Ozone Flux Research Articles

Intercomparison of fast airborne ozone instruments to measure eddy covariance fluxes: spatial variability in deposition at the ocean surface and evidence for cloud processing

Abstract. The air–sea exchange of ozone (O3) is controlled by chemistry involving halogens, dissolved organic carbon, and sulfur in the sea surface microlayer. Calculations also indicate faster ozone photolysis at aqueous surfaces, but the role of clouds as an ozone sink is currently not well established. Fast-response ozone sensors offer opportunities to measure eddy covariance (EC) ozone fluxes in the marine boundary layer. However, intercomparisons of fast airborne O3 sensors and EC O3 fluxes measured on aircraft have not been conducted before. In April 2022, the Technological Innovation Into Iodine and GV Environmental Research (TI3GER) field campaign deployed three fast ozone sensors (gas chemiluminescence and a combination of UV absorption with coumarin chemiluminescence detection, CID) together with a fast water vapor sensor and anemometer to study iodine chemistry in the troposphere and stratosphere over Colorado and over the Pacific Ocean near Hawaii and Alaska. Here, we present an instrument comparison between the NCAR Fast O3 instrument (FO3, gas-phase CID) and two KIT Fast AIRborne Ozone instruments (FAIRO, UV absorption and coumarin CID). The sensors have comparable precision < 0.4 % Hz−0.5 (0.15 ppbv Hz−0.5), and ozone volume mixing ratios (VMRs) generally agreed within 2 % over a wide range of environmental conditions: 10 < O3 < 1000 ppbv, below detection < NOx < 7 ppbv, and 2 ppmv < H2O < 4 % VMR. Both instrument designs are demonstrated to be suitable for EC flux measurements and were able to detect O3 fluxes with exchange velocities (defined as positive for upward) as slow as −0.010 ± 0.004 cm s−1, which is in the lower range of previously reported measurements. Additionally, we present two case studies. In one, the direction of ozone and water vapor fluxes was reversed (vO3 = +0.134 ± 0.005 cm s−1), suggesting that overhead evaporating clouds could be a strong ozone sink. Further work is needed to better understand the role of clouds as a possibly widespread sink of ozone in the remote marine boundary layer. In the second case study, vO3 values are negative (varying by a factor of 6–10 from −0.036 ± 0.006 to −0.003 ± 0.004 cm s−1), while the water vapor fluxes are consistently positive due to evaporation from the ocean surface and spatially homogeneous. This case study demonstrates that the processes governing ozone and water vapor fluxes can become decoupled and illustrates the need to elucidate possible drivers (physical, chemical, or biological) of the variability in ozone exchange velocities on fine spatial scales (∼ 20 km) over remote oceans.

Analysis of the spatiotemporal changes in global tropospheric ozone concentrations from 1980 to 2020

Tropospheric ozone affects human health, ecosystems, and climate change. Previous studies on Tropospheric Column Ozone (TCO) have primarily concentrated on specific regions or global geographic divisions. This has led to insufficient exploration of the spatiotemporal characteristics and influencing factors of TCO in global and rational subregions. In this study, TCO is calculated using the Modern Era Retrospective analysis for Research and Applications version 2 (MERRA-2) reanalysis data and corrected using satellite data. Cluster analysis is conducted to explore the temporal characteristics of TCO variations in different regions. The results show that the global TCO is basically distributed latitudinally, with higher TCO in the northern hemisphere, which is related to atmospheric circulation, radiation, stratospheric transport, and the distribution of ozone precursors. Between 1980 and 2020, the global average annual TCO showed an increasing trend at 0.09 DU yr−1 due to rising anthropogenic emissions of ozone precursors (NOx at 589547.86 t yr−1 and NMVOC at 1070818.24 t yr−1), increasing tropopause height (−0.10 hPa yr−1), and the enhanced ozone flux at the tropopause (0.22 ppbv m s−2 yr−1). Cluster analysis reveals different trends in TCO changes across regions. The ocean south of 60°S and parts of West Antarctica (Region 2), the region from 30°N to 60°N and the western oceanic region of 30°S (Region 3), and the region from the equator to 60°S and the region north of 60°N (Region 5) exhibit increasing trends (with rates of 0.08 DU yr−1, 0.07 DU yr−1, and 0.11 DU yr−1, respectively), linked to the enhanced ozone flux at the tropopause, the rising tropopause height and increasing ozone p precursors. Conversely, the decreasing TCO trends in the equatorial Pacific (Region 1) and East Antarctica (Region 4) (with rates of −0.01 DU yr−1 and -0.02 DU yr−1) may be related to increased cloudiness and weakened photochemical reactions.

