O3 Deposition Research Articles

Comparison of Surface Ozone Variability in Mountainous Forest Areas and Lowland Urban Areas in Southeast China

The ozone (O3) variations in southeast China are largely different between mountainous forest areas located inland, and lowland urban areas located near the coast. Here, we selected these two kinds of areas to compare their similarities and differences in surface O3 variability from diurnal to seasonal scales. Our results show that in comparison with the lowland urban areas (coastal areas), the mountainous forest areas (inland areas) are characterized with less human activates, lower precursor emissions, wetter and colder meteorological conditions, and denser vegetation covers. This can lead to lower chemical O3 production and higher O3 deposition rates in the inland areas. The annual mean of 8-h O3 maximum concentrations (MDA8 O3) in the inland areas are ~15 μg·m−3 (i.e. ~15%) lower than that in the coastal areas. The day-to-day variation in surface O3 in the two types of the areas is rather similar, with a correlation coefficient of 0.75 between them, suggesting similar influences on large scales, such as weather patterns, regional O3 transport, and background O3. Over 2016–2020, O3 concentrations in all the areas shows a trend of “rising and then falling”, with a peak in 2017 and 2018. Daily MDA8 O3 correlates with solar radiation most in the coastal areas, while in the inland areas, it is correlated with relative humidity most. Diurnally, during the morning, O3 concentrations in the inland areas increase faster than in the coastal areas in most seasons, mainly due to a faster increase in temperature and decrease in humidity. While in the evening, O3 concentrations decrease faster in the inland areas than in the coastal areas, mostly attributable to a higher titration effect in the inland areas. Seasonally, both areas share a double-peak variation in O3 concentrations, with two peaks in spring and autumn and two valleys in summer and winter. We found that the valley in summer is related to the summer Asian monsoon that induces large-scale convections bringing local O3 upward but blocking inflow of O3 downward, while the one in winter is due to low O3 production. The coastal areas experienced more exceedance days (~30 days per year) than inland areas (~5-10 days per year), with O3 sources largely from the northeast. Overall, the similarities and differences in O3 concentrations between inland and coastal areas in southeastern China are rather unique, reflecting the collective impact of geographic-related meteorology, O3 precursor emissions, and vegetation on surface O3 concentrations.

Production of oxygenated volatile organic compounds from the ozonolysis of coastal seawater

Abstract. Dry deposition of ozone (O3) to the ocean surface and the ozonolysis of organics in the sea surface microlayer (SSML) are potential sources of volatile organic compounds (VOCs) to the marine atmosphere. We use a gas chromatography system coupled to a Vocus proton-transfer-reaction time-of-flight mass spectrometer to determine the chemical composition and product yield of select VOCs formed from ozonolysis of coastal seawater collected from Scripps Pier in La Jolla, California. Laboratory-derived results are interpreted in the context of direct VOC vertical flux measurements made at Scripps Pier. The dominant products of laboratory ozonolysis experiments and the largest non-sulfur emission fluxes measured in the field correspond to Vocus CxHy+ and CxHyOz+ ions. Gas chromatography (GC) analysis suggests that C5–C11 oxygenated VOCs, primarily aldehydes, are the largest contributors to these ion signals. In the laboratory, using a flow reactor experiment, we determine a VOC yield of 0.43–0.62. In the field at Scripps Pier, we determine a maximum VOC yield of 0.04–0.06. Scaling the field and lab VOC yields for an average O3 deposition flux and an average VOC structure results in an emission source of 10.7 to 167 Tg C yr−1, competitive with the DMS source of approximately 20.3 Tg C yr−1. This study reveals that O3 reactivity to dissolved organic carbon can be a significant carbon source to the marine atmosphere and warrants further investigation into the speciated VOC composition from different seawater samples and the reactivities and secondary organic aerosol (SOA) yields of these molecules in marine-relevant, low NOx conditions.

