm s−1 respectively). The calculated ozone deposition velocity varies from 0.009 cm s−1 in polar waters to 0.040 cm s−1 at the tropics. This improves comparisons to observations. The variability is driven mainly by the temperature dependant rate constant for the reaction between iodide and ozone, the temperature dependence of the solubility and variations in the ocean iodide concentration. The calculated annual deposition flux of ozone to the ocean is reduced from 222 Tg yr−1 to 112 Tg yr−1, and overall deposition of ozone to all surface types reduces from 862 Tg yr−1 to 758 Tg yr−1. Tropospheric ozone burdens and global mean OH increase from 324 Tg to 328 Tg, and from 1.17 × 106 molec cm−3 to 1.18 × 106 molec cm−3, respectively. 34 % of surface grid boxes experience a 10 % or greater increase in ozone concentration. Comparisons between observations of surface ozone and the model are improved with the new parameterization notably around the Southern Ocean. Process level representation of oceanic deposition of ozone thus appears essential for representing the concentration of surface ozone over the planet.

Characterisation of GOME-2 formaldehyde retrieval sensitivity

Formaldehyde (CH2O) is an important tracer of tropospheric photochemistry, whose slant column abundance can be retrieved from satellite measurements of solar backscattered UV radiation, using differential absorption retrieval techniques. In this work a spectral fitting sensitivity analysis is conducted on CH2O slant columns retrieved from the Global Ozone Monitoring Experiment 2 (GOME-2) instrument. Despite quite different spectral fitting approaches, the retrieved CH2O slant columns have geographic distributions that generally match expected CH2O sources, though the slant column magnitudes and corresponding uncertainties are particularly sensitive to the retrieval set-up. The choice of spectral fitting window, polynomial order, I0 correction, and inclusion of minor absorbers tend to result in the largest modulations of retrieved slant column magnitude and fit quality. However, application of a reference sector correction using observations over the remote Pacific Ocean is shown to largely homogenise the resulting CH2O vertical columns obtained with different retrieval settings, thereby largely reducing any systematic error sources from spectral fitting.

Characterisation of GOME-2 formaldehyde retrieval sensitivity

Formaldehyde (HCHO) is an important tracer of tropospheric photochemistry, whose slant column abundance can be retrieved from satellite measurements of solar backscattered UV radiation, using differential absorption retrieval techniques. In this work a spectral fitting sensitivity analysis is conducted on HCHO slant columns retrieved from the Global Ozone Monitoring Experiment 2 (GOME-2) instrument. Despite quite different spectral fitting approaches, the retrieved HCHO slant columns have geographic distributions that generally match expected HCHO sources, though the slant column magnitudes and corresponding uncertainties are particularly sensitive to the retrieval set-up. The choice of spectral fitting window, polynomial order, I0 correction, and inclusion of minor absorbers tend to have the largest impact on the fit residuals. However, application of a reference sector correction using observations over the remote Pacific Ocean, is shown to largely homogenise the resulting HCHO vertical columns, thereby largely reducing any systematic erroneous spectral fitting.