Ozone pollution contributes to the yield gap for beans in Uganda, East Africa, and is co-located with other agricultural stresses

Air quality negatively impacts agriculture, reducing the yield of staple food crops. While measured data on African ground-level ozone levels are scarce, experimental studies demonstrate the damaging impact of ozone on crops. Common beans (Phaseolus vulgaris), an ozone-sensitive crop, are widely grown in Uganda. Using modelled ozone flux, agricultural surveys, and a flux-effect relationship, this study estimates yield and production losses due to ozone for Ugandan beans in 2015. Analysis at this scale allows the use of localised data, and results can be presented at a sub-regional level. Soil nutrient stress, drought, flood risk, temperature and deprivation were also mapped to investigate where stresses may coincide. Average bean yield losses due to ozone were 17% and 14% (first and second growing season respectively), equating to 184 thousand tonnes production loss. However, for some sub-regions, losses were up to 27.5% and other crop stresses also coincided in these areas. This methodology could be applied widely, allowing estimates of ozone impact for countries lacking air quality and/or experimental data. As crop productivity is below its potential in many areas of the world, changing agricultural practices to mitigate against losses due to ozone could help to reduce the crop yield gap.

Continuous ultrasonic ozone coupling technology-assisted control of ceramic membrane fouling coupled enhanced multiphase mixing to treat dye wastewater and CFD flow field simulation

In this study, ozone catalysts (hydrogenation-modified red mud, HM-RM) successfully prepared by hydrogenation-modification of industrial hazardous solid waste red mud (RM) as a raw material in accordance with the viewpoint of treating waste with waste and using waste. Meanwhile, as for the common phenomenon of membrane fouling, uneven distribution of multiphase solid catalysts and ozone in liquids, the addition of ultrasound can not only disperse materials, but also play a role in online cleaning of ceramic membranes and catalysts. The optimum treatment conditions for Rhodamine B (RhB) solution with volume of 2 L and concentration of 40 mg/L were catalyst concentration of 0.4 mg/L, reaction temperature of 45 °C, ultrasonic time of 1 h, ultrasonic intensity of 600 W, removal rate of RhB was up to 90 %. In addition, the computational fluid dynamics (CFD) simulation method was used to investigate the fluid flow between the two gas-liquid phases and the effect of the negative pressure of the membrane pump on the fluid by the analysis of flow, pressure and ozone flux of the ceramic membrane(CM) reaction apparatus. The CFD simulation results showed that at the inlet gas-liquid flow rate of 3 m/s and the negative pressure of 20,000 Pa, the maximum flow rates of CM-1 were 3 m/s, 0.752 m/s for CM-2, and 0.228 m/s for CM-3, respectively. Vortices, which are beneficial to solid-liquid mixing and gas-liquid mass transfer, formed between the suction port CM-1 of CM-1 and the inlets of CM-2 and CM-3. This discovery is consistent with relevant experimental research results. Significantly higher concentrations of both •OH and dissolved ozone were observed in the US/HM-RM/O3 system compared to other systems, indicating the significant improvement in ozone utilization rate through the application of ultrasound. The superiority of the US/HM-RM/O3 device was demonstrated. The real dye effluent was tested under optimum operating conditions and the results showed that COD and TOC were reduced by 81.34 % and 60.23 % respectively after 180 min of treatment. The above research can provide technical support for the treatment of dye wastewater using Ultrasound-enhanced ozone oxidation ceramic membranes.