Observation of ozone deposition flux and its contribution to stomatal uptake over a winter wheat field in eastern China

Ground-level ozone (O3) poses a significant threat to food security in China. Therefore, it is imperative to conduct a comprehensive scientific evaluation of the potential hazards posed by O3 to agricultural crops. This study continuously observed variation in meteorological factors, O3 concentration, O3 deposition rate and flux, and quantified the distribution characteristics of O3 deposition flux in stomatal and non-stomatal pathways. Results suggested that the O3 dry deposition rate and flux in winter wheat fields exhibited relatively stable variations at night but pronounced fluctuations during the day. Their mean values were 0.31 cm s−1 and -0.0044 μmol m−2·s−1, respectively, with peak values occurring at 08:30 and 14:00. The cumulative O3 total flux during the main growth season of winter wheat was 26.1 mmol m−2, with stomatal and non-stomatal fluxes accounting for 7.7 mmol m−2 and 18.4 mmol m−2, respectively. The proportions of total O3 flux in stomatal and non-stomatal channels were 29.5% and 70.5%, respectively, with daytime proportions being 39.7% and 60.3%, respectively. These findings provide crucial insights for future accurate assessments of crop yield loss due to O3 at the earth's surface.

An Analysis of CMAQ Gas Phase Dry Deposition over North America Through Grid-Scale and Land-Use Specific Diagnostics in the Context of AQMEII4.

The fourth phase of the Air Quality Model Evaluation International Initiative (AQMEII4) is conducting a diagnostic intercomparison and evaluation of deposition simulated by regional-scale air quality models over North America and Europe. In this study, we analyze annual AQMEII4 simulations performed with the Community Multiscale Air Quality Model (CMAQ) version 5.3.1 over North America. These simulations were configured with both the M3Dry and Surface Tiled Aerosol and Gas Exchange (STAGE) dry deposition schemes available in CMAQ. A comparison of observed and modeled concentrations and wet deposition fluxes shows that the AQMEII4 CMAQ simulations perform similarly to other contemporary regional-scale modeling studies. During summer, M3Dry has higher ozone (O3) deposition velocities (Vd) and lower mixing ratios than STAGE for much of the eastern U.S. while the reverse is the case over eastern Canada and along the West Coast. In contrast, during winter STAGE has higher O3 Vd and lower mixing ratios than M3Dry over most of the southern half of the modeling domain while the reverse is the case for much of the northern U.S. and southern Canada. Analysis of the diagnostic variables defined for the AQMEII4 project, i.e. grid-scale and land-use (LU) specific effective conductances and deposition fluxes for the major dry deposition pathways, reveals generally higher summertime stomatal and wintertime cuticular grid-scale effective conductances for M3Dry and generally higher soil grid-scale effective conductances (for both vegetated and bare soil) for STAGE in both summer and winter. On a domain-wide basis, the stomatal grid-scale effective conductances account for about half of the total O3 Vd during daytime hours in summer for both schemes. Employing LU-specific diagnostics, results show that daytime Vd varies by a factor of 2 between LU categories. Furthermore, M3Dry vs. STAGE differences are most pronounced for the stomatal and vegetated soil pathway for the forest LU categories, with M3Dry estimating larger effective conductances for the stomatal pathway and STAGE estimating larger effective conductances for the vegetated soil pathway for these LU categories. Annual domain total O3 deposition fluxes differ only slightly between M3Dry (74.4 Tg/year) and STAGE (76.2 Tg/yr), but pathway-specific fluxes to individual LU types can vary more substantially on both annual and seasonal scales which would affect estimates of O3 damages to sensitive vegetation. A comparison of two simulations differing only in their LU classification scheme shows that the differences in LU cause seasonal mean O3 mixing ratio differences on the order of 1 ppb across large portions of the domain, with the differences generally largest during summer and in areas characterized by the largest differences in the fractional coverages of the forest, planted/cultivated, and grassland LU categories. These differences are generally smaller than the M3Dry vs. STAGE differences outside the summer season but have a similar magnitude during summer. Results indicate that the deposition impacts of LU differences are caused both by differences in the fractional coverages and spatial distributions of different LU categories as well as the characterization of these categories through variables like surface roughness and vegetation fraction in look-up tables used in the land-surface model and deposition schemes. Overall, the analyses and results presented in this study illustrate how the diagnostic grid-scale and LU-specific dry deposition variables adopted for AQMEII4 can provide insights into similarities and differences between the CMAQ M3Dry and STAGE dry deposition schemes that affect simulated pollutant budgets and ecosystem impacts from atmospheric pollution.

