Particulate nitrate ([Formula: see text]) has long been considered a permanent sink for NOx (NO and NO2), removing a gaseous pollutant that is central to air quality and that influences the global self-cleansing capacity of the atmosphere. Evidence is emerging that photolysis of [Formula: see text] can recycle HONO and NOx back to the gas phase with potentially important implications for tropospheric ozone and OH budgets; however, there are substantial discrepancies in "renoxification" photolysis rate constants. Using aircraft and ground-based HONO observations in the remote Atlantic troposphere, we show evidence for renoxification occurring on mixed marine aerosols with an efficiency that increases with relative humidity and decreases with the concentration of [Formula: see text], thus largely reconciling the very large discrepancies in renoxification photolysis rate constants found across multiple laboratory and field studies. Active release of HONO from aerosol has important implications for atmospheric oxidants such as OH and O3 in both polluted and clean environments.
After the 1980s, atmospheric sulfate reduction is slower than the dramatic reductions in sulfur dioxide (SO2) emissions. However, a lack of observational evidence has hindered the identification of causal feedback mechanisms. Here, we report an increase in the oxygen isotopic composition of sulfate ([Formula: see text]) in a Greenland ice core, implying an enhanced role of acidity-dependent in-cloud oxidation by ozone (up to 17 to 27%) in sulfate production since the 1960s. A global chemical transport model reproduces the magnitude of the increase in observed [Formula: see text] with a 10 to 15% enhancement in the conversion efficiency from SO2 to sulfate in Eastern North America and Western Europe. With an expected continued decrease in atmospheric acidity, this feedback will continue in the future and partially hinder air quality improvements.
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 (O3) and air quality by reducing extreme O3 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 O3 is believed to be the largest single source of gaseous iodine to the atmosphere. Due to increased anthropogenic O3, 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.
Marine cloud brightening (MCB) is proposed to offset global warming by emitting sea salt aerosols to the tropical marine boundary layer, which increases aerosol and cloud albedo. Sea salt aerosol is the main source of tropospheric reactive chlorine (Cl y ) and bromine (Br y ). The effects of additional sea salt on atmospheric chemistry have not been explored. We simulate sea salt aerosol injections for MCB under two scenarios (212-569 Tg/a) in the GEOS-Chem global chemical transport model, only considering their impacts as a halogen source. Globally, tropospheric Cl y and Br y increase (20-40%), leading to decreased ozone (-3 to -6%). Consequently, OH decreases (-3 to -5%), which increases the methane lifetime (3-6%). Our results suggest that the chemistry of the additional sea salt leads to minor total radiative forcing compared to that of the sea salt aerosol itself (~2%) but may have potential implications for surface ozone pollution in tropical coastal regions.
The global oxidation capacity, defined as the tropospheric mean concentration of the hydroxyl radical (OH), controls the lifetime of reactive trace gases in the atmosphere such as methane and carbon monoxide (CO). Models tend to underestimate the methane lifetime and CO concentrations throughout the troposphere, which is consistent with excessive OH. Approximately half of the oxidation of methane and non-methane volatile organic compounds (VOCs) is thought to occur over the oceans where oxidant chemistry has received little validation due to a lack of observational constraints. We use observations from the first two deployments of the NASA ATom aircraft campaign during July-August 2016 and January-February 2017 to evaluate the oxidation capacity over the remote oceans and its representation by the GEOS-Chem chemical transport model. The model successfully simulates the magnitude and vertical profile of remote OH within the measurement uncertainties. Comparisons against the drivers of OH production (water vapor, ozone, and NO y concentrations, ozone photolysis frequencies) also show minimal bias, with the exception of wintertime NO y . The severe model overestimate of NO y during this period may indicate insufficient wet scavenging and/or missing loss on sea-salt aerosols. Large uncertainties in these processes require further study to improve simulated NO y partitioning and removal in the troposphere, but preliminary tests suggest that their overall impact could marginally reduce the model bias in tropospheric OH. During the ATom-1 deployment, OH reactivity (OHR) below 3 km is significantly enhanced, and this is not captured by the sum of its measured components (cOHRobs) or by the model (cOHRmod). This enhancement could suggest missing reactive VOCs but cannot be explained by a comprehensive simulation of both biotic and abiotic ocean sources of VOCs. Additional sources of VOC reactivity in this region are difficult to reconcile with the full suite of ATom measurement constraints. The model generally reproduces the magnitude and seasonality of cOHRobs but underestimates the contribution of oxygenated VOCs, mainly acetaldehyde, which is severely underestimated throughout the troposphere despite its calculated lifetime of less than a day. Missing model acetaldehyde in previous studies was attributed to measurement uncertainties that have been largely resolved. Observations of peroxyacetic acid (PAA) provide new support for remote levels of acetaldehyde. The underestimate in both model acetaldehyde and PAA is present throughout the year in both hemispheres and peaks during Northern Hemisphere summer. The addition of ocean sources of VOCs in the model increases cOHRmod by 3% to 9% and improves model-measurement agreement for acetaldehyde, particularly in winter, but cannot resolve the model summertime bias. Doing so would require 100 Tg yr-1 of a long-lived unknown precursor throughout the year with significant additional emissions in the Northern Hemisphere summer. Improving the model bias for remote acetaldehyde and PAA is unlikely to fully resolve previously reported model global biases in OH and methane lifetime, suggesting that future work should examine the sources and sinks of OH over land.