Modeling of tubular membrane contactors for ozonation of water reveals reduced bromate formation with static mixers

Bromate formation and insufficient micropollutant degradation are two major problems in wastewater ozonation. The conventional process using bubble columns has the drawback of an inhomogeneous ozone distribution, causing increased bromate formation. Membrane contactors are a promising alternative as they can dissolve ozone bubble-free. This work presents a simulation of a tubular membrane contactor in COMSOL Multiphysics that includes flow, mass transfer, ozone decay, and reactions of organic molecules and bromide with ozone and hydroxyl radicals. Gaseous ozone and water flow on the lumen and shell side of the membrane, respectively. Static mixers are placed in the water channel, coaxial between the membrane and housing. The simulations show a 75% increase in ozone flux through the membrane, a homogenized ozone distribution, and 13 times higher degradation of a medium-oxidizable micropollutant in the presence of additional static mixers. Furthermore, static mixers enable the use of a lower gaseous ozone concentration, resulting in 31% lower bromate formation at the same ozone exposure without affecting micropollutant degradation. Overall, we demonstrate that membrane contactors with static mixers can be used as a strategy to reduce bromate formation.

Combined electrolytic iron dissolution and ozonation process for arsenic removal from water

In some regions, underground water contains dissolved arsenic and this is a health risk for the population. In this work, arsenic was reduced to acceptable levels. Water from Zacatecas, Mexico, containing 1.58, 1.72 and 2.03 mg/L of As, Fe and Mn respectively, and pH 2.0, was treated with Fe from electrolytic dissolution, then with a mixture of ozone and air. The parameters considered during the treatment were agitation rate, ozone flux, pH, temperature, and dissolution time of iron. The concentration of As was reduced by co-precipitation with Fe from the electrolytic dissolution and by co-precipitation with Mn contained in the water when ozone was injected. The results indicated that the co-precipitation reactions depended on the mass transport. The ozone oxidizes the Mn in two steps (pH 2): firstly, the Mn (II) is oxidized to Mn (IV) and precipitated and secondly, the precipitated Mn (IV) is oxidized and dissolved as Mn (VII). Arsenic co-precipitated in the first Mn oxidation step, and then it turned into a solution together with the Mn at high flow of ozone. The residual concentrations of Fe, Mn and As in the water at pH 7 are 0.014, 0.07 and 0.00512 mg/L, respectively.

Ozone Fluxes Over a Boreal Lake Exhibit Enhanced Deposition at Nights

AbstractA few studies on ozone deposition over lake water are available and so far only one using the eddy covariance technique (Wesely et al., 1981, https://doi.org/10.1007/BF00122295). A 23‐day field campaign was held in August‐September 2012 at the Lake Kuivajärvi in Hyytiälä, Finland. The results showed a mean flux of −30 ± 1 ng m−2 s−1 and deposition velocity of 0.86 ± 0.05 mm s−1. Deposition velocity showed a weak diurnal cycle over the lake with elevated values during the nighttime. The daytime and nighttime portions of the data set differed statistically. Analysis showed that waterside convective mixing enhanced deposition and such conditions pre‐dominantly occurred during nighttime. We compared the measured deposition velocities with the dry deposition model of air‐sea exchange, adjusted for the chemical sinks relevant for the lake. We suggest that the buoyant mixing and unaccounted chemistry can be responsible for the difference between the model results and observations.

Oxidative abatement of saccharin by ozone and its influence on DBPs formation during postchlorination

As one of artificial sweeteners, saccharin (SAC) is widely used in food, personal care products and animal feed industry. SAC cannot be effectively metabolized by organisms and most of them are discharged into the water environment through multiple channels, leading to general detection in water source. In this study, the fate of SAC in the advanced ozone treatment of drinking water and subsequent chlorination disinfection was investigated. The results showed ozone could effectively degrade SAC and >99 % of 20 mg/L SAC could be removed under 7.10 mg/min ozone flow within 60 min. While, the mineralization was comparably low by 80 %, which indicated that ozone converted SAC into organic intermediate products. Therefore, SAC characterized with anti-chlorination property was changed to disinfection by-product precursor. Disinfection by-products including trichloromethane (TCM), dichloroacetic acid (DCAA), trichloroacetic acid (TCAA) and dichloroacetonitrile (DCAN) were found during subsequent chlorination. The yields of TCM, DCAA, TCAA and DCAN were found to be 8.1, 0.4, 1.2 and 0.1 μg/mg SAC, respectively, 3, 39, 41 and 178 times of those produced by direct chlorination. In addition, the increase of ozone flux promoted the formation of disinfection by-products. Meta-alkalescence was conducive to the formation of DCAA, TCAA and DCAN in pH range of 6 to 8. The presence of anions including Cl−, NO3− and CO32− reduced the formation of TCM, DCAA and DCAN.