Development of an ecophysiology module in the GEOS-Chem chemical transport model version 12.2.0 to represent biosphere–atmosphere fluxes relevant for ozone air quality

Abstract. Ground-level ozone (O3) is a major air pollutant that adversely affects human health and ecosystem productivity. Removal of tropospheric O3 by plant stomatal uptake can in turn cause damage to plant tissues with ramifications for ecosystem and crop health. In many atmospheric and land surface models, the functionality of stomata opening is represented by a bulk stomatal conductance, which is often semi-empirically parameterized and highly fitted to historical observations. A lack of mechanistic linkage to ecophysiological processes such as photosynthesis may render models inadequate to represent plant-mediated responses of atmospheric chemistry to long-term changes in CO2, climate, and short-lived air pollutant concentrations. A new ecophysiology module was thus developed to mechanistically simulate land−atmosphere exchange of important gas species in GEOS-Chem, a chemical transport model widely used in atmospheric chemistry studies. The implementation not only allows for dry deposition to be coupled with plant ecophysiology but also enables plant and crop productivity and functions to respond dynamically to atmospheric chemical changes. We conduct simulations to evaluate the effects of the ecophysiology module on simulated dry deposition velocity and concentration of surface O3 against an observation-derived dataset known as SynFlux. Our estimated stomatal conductance and dry deposition velocity of O3 are close to SynFlux with root-mean-squared errors (RMSEs) below 0.3 cm s−1 across different plant functional types (PFTs), despite an overall positive bias in surface O3 concentration (by up to 16 ppbv). Representing ecophysiology was found to reduce the simulated biases in deposition fluxes from the prior model but worsen the positive biases in simulated O3 concentrations. The increase in positive concentration biases is mostly attributable to the ecophysiology-based stomatal conductance being generally smaller (and closer to SynFlux values) than that estimated by the prior semi-empirical formulation, calling for further improvements in non-stomatal depositional and non-depositional processes relevant for O3 simulations. The estimated global O3 deposition flux is 864 Tg O3 yr−1 with GEOS-Chem, and the new module decreases this estimate by 92 Tg O3 yr−1. Estimated global gross primary production (GPP) without O3 damage is 119 Pg C yr−1. O3-induced reduction in GPP is 4.2 Pg C yr−1 (3.5 %). An elevated CO2 scenario (580 ppm) yields higher global GPP (+16.8 %) and lower global O3 depositional sink (−3.3 %). Global isoprene emission simulated with a photosynthesis-based scheme is 317.9 Tg C yr−1, which is 31.2 Tg C yr−1 (−8.9 %) less than that calculated using the MEGAN (Model of Emissions of Gases and Aerosols from Nature) emission algorithm. This new model development dynamically represents the two-way interactions between vegetation and air pollutants and thus provides a unique capability in evaluating vegetation-mediated processes and feedbacks that can shape atmospheric chemistry and air quality, as well as pollutant impacts on vegetation health, especially for any timescales shorter than the multidecadal timescale.

Low ozone dry deposition rates to sea ice during the MOSAiC field campaign: Implications for the Arctic boundary layer ozone budget

Dry deposition to the surface is one of the main removal pathways of tropospheric ozone (O3). We quantified for the first time the impact of O3 deposition to the Arctic sea ice on the planetary boundary layer (PBL) O3 concentration and budget using year-round flux and concentration observations from the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) campaign and simulations with a single-column atmospheric chemistry and meteorological model (SCM). Based on eddy-covariance O3 surface flux observations, we find a median surface resistance on the order of 20,000 s m−1, resulting in a dry deposition velocity of approximately 0.005 cm s−1. This surface resistance is up to an order of magnitude larger than traditionally used values in many atmospheric chemistry and transport models. The SCM is able to accurately represent the yearly cycle, with maxima above 40 ppb in the winter and minima around 15 ppb at the end of summer. However, the observed springtime ozone depletion events are not captured by the SCM. In winter, the modelled PBL O3 budget is governed by dry deposition at the surface mostly compensated by downward turbulent transport of O3 towards the surface. Advection, which is accounted for implicitly by nudging to reanalysis data, poses a substantial, mostly negative, contribution to the simulated PBL O3 budget in summer. During episodes with low wind speed (<5 m s−1) and shallow PBL (<50 m), the 7-day mean dry deposition removal rate can reach up to 1.0 ppb h−1. Our study highlights the importance of an accurate description of dry deposition to Arctic sea ice in models to quantify the current and future O3 sink in the Arctic, impacting the tropospheric O3 budget, which has been modified in the last century largely due to anthropogenic activities.