The marine iodine cycle has significant impacts on air quality and atmospheric chemistry. Specifically, the reaction of iodide with ozone in the top few micrometres of the surface ocean is an important sink for tropospheric ozone (a pollutant gas) and the dominant source of reactive iodine to the atmosphere. Sea surface iodide parameterisations are now being implemented in air quality models, but these are currently a major source of uncertainty. Relatively little observational data is available to estimate the global surface iodide concentrations, and this data has not hitherto been openly available in a collated, digital form. Here we present all available sea surface (<20 m depth) iodide observations. The dataset includes values digitised from published manuscripts, published and unpublished data supplied directly by the originators, and data obtained from repositories. It contains 1342 data points, and spans latitudes from 70°S to 68°N, representing all major basins. The data may be used to model sea surface iodide concentrations or as a reference for future observations.
Bromine and iodine chemistry has been updated in the Community Multiscale Air Quality (CMAQ) model to better capture the influence of natural emissions from the oceans on ozone concentrations. Annual simulations were performed using the hemispheric CMAQ model without and with bromine and iodine chemistry. Model results over the Northern Hemisphere show that including bromine and iodine chemistry in CMAQ not only reduces ozone concentrations within the marine boundary layer but also aloft and inland. Bromine and iodine chemistry reduces annual mean surface ozone over seawater by 25%, with lesser ozone reductions over land. The bromine and iodine chemistry decreases ozone concentration without changing the diurnal profile and is active throughout the year. However, it does not have a strong seasonal influence on ozone over the Northern Hemisphere. Model performance of CMAQ is improved by the bromine and iodine chemistry when compared to observations, especially at coastal sites and over seawater. Relative to bromine, iodine chemistry is approximately four times more effective in reducing ozone over seawater over the Northern Hemisphere (on an annual basis). Model results suggest that the chemistry modulates intercontinental transport and lowers the background ozone imported to the United States.
Iodine is an important nutrient and a significant sink of tropospheric ozone, a climate-forcing gas and air pollutant. Ozone interacts with seawater iodide, leading to volatile inorganic iodine release that likely represents the largest source of atmospheric iodine. Increasing ozone concentrations since the preindustrial period imply that iodine chemistry and its associated ozone destruction is now substantially more active. However, the lack of historical observations of ozone and iodine means that such estimates rely primarily on model calculations. Here we use seasonally resolved records from an Alpine ice core to investigate 20th century changes in atmospheric iodine. After carefully considering possible postdepositional changes in the ice core record, we conclude that iodine deposition over the Alps increased by at least a factor of 3 from 1950 to the 1990s in the summer months, with smaller increases during the winter months. We reproduce these general trends using a chemical transport model and show that they are due to increased oceanic iodine emissions, coupled to a change in iodine speciation over Europe from enhanced nitrogen oxide emissions. The model underestimates the increase in iodine deposition by a factor of 2, however, which may be due to an underestimate in the 20th century ozone increase. Our results suggest that iodine's impact on the Northern Hemisphere atmosphere accelerated over the 20th century and show a coupling between anthropogenic pollution and the availability of iodine as an essential nutrient to the terrestrial biosphere.
Air Pollutants/chemistry , Ice/analysis , Iodine/chemistry , Seawater/chemistry , Atmosphere , Climate , Europe , Ozone/chemistry , Seasons
There is growing global consumption of non-fossil fuels such as ethanol made from renewable biomass. Previous studies have shown that one of the main air quality disadvantages of using ethanol blended fuels is a significant increase in the production of acetaldehyde, an unregulated and toxic pollutant. Most studies on the impacts of ethanol blended gasoline have been carried out in the US and Brazil, with much less focus on the UK and Europe. We report time resolved measurements of ethanol in London during the winter and summer of 2012. In both seasons the mean mixing ratio of ethanol was around 5 ppb, with maximum values over 30 ppb, making ethanol currently the most abundant VOC in London air. We identify a road transport related source, with 'rush-hour' peaks observed. Ethanol is strongly correlated with other road transport-related emissions, such as small aromatics and light alkanes, and has no relationship to summer biogenic emissions. To determine the impact of road transport-related ethanol emission on secondary species (i.e. acetaldehyde and ozone), we use both a chemically detailed box model (incorporating the Master Chemical Mechanism, MCM) and a global and nested regional scale chemical transport model (GEOS-Chem), on various processing time scales. Using the MCM model, only 16% of the modelled acetaldehyde was formed from ethanol oxidation. However, the model significantly underpredicts the total levels of acetaldehyde, indicating a missing primary emission source, that appears to be traffic-related. Further support for a primary emission source comes from the regional scale model simulations, where the observed concentrations of ethanol and acetaldehyde can only be reconciled with the inclusion of large primary emissions. Although only constrained by one set of observations, the regional modelling suggests a European ethanol source similar in magnitude to that of ethane (â¼60 Gg per year) and greater than that of acetaldehyde (â¼10 Gg per year). The increased concentrations of ethanol and acetaldehyde from primary emissions impacts both radical and NOx cycling over Europe, resulting in significant regional impacts on NOy speciation and O3 concentrations, with potential changes to human exposure to air pollutants.
Air Pollution/analysis , Ethanol/analysis , Acetaldehyde/analysis , Chromatography, Gas , Ethanol/chemistry , Linear Models , London , Nitrogen Oxides/analysis , Oxidation-Reduction , Ozone/analysis , Seasons