Application of the Multi-Scale Infrastructure for Chemistry and Aerosols version 0 (MUSICAv0) for air quality research in Africa

Abstract. The Multi-Scale Infrastructure for Chemistry and Aerosols Version 0 (MUSICAv0) is a new community modeling infrastructure that enables the study of atmospheric composition and chemistry across all relevant scales. We develop a MUSICAv0 grid with Africa refinement (∼ 28 km × 28 km over Africa). We evaluate the MUSICAv0 simulation for 2017 with in situ observations and compare the model results to satellite products over Africa. A simulation from the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem), a regional model that is widely used in Africa studies, is also included in the analyses as a reference. Overall, the performance of MUSICAv0 is comparable to WRF-Chem. Both models underestimate carbon monoxide (CO) compared to in situ observations and satellite CO column retrievals from the Measurements of Pollution in the Troposphere (MOPITT) satellite instrument. MUSICAv0 tends to overestimate ozone (O3), likely due to overestimated stratosphere-to-troposphere flux of ozone. Both models significantly underestimate fine particulate matter (PM2.5) at two surface sites in East Africa. The MUSICAv0 simulation agrees better with aerosol optical depth (AOD) retrievals from the Moderate Resolution Imaging Spectroradiometer (MODIS) and tropospheric nitrogen dioxide (NO2) column retrievals from the Ozone Monitoring Instrument (OMI) than WRF-Chem. MUSICAv0 has a consistently lower tropospheric formaldehyde (HCHO) column than OMI retrievals. Based on model–satellite discrepancies between MUSICAv0 and WRF-Chem and MOPITT CO, MODIS AOD, and OMI tropospheric NO2, we find that future field campaign(s) and more in situ observations in the East African region (5∘ S–5∘ N, 30–45∘ E) could substantially improve the predictive skill of atmospheric chemistry model(s). This suggested focus region exhibits the largest model–in situ observation discrepancies, as well as targets for high population density, land cover variability, and anthropogenic pollution sources.

Chemical kinetics of near-surface ozone at a suburban location in India

The spatial gradient in near-surface ozone (O3) is controlled by its production, sink, and net transport (advection/convection and diffusive) in the atmosphere. In this work, we used continuous long-term measurements of O3, oxides of nitrogen (NOx = NO + NO2), and meteorological data in the suburban location of Shadnagar, India. Data analyses were performed to investigate the governing processes that control O3 variability on diurnal and seasonal time scales. The role of chemistry in O3 variability, including both formation and destruction processes, was investigated using known chemical kinetics and a radiative transfer model. The residual between observations and chemical estimation was further analyzed to examine the role of transport and unresolved processes/uncertainty in the dataset. The O3 residual was duly validated using model reanalysis data of O3 and meteorological parameters to further estimate the O3 transport. Our analyses show that the average net production and net transport of near-surface O3 are 3.18 and 0.87 ppbv/h, respectively, while horizontal advection is 0.01 ppbv/h in the daytime. The production of ozone was found to be dominant, indicating the influx of ozone at the site. Overall, our results highlight that spatio-temporal variability in near-surface ozone is strongly controlled by net production in Shadnagar and may be applicable in similar environments globally.

A single-point modeling approach for the intercomparison and evaluation of ozone dry deposition across chemical transport models (Activity 2 of AQMEII4).