A Monolayer MoS2 FET with an EOT of 1.1nm Achieved by the Direct Formation of a High-κ Er2 O3 Insulator Through Thermal Evaporation.

Achieving the direct growth of an ultrathin gate insulator with high uniformity and high quality on monolayer transition metal dichalcogenides (TMDCs) remains a challenge due to the chemically inert surface of TMDCs. Although the main solution for this challenge is utilizing buffer layers before oxide is deposited on the atomic layer, this method drastically degrades the total capacitance of the gate stack. In this work, weconstructed a novel direct high-κ Er2 O3 deposition system based on thermal evaporation in a differential-pressure-type chamber. A uniform Er2 O3 layer with an equivalent oxide thickness of 1.1nm wasachieved as the gate insulator for top-gated MoS2 field-effect transistors (FETs). The top gate Er2 O3 insulator without the buffer layer on MoS2 exhibited a high dielectric constant that reached 18.0, which is comparable to that of bulk Er2 O3 and is the highest among thin insulators (< 10nm) on TMDCs to date. Furthermore, the Er2 O3 /MoS2 interface (Dit ≈ 6 × 1011 cm-2 eV-1 ) is confirmed to be clean and is comparable with that of the h-BN/MoS2 heterostructure. These results prove that high-quality dielectric properties with retained interface quality can be achieved by this novel deposition technique, facilitating the future development of 2D electronics.

Estimation of the historical dry deposition of air pollution indoors to the monumental paintings by Edvard Munch in the University Aula, in Oslo, Norway

The historical (1835–2020) deposition of major air pollutants (SO2, NOx, O3 and PM2.5) indoors, as represented by the monumental Edvard Munch paintings (c. 220 m2) installed in 1916 in the Oslo University Aula in Norway, were approximated from the outdoor air concentrations, indoor to outdoor concentration ratios and dry deposition velocities. The annual deposition of the pollutants to the paintings was found to have been 4–25 times lower than has been reported to buildings outdoors in the urban background in the centre of Oslo. It reflected the outdoor deposition but varied less, from 0.3 to 1.2 g m−2 a−1. The accumulated deposition since 1916, and then not considering the regularly performed cleaning of the paintings, was found to have been 43 ± 13 g m−2, and 110 ± 40 g m−2 in a similar situation since 1835. The ozone deposition, and the PM2.5 deposition before the 1960s, were a relatively larger part of the accumulated total indoor (to the paintings) than reported outdoor deposition. About 18 and 33 times more O3 than NOx and PM2.5 deposition was estimated to the paintings in 2020, as compared to the about similar reported outdoor dry deposition of O3 and NOx. The deposition of PM2.5 to the paintings was probably reduced with about 62% (50–80%) after installation of mechanical filtration in 1975 and was estimated to be 0.011 (± 0.006) g m−2 in 2020.Graphical

Multiferroic behavior of the functionalized surface of a flexible substrate by deposition of Bi2 O3 and Fe2 O3.

Thin films of bismuth and iron oxides were obtained by atomic layer deposition (ALD) on the surface of a flexible substrate poly(4,4'-oxydiphenylene-pyromellitimide) (Kapton) at a temperature of 250°C. The layer thickness was 50 nm. The samples were examined by secondary-ion mass spectrometry, and uniform distribution of elements in the film layer was observed. Surface morphology, electrical polarization, and mechanical properties were investigated by atomic force microscope, piezoelectric force microscopy, and force modulation microscopy. The values of current in the near-surface layer varied in the range of ±80 pA when a potential of 5V was applied. Chemical analysis was performed by X-ray photoelectron spectroscopy, where the formation of Bi2 O3 and Fe2 O3 phases, as well as intermediate phases in the Bi-Fe-O system, was observed. Magnetic measurements were carried out by a vibrating sample magnetometer that showed a ferromagnetic response. The low-temperature method of functionalization of the Kapton surface with bismuth and iron oxides will make it possible to adapt the Bi-Fe-O system to flexible electronics.

Historical dry deposition of air pollution in the urban background in Oslo, Norway, compared to Western European data

The historical (1835–2020) dry deposition of major air pollutants (SO2, NOx, O3 and PM2.5) in the urban background in Oslo, Norway, in a situation that could represent the building facades, was approximated from reported fuel combustion, emission factors, air concentrations since 1960, and dry deposition velocities. The annual accumulated dry deposition (and thus not considering the removal processes) of the pollutants, together, was found to have varied from about 2.3 to 27 g m−2, with the maximum in the 1960s caused by high SO2 emissions from the combustion of fuel oils, and with 1.6 kg m−2 having deposited over all the years. The deposition of PM2.5 was found to have dominated from 1835, have increased to a maximum in 1875 and then slowly decreased. The SO2 deposition decreased to a low value around 1990. The NOx deposition was also at its highest in the 1960s to about 1970, it became the largest from the 1980s, and then showed a clear decrease from about 2010. The O3 deposition was lower in the years of the maximum total and NOx deposition. The dry deposition of O3 and NOx were found to be about similar in 2020, more than two times that of PM2.5 and more than four times that of SO2. The trends of the NOx emissions were found to reflect the relative (1975) and absolute (∼2000) turning points of the environmental Kuznets curves (EKC) that has been suggested for Norway, whereas the trend of the SO2 emissions seems to have “shortcut” this development by the strong regulations in the emissions from 1970 that lead to near simultaneous relative and absolute reductions. The gradual decrease of the PM2.5 emissions from about 1945 seems to correspond with the decrease in combustion energy intensity in the economy as wood was substituted with more energy efficient fuels and then with the continued reduction in the wood burning.

Ozone Effects on Douro Vineyards under Climate Change

Tropospheric ozone (O3) levels in southern Europe have an increasing tendency, in close relation with the higher incidence of hot summers and heatwaves. Given that O3 is one of the most damaging pollutants for vegetation, known to affect productivity and quality of crops, it is necessary to develop more rigorous and consistent methods of risk assessment that consider climate change conditions. Studying the O3 deposition over the Douro Demarcated Region (DDR), which is one of the most productive wine areas in Portugal, and assessing its potential effects under a climate change scenario, was the purpose of this study. To that end, the chemical transport model CHIMERE, with a spatial resolution of 1 km2, fed by meteorological data from the WRF model, was applied for a recent past climate (2003 to 2005) and future mid-term (2049 and 2064) and long-term (2096 and 2097) scenarios. Simulations for future climate were performed considering: (i) only the climate change effect, and (ii) the effect of climate change together with future air pollutant emissions. The assessment of the potential damage in terms of wine productivity and quality (sugar content) was performed through analysis of O3 deposition and the application of concentration–response functions, based on AOT40 values. Modeling results show that a reduction in emission of O3 precursors can successfully decrease AOT40 levels in the DDR, but it is not enough to accomplish the European Commission target value for the protection of vegetation. If the emissions remain constant, the exposure–response functions indicate that, in the long-term, AOT40 levels could worsen wine productivity and quality.

Wheat Cultivar Growth, Biochemical, Physiological and Yield Attributes Response to Combined Exposure to Tropospheric Ozone, Particulate Matter Deposition and Ascorbic Acid Application.

In the present study wheat (Triticum aestivum) cultivar HD 2967 was exposed to ambient and elevated levels of O3 and PM deposition, with and without exogenous application of ascorbic acid (AA). Cultivar HD 2967 exposed to eight treatments in free air O3 enrichment facility and the assessed results showed that wheat cultivar, growth, biochemical, physiological and yield attributes were variably but adversely affected by combined exposure to O3 and PM deposition. PM deposition clogged stomata and enhanced leaf temperature. However, plants exposed to O3 and PM deposition and treated with AA exhibited less reduction in yield as compared to plants exposed to O3 and PM deposition without AA treatment. The decline in grain yield of HD 2967 due to combined exposure of O3 and PM deposition were in the range of 4%-17%. AA spray partially mitigated ozone and PM deposition adverse impact and enhanced wheat yield by 16%.

Enhancement of the anticoagulant capacity of polyvinyl chloride tubing for cardiopulmonary bypass circuit using aluminum oxide nanoscale coating applied through atomic layer deposition.