A primary sink of air pollutants and their precursors is dry deposition. Dry deposition estimates differ across chemical transport models, yet an understanding of the model spread is incomplete. Here, we introduce Activity 2 of the Air Quality Model Evaluation International Initiative Phase 4 (AQMEII4). We examine 18 dry deposition schemes from regional and global chemical transport models as well as standalone models used for impact assessments or process understanding. We configure the schemes as single-point models at eight Northern Hemisphere locations with observed ozone fluxes. Single-point models are driven by a common set of site-specific meteorological and environmental conditions. Five of eight sites have at least 3 years and up to 12 years of ozone fluxes. The interquartile range across models in multiyear mean ozone deposition velocities ranges from a factor of 1.2 to 1.9 annually across sites and tends to be highest during winter compared with summer. No model is within 50 % of observed multiyear averages across all sites and seasons, but some models perform well for some sites and seasons. For the first time, we demonstrate how contributions from depositional pathways vary across models. Models can disagree with respect to relative contributions from the pathways, even when they predict similar deposition velocities, or agree with respect to the relative contributions but predict different deposition velocities. Both stomatal and nonstomatal uptake contribute to the large model spread across sites. Our findings are the beginning of results from AQMEII4 Activity 2, which brings scientists who model air quality and dry deposition together with scientists who measure ozone fluxes to evaluate and improve dry deposition schemes in the chemical transport models used for research, planning, and regulatory purposes.

Horizontal flux of ozone in the planetary boundary layer in Hong Kong using wind LiDAR measurements

While the crucial roles of ozone (O3) transport in the planetary boundary layer (PBL) have been acknowledged for some time, there is currently limited knowledge about this aspect primarily due to the limited availability of measurements to determine the characteristics of the PBL. In this study, measurements from a wind Light Detection and Ranging (LiDAR) system were taken to monitor vertical profile of wind pattern at an urban site in Hong Kong in September 2022, a period when the city was frequently impacted by tropical cyclones and experienced severe O3 pollution levels. The PBL height was identified based on the vertical profile of wind speed shear. By combining information on the PBL height, vertical wind profile, and O3 concentration, we performed a cross-sectional analysis to explore the total horizontal flux (THF) of O3 across the PBL in Hong Kong. Throughout the entire study month, the THF of O3 exhibited a predominant easterly component. However, during the O3 pollution episodes, the THF of O3 exhibited a predominant westerly component, indicating an increased regional transport from Greater Bay Area (GBA). The westerly winds between 240° and 300° contributed 61.2% to the total flux of O3 in the PBL during these episodes. In addition, clockwise veering winds were observed from the ground to the top of the PBL, which can be attributed to the Ekman spiral. As a result, during the O3 pollution episodes, the wind with the peak O3 flux shifted from westerly to northwesterly as the height increased in the PBL. The northwesterly THF of O3 between 290° and 300° reached its peak at 600 m above ground level during these episodes. These findings enhance our understanding of the 3D pollutant transports for both long-term averages and short-term pollution episodes in the GBA and Hong Kong.

Quantification of Ozone Pollution Transport Based on Four-dimensional Flux Method in Foshan, China

Quantifying the contribution of transport processes to air pollution events has been a prominent challenge and an important need in regional air pollution prevention and control. The WRF-Chem model was used to simulate a typical regional ozone (O3) pollution event in Foshan, and the four-dimensional flux method was applied to quantify the transport fluxes of ozone and its precursors from the surrounding areas to Foshan and to clarify the contributions of the direct transport of ozone and transport of precursors. The average ozone flux from the surrounding areas to Foshan was 120.3 t·h-1, the volatile organic compound (VOCs) flux was 30.2 t·h-1, and the corresponding ozone formation potential (OFP) was 114.8 t·h-1. By counting the transport fluxes of each ozone pollution event, it was found that the city with the largest ozone flux into Foshan during the pollution period was Guangzhou (contributed 44%); the city with the largest input VOCs flux was Zhaoqing (contributed 48%). The analysis of ozone generation potential due to transported VOCs emissions found that oxygenated volatile organic compounds (OVOCs) contributed the most to OFP, accounting for 47% of the "maximum input events." OVOCs and aromatic hydrocarbons such as formaldehyde, xylenes, aldehydes, acetone, and phenols were the top five species contributing to the OFP, contributing more than 50% of the total OFP, mainly from industrial solvent sources.