For cardiopulmonary bypass, the polyvinyl chloride (PVC) circuit which can initiate the activation of platelets and the coagulation cascade after blood cell contacting is the possible detrimental effect. Surface coating of the PVC tubing system can be an effective approach to enhance circuit's hemocompatibility. In this study, aluminum oxide (Al2 O3 ) thin films were deposited through thermal atomic layer deposition (T-ALD) or plasma-enhanced ALD (PE-ALD) on PVC samples, and the anticoagulation of the Al2 O3 -coated PVC samples was demonstrated. The results revealed that Al2 O3 deposition through ALD increased surface roughness, whereas T-ALD had a relative hydrophilicity compared with blank PVC and PE-ALD. Whole blood immersion tests showed that blood clots formed on blank PVC and that a large amount of red blood cells was found on PE-ALD substrates, whereas less blood cells were noted in T-ALD samples. Both T-ALD and PE-ALD Al2 O3 films did not cause activation of blood cells, as evidenced in CD3+ /CD4+ /CD8+ , CD61+ /CD62P+ , and CD45+ /CD42b+ populations. Analysis of serum coagulation factors showed that a lower amount of prothrombin was absorbed on T-ALD Al2 O3 samples than that on blank PVC. For albumin and fibrinogen immersion tests, immunostaining and scanning electron microscopy further revealed that a thin albumin layer was absorbed on T-ALD Al2 O3 substrates but not on PVC samples. This study revealed that deposition of Al2 O3 films by T-ALD can improve anticoagulation of the PVC tubing system.

Role of oceanic ozone deposition in explaining temporal variability in surface ozone at High Arctic sites

Abstract. Dry deposition is an important removal mechanism for tropospheric ozone (O3). Currently, O3 deposition to oceans in atmospheric chemistry and transport models (ACTMs) is generally represented using constant surface uptake resistances. This occurs despite the role of solubility, waterside turbulence and O3 reacting with ocean water reactants such as iodide resulting in substantial spatiotemporal variability in O3 deposition and concentrations in marine boundary layers. We hypothesize that O3 deposition to the Arctic Ocean, having a relatively low reactivity, is overestimated in current models with consequences for the tropospheric concentrations, lifetime and long-range transport of O3. We investigate the impact of the representation of oceanic O3 deposition to the simulated magnitude and spatiotemporal variability in Arctic surface O3. We have integrated the Coupled Ocean-Atmosphere Response Experiment Gas transfer algorithm (COAREG) into the mesoscale meteorology and atmospheric chemistry model Polar-WRF-Chem (WRF) which introduces a dependence of O3 deposition on physical and biogeochemical drivers of oceanic O3 deposition. Also, we reduced the O3 deposition to sea ice and snow. Here, we evaluate WRF and CAMS reanalysis data against hourly averaged surface O3 observations at 25 sites (latitudes &gt; 60∘ N). This is the first time such a coupled modeling system has been evaluated against hourly observations at pan-Arctic sites to study the sensitivity of the magnitude and temporal variability in Arctic surface O3 on the deposition scheme. We find that it is important to nudge WRF to the ECMWF ERA5 reanalysis data to ensure adequate meteorological conditions to evaluate surface O3. We show that the mechanistic representation of O3 deposition over oceans and reduced snow/ice deposition improves simulated Arctic O3 mixing ratios both in magnitude and temporal variability compared to the constant resistance approach. Using COAREG, O3 deposition velocities are in the order of 0.01 cm s−1 compared to ∼ 0.05 cm s−1 in the constant resistance approach. The simulated monthly mean spatial variability in the mechanistic approach (0.01 to 0.018 cm s−1) expresses the sensitivity to chemical enhancement with dissolved iodide, whereas the temporal variability (up to ±20 % around the mean) expresses mainly differences in waterside turbulent transport. The mean bias for six sites above 70∘ N reduced from −3.8 to 0.3 ppb with the revision to ocean and snow/ice deposition. Our study confirms that O3 deposition to high-latitude oceans and snow/ice is generally overestimated in ACTMs. We recommend that a mechanistic representation of oceanic O3 deposition is preferred in ACTMs to improve the modeled Arctic surface O3 concentrations in terms of magnitude and temporal variability.