Theoretical Foundation of the Linear Relationship between the Midlatitude Eddy Heat Flux and Fall-to-Spring Polar Ozone Buildup

Abstract It has been demonstrated that there is a globally unified linear relationship between the interannual variations of the fall-to-spring polar ozone accumulation and the winter-mean poleward eddy heat flux on the 100 hPa pressure surface. The foundation of this relationship is investigated using time-slice experiments on a chemistry–climate model with two levels of ozone-depleting substances (ODSs). The features of the transport field are interpreted by decomposing the horizontal ozone flux caused by the residual circulation into contributing processes including the eddy heat flux with the aid of the transformed Eulerian-mean momentum equation followed by rearrangement of terms. The linear relationship between the interannual variations of the fall-to-spring ozone buildup integrated poleward and above a reference point Pref on a meridional plane and the poleward eddy heat flux during the corresponding period at Pref is realized for each hemisphere implying that the interhemispheric unification should be treated with caution. This relationship is interpreted using the fact that the interannual variation of poleward ozone transport in the upper stratosphere is captured well by the vertical convergence of the constituent-based Eliassen–Palm (EP) flux (), which is defined as the product of the constituent (ozone) mixing ratio and EP flux. The eddy momentum flux contributes to the meridional ozone transport in combination with the eddy heat flux in the form of the divergence of , although it is not responsible for realizing the linear relationship. The dependence of the linearity on the location of Pref and ODS levels is discussed.

Response of Total Column Ozone at High Latitudes to Sudden Stratospheric Warmings

The total column ozone (TCO) at northern high latitudes is increased over a course of 1–2 months after a major sudden stratospheric warming as a consequence of enhanced ozone eddy transport and diffusive ozone fluxes. We analyzed ground-based measurements of TCO from Oslo, Andøya and Ny Ålesund from 2000 to 2020. During this time interval, 15 major sudden stratospheric warmings (SSWs) occurred. The observed TCO variations are in a good agreement with those of ECMWF Reanalysis v5 (ERA5), showing that TCO from ERA5 is reliable, even during dynamically active periods. ERA5 has the advantage that it has no data gaps during the polar night. We found that TCO was increased by up to 190 DU after the SSW of February 2010, over one month. The composite analysis of the 15 SSWs provided the result that TCO is increased on average by about 50 DU over one month after the central date of the SSW.

High urban NOx triggers a substantial chemical downward flux of ozone.

Nitrogen oxides (NOx) play a central role in catalyzing tropospheric ozone formation. Nitrogen dioxide (NO2) has recently reemerged as a key target for air pollution control measures, and observational evidence points toward a limited understanding of ozone in high-NOx environments. A complete understanding of the mechanisms controlling the rapid atmospheric cycling between ozone (O3)-nitric oxide (NO)-NO2 in high-NOx regimes at the surface is therefore paramount but remains challenging because of competing dynamical and chemical effects. Here, we present long-term eddy covariance measurements of O3, NO, and NO2, over an urban area, that allow disentangling important physical and chemical processes. When generalized, our findings suggest that the depositional O3 flux near the surface in urban environments is negligible compared to the flux caused by chemical conversion of O3. This leads to an underestimation of the Leighton ratio and is a key process for modulating urban NO2 mixing ratios. As a consequence, primary NO2 emissions have been significantly overestimated.

Effect of corrections for water vapor sensitivity of coumarin targets and for density fluctuations (WPL) on O3 fluxes measured with the eddy covariance technique

Ozone vertical fluxes above land surfaces are commonly measured with the eddy covariance (EC) technique which requires non-conventional ozone fast analyzer mostly based on a chemiluminescence reaction of ozone with a reagent, either gaseous or solid. Currently, the most adopted reagent for this kind of O3 analyzers is a coumarin-47 solid dye absorbed on silica gel targets. However, ozone-induced chemiluminescence of coumarin-47 is enhanced by the presence of water vapor in the air sample. The aim of this paper is to evaluate the magnitude of the corrections to the ozone flux measurements due to coumarin-47 sensitivity to water vapor fluctuations, performed above a forest ecosystem from 2013 to 2020, and the combined effect with the WPL correction (Webb–Pearman–Leuning correction), another well-established correction for density fluctuations related to water vapor and sensible heat fluxes. Results confirm that water vapor sensitivity correction for the chemiluminescence reaction between coumarin-47 and ozone is quite small and negligible in most of the environmental conditions. On the contrary, WPL correction is almost one order of magnitude greater than the former correction. The combination of the two corrections results, on average, in a 6.6% reduction of the absolute value of the uncorrected ozone fluxes. Since the combined effect of the two corrections can be remarkable depending on the seasonal period of measurements, both corrections to the measured ozone fluxes are recommended, as well as the indication of their application in the published works.