Eddy covariance measurements of ozone flux above and below a southern subtropical forest canopy

While extensive eddy covariance (EC) measurements of ozone (O3) flux have been reported in American and European forests, such measurements in Asian forests are scarce. Here, we presented the first EC measurements of O3 flux at two levels (above and below the canopy) in a Chinese forest. Above the canopy, O3 always moved downward, with a maximum O3 flux intensity of −15 ~ −10 nmol m−2 s−1 occurring at 9:00–14:00 LT and a maximum O3 deposition velocity of 1.23 cm s−1 occurring at 9:00 LT; both of these values fell to nearly 0 at night. The O3 deposition flux and O3 deposition velocity below the canopy were both lower than those above the canopy. This discrepancy reached the maximum at 9:00–15:00 local time (LT), with the O3 deposition flux and O3 deposition velocity below the canopy being approximately 35 and 42% of those above the canopy, respectively. The O3 flux was well correlated with the CO2 flux and the latent heat flux, suggesting the important role of stomatal uptake in O3 deposition. The O3 deposition velocity increased with the increase in the air temperature, relative humidity, photosynthetically active radiation and friction velocity, but when these meteorological factors exceeded their optimum values, the increase in the O3 deposition velocity tended to be flat. These findings advanced our understanding of the interactions between forests and the atmosphere. This unique dataset is also of great significance for the validation of relevant models concerned with the various impacts of the rapid increase in global O3 concentrations.

Tailoring the Microporosity of Polymers of Intrinsic Microporosity for Advanced Gas Separation by Atomic Layer Deposition

Tailoring the microporosity of intrinsically microporous polymers at the atomic level is one of the biggest challenges in achieving high-performance polymeric gas separation membranes. In this study , for the first time, the Al 2 O 3 atomic layer deposition (ALD) technique was used to modify the microporosity of a typical polymer of intrinsic microporosity (PIM-1) at the atomic level. PIM-1 with six ALD cycles (PIM-1-Al 2 O 3 -6) exhibited simultaneous high thermal, mechanical, pure- and mixed-gas separation, and anti-aging properties. The O 2 /N 2 , H 2 /N 2 , and H 2 /CH 4 separation performances were adequate above the latest trade-off lines. PIM-1-Al 2 O 3 -6 showed CO 2 and O 2 permeabilities of 624 and 188 Barrer, combined with CO 2 /CH 4 and O 2 /N 2 selectivities of 56.2 and 8.8, respectively. This significantly enhanced performance was attributed to the strong size sieving effect induced by the Al 2 O 3 deposition.

Simultaneous Measurements of O3 and HCOOH Vertical Fluxes Indicate Rapid In‐Canopy Terpene Chemistry Enhances O3 Removal Over Mixed Temperate Forests

AbstractDry deposition, the second largest removal process of ozone (O3) in the troposphere, plays a role in controlling the natural variability of surface O3 concentrations. Terrestrial ecosystems remove O3 either through stomatal uptake or nonstomatal processes. In chemical transport models, nonstomatal pathways are roughly constrained and may not correctly capture total O3 loss. To address this, the first simultaneous eddy covariance measurements of O3 and formic acid (HCOOH), a tracer of in‐canopy oxidation of biogenic terpenes, were made in a mixed temperate forest in Northern Wisconsin. Daytime maximum O3 deposition velocities, vd (O3), ranged between 0.5 and 1.2 cm s−1. Comparison of observed vd (O3) with observationally constrained estimates of stomatal uptake and parameterized estimates of cuticular and soil uptake reveal a large (10%–90%) residual nonstomatal contribution to vd (O3). The residual downward flux of O3 was well correlated with measurements of HCOOH upward flux, suggesting unaccounted for in‐canopy gas‐phase chemistry.

Ozone deposition to a coastal sea: comparison of eddy covariance observations with reactive air–sea exchange models

Abstract. A fast-response (10 Hz) chemiluminescence detector for ozone (O3) was used to determine O3 fluxes using the eddy covariance technique at the Penlee Point Atmospheric Observatory (PPAO) on the south coast of the UK during April and May 2018. The median O3 flux was −0.132 mg m−2 h−1 (0.018 ppbv m s−1), corresponding to a deposition velocity of 0.037 cm s−1 (interquartile range 0.017–0.065 cm s−1) – similar to the higher values previously reported for open-ocean flux measurements but not as high as some other coastal results. We demonstrate that a typical single flux observation was above the 2σ limit of detection but had considerable uncertainty. The median 2σ uncertainty of deposition velocity was 0.031 cm s−1 for each 20 min period, which reduces with the square root of the sample size. Eddy covariance footprint analysis of the site indicates that the flux footprint was predominantly over water (&gt; 96 %), varying with atmospheric stability and, to a lesser extent, with the tide. At very low wind speeds when the atmosphere was typically unstable, the observed ozone deposition velocity was elevated, most likely because the footprint contracted to include a greater land contribution in these conditions. At moderate to high wind speeds when atmospheric stability was near-neutral, the ozone deposition velocity increased with wind speed and showed a linear dependence with friction velocity. This observed dependence on friction velocity (and therefore also wind speed) is consistent with the predictions from the one-layer model of Fairall et al. (2007), which parameterises the oceanic deposition of ozone from the fundamental conservation equation, accounting for both ocean turbulence and near-surface chemical destruction, while assuming that chemical O3 destruction by iodide is distributed over depth. In contrast to our observations, the deposition velocity predicted by the recently developed two-layer model of Luhar et al. (2018) (which considers iodide reactivity in both layers but with molecular diffusivity dominating over turbulent diffusivity in the first layer) shows no major dependence of deposition velocity on wind speed and underestimates the measured deposition velocities. These results call for further investigation into the mechanisms and control of oceanic O3 deposition.