The influence of personal care products on ozone-skin surface chemistry.

Personal care products are increasingly being marketed to protect skin from the potentially harmful effects of air pollution. Here, we experimentally measure ozone deposition rates to skin and the generation rates and yields of oxidized products from bare skin and skin coated with various lotion formulations. Lotions reduced the ozone flux to the skin surface by 12% to 25%; this may be due to dilution of reactive skin lipids with inert lotion compounds or by reducing ozone diffusivity within the resulting mixture. The yields of volatile squalene oxidation products were 25% to 70% lower for a commercial sunscreen and for a base lotion with an added polymer or with antioxidants. Lower yields are likely due to competitive reactions of ozone with lotion ingredients including some ingredients that are not intended to be ozone sinks. The dynamics of the emissions of squalene ozonation product 6 methyl-2-heptenone (6MHO) suggest that lotions can dramatically reduce the solubility of products in the skin film. While some lotions appear to reduce the rate of oxidation of squalene by ozone, this evidence does not yet demonstrate that the lotions reduce the impact of air pollution on skin health.

Interannual variability of ozone fluxes in a broadleaf deciduous forest in Italy

Multiannual measurements of ozone (O3) fluxes were performed from 2012 to 2020 in a broadleaf deciduous forest of the Po Valley, Italy. Fluxes were measured with the eddy covariance technique on a 41-m high tower, 15 m above the forest canopy. Different partition methodologies, based on concomitant water and carbon dioxide measurements, were compared for the calculation of the stomatal and non-stomatal components of the O3 fluxes. Total O3 fluxes revealed a marked interannual variability that was mainly driven by the stomatal activity in summer. Therefore, those factors that influence stomatal conductance were responsible for the flux variability, with soil water content being the main physiological driver. Despite the variability of the total O3 fluxes, the annual mean of the stomatal fraction was similar in the different years, around 42% on a 24-h basis, with an average summer value of 52% and a maximum around 60% during the summer daylight hours. The non-stomatal deposition was mainly driven by air humidity, surface wetness, and chemical sinks such as reaction of O3 with nitric oxide. Wind speed, turbulence intensity, and surface temperature showed a negative relationship with the non-stomatal fraction, but this was probably the result of a temporal misalignment between the daily cycles of non-stomatal conductance and those of temperature, turbulence, and wind speed. During the 7 years of measurements, the forest experienced a phytotoxic O3 dose of 10.55 mmolO3 m−2, as annual average, with an estimated reduction of the forest growth rate around 3% yr−1 according to the dose–effect relationships of the United Nations Economic Commission for Europe for broadleaf deciduous forests. Besides their implication for the O3 risk assessment for vegetation, these long-term measurements could be useful to test the deposition models used to correctly assess the O3 budget in troposphere on a multiannual time span.

The human oxidation field.

Hydroxyl (OH) radicals are highly reactive species that can oxidize most pollutant gases. In this study, high concentrations of OH radicals were found when people were exposed to ozone in a climate-controlled chamber. OH concentrations calculated by two methods using measurements of total OH reactivity, speciated alkenes, and oxidation products were consistent with those obtained from a chemically explicit model. Key to establishing this human-induced oxidation field is 6-methyl-5-hepten-2-one (6-MHO), which forms when ozone reacts with the skin-oil squalene and subsequently generates OH efficiently through gas-phase reaction with ozone. A dynamic model was used to show the spatial extent of the human-generated OH oxidation field and its dependency on ozone influx through ventilation. This finding has implications for the oxidation, lifetime, and perception of chemicals indoors and, ultimately, human health.