A cavity-enhanced ultraviolet absorption instrument for high-precision, fast-time-response ozone measurements

Abstract. The NASA Rapid Ozone Experiment (ROZE) is a broadband cavity-enhanced UV (ultraviolet) absorption instrument for the detection of in situ ozone (O3). ROZE uses an incoherent LED (light-emitting diode) light source coupled to a high-finesse optical cavity to achieve an effective pathlength of ∼ 104 m. Due to its high sensitivity and small optical cell volume, ROZE demonstrates a 1σ precision of 80 pptv (parts per trillion by volume) in 0.1 s and 31 pptv in a 1 s integration time, as well as an e-fold time response of 50 ms. ROZE can be operated in a range of field environments, including low- and high-altitude research aircraft, and is particularly suited to O3 vertical-flux measurements using the eddy covariance technique. ROZE was successfully integrated aboard the NASA DC-8 aircraft during July–September 2019 and validated against a well-established chemiluminescence measurement of O3. A flight within the marine boundary layer also demonstrated flux measurement capabilities, and we observed a mean O3 deposition velocity of 0.029 ± 0.005 cm s−1 to the ocean surface. The performance characteristics detailed below make ROZE a robust, versatile instrument for field measurements of O3.

Discrepancies between MICS-Asia III simulation and observation for surface ozone in the marine atmosphere over the northwestern Pacific Asian Rim region

Abstract. In order to identify the causes of overestimate of the surface-level O3 mixing ratio simulated by three regional chemical-transport models, NAQPMS v.3 (abbreviated as NAQM in this paper), CMAQ v.5.0.2, and CMAQ v.4.7.1, compared to the EANET observational data at a marine remote site at Oki in July 2010, analyses of hourly O3 mixing ratios and net ozone production were made in the context of MICS-Asia III. In addition to Oki, model-simulated and observational data for two other EANET marine sites, Hedo and Ogasawara, were also examined. Three factors, i.e., long-range transport from the continent, in situ photochemical formation, and dry deposition of O3 on seawater, have been identified as contributing to the overestimate by these regional models at Oki. The calculated O3 mixing ratios during long-range transport from the continent were much higher for all three models than those of the observation. In situ photochemical formation, demonstrated by a distinct diurnal variation which was not discerned in the observational data, was seen in the simulated data of all three models and ascribed to the virtual transport of NOx from the southern urban areas of the main island of Japan. The overestimate of the O3 mixing ratio in the background oceanic air mass has been discussed referring to dry deposition velocity (Vd) of O3 over oceanic water. Sensitivity analysis of the dry deposition velocity to the concentration of O3 was made for Oki in July. An increase in Vd from 0.0005 to 0.001 cm s−1 used in the standard runs for CMAQ by a factor of 10 decreases the O3 mixing ratio by more than 20 ppbv on an event basis in certain periods of time and by ca. 4.9 ppbv as a monthly mean in July. The dry deposition velocity of O3 in Bohai Bay and the Yellow Sea has been assumed to be comparable to that of the open ocean in all three models, which could have resulted in the overestimate of O3 mixing ratios in this area and also in the long-range transport of O3 from the continent to Oki. A higher value of dry deposition velocity in this marine area is expected considering the higher content of organics in the surface sea layer brought by rivers and atmospheric wet deposition. Empirical measurements of the mixing ratios and dry deposition flux of O3 in this area are highly recommended, since they would affect the simulated mixing ratios in the downwind region in the Pacific Rim region.