Photochemical Model Research Articles

Distribution characteristics and photochemical effects of isoprene in a coastal city of southeast China

As forest coverage and urban greening increase in China, the impact of biogenic volatile organic compounds (BVOCs) on urban atmospheric environment cannot be neglected. As one of the most abundant and reactive BVOCs globally, isoprene plays a crucial role in atmospheric radical chemistry. However, the reports on quantifying the impact of isoprene on atmospheric photochemistry remain scarce. This study selected Xiamen, a typical coastal city in Fujian Province, as the research area. By employing field observation and Photochemical Box Model (PBM), the study investigated the distribution characteristics, pollution mechanisms, and impact on O3 of the atmospheric photochemical active species isoprene in coastal urban area. The study found that the average concentration of isoprene in summer was 4.7 times higher than that in autumn. Isoprene degradation primarily occurred through oxidation by OH· radicals, reaching 88 % and 86 % in summer and autumn, respectively. Based on scenario simulations using the PBM model, it was observed that isoprene photochemistry led to increased daytime concentrations of ROx radicals (summer: 24 %, autumn: 23 %), peroxyacetyl nitrate (PAN, 49 %, 44 %), and formaldehyde (HCHO, 37 %, 38 %). Additionally, isoprene photochemistry enhanced reaction rates of HO₂· + NO (summer: 21 %, autumn: 16 %) and RO₂· + NO (50 %, 52 %), ultimately resulting in a 19 % and 15 % increase in net O3 production rates in summer and autumn, respectively. This study provides scientific evidence for exploring the photochemical mechanisms and pollution control strategies of O3 in coastal atmospheric environments.

Methods for Quantifying Source-Specific Air Pollution Exposure to Serve Epidemiology, Risk Assessment, and Environmental Justice.

Identifying sources of air pollution exposure is crucial for addressing their health impacts and associated inequities. Researchers have developed modeling approaches to resolve source-specific exposure for application in exposure assessments, epidemiology, risk assessments, and environmental justice. We explore six source-specific air pollution exposure assessment approaches: Photochemical Grid Models (PGMs), Data-Driven Statistical Models, Dispersion Models, Reduced Complexity chemical transport Models (RCMs), Receptor Models, and Proximity Exposure Estimation Models. These models have been applied to estimate exposure from sources such as on-road vehicles, power plants, industrial sources, and wildfires. We categorize these models based on their approaches for assessing emissions and atmospheric processes (e.g., statistical or first principles), their exposure units (direct physical measures or indirect measures/scaled indices), and their temporal and spatial scales. While most of the studies we discuss are from the United States, the methodologies and models are applicable to other countries and regions. We recommend identifying the key physical processes that determine exposure from a given source and using a model that sufficiently accounts for these processes. For instance, PGMs use first principles parameterizations of atmospheric processes and provide source impacts exposure variability in concentration units, although approaches within PGMs for source attribution introduce uncertainties relative to the base model and are difficult to evaluate. Evaluation is important but difficult-since source-specific exposure is difficult to observe, the most direct evaluation methods involve comparisons with alternative models.

Stratospheric aerosols and C6H6 in Jupiter’s south polar region from JWST/MIRI observations

Context. The polar atmosphere of Jupiter is significantly affected by auroral activity, which can induce both thermal and chemical differences compared to the rest of the atmosphere. In particular, auroral activity enhances the production of various hydrocarbons, including benzene. Benzene could be a potential precursor to the formation of the stratospheric hazes. Aims. We investigated the spatial distribution of the benzene abundance across latitudes ranging from 50°S to 81°S and 17°S to 25°S. Additionally, we examined the chemical origin of polar aerosols and their latitudinal distribution. Methods. We employed James Webb Space Telescope (JWST) Mid InfraRed Instrument (MIRI) observations to measure the benzene abundance based on its emission at 674 cm−1. Additionally, we examined the spectral dependence of the aerosol opacity within the 680–760 and 1380–1500 cm−1 spectral ranges, and mapped their distribution from 80°S–50°S. Results. At latitudes lower than 60°S, benzene is found to be up to ten times more abundant compared to lower latitudes. This enhancement of C6H6 is well mixed longitudinally and not particularly concentrated inside the auroral oval. Photochemical models predict a decrease in the abundance as we approach the mid latitudes, but fail at polar latitudes as they do not include ion-neutral chemistry. Moreover, we find that the southern polar atmosphere is enriched with aerosols at ~10 mbar. The optical depth of the aerosols increases at latitudes poleward of ~60°S, similar to the enhancement of C6H6. These aerosols have spectral features similar to the aerosols of Titan and Saturn, and the mass loading is of ~1.2 ± 0.2 × 10−4 g cm−2. Finally, we quantified the impact of these aerosols on the retrieved temperature structure, causing a decrease in the temperature at pressure levels deeper than 10 mbar. Conclusions. We find that the auroral precipitation produces abundant stratospheric aerosols, which must play an important role in the chemistry and dynamics of the planet.

On the chemistry of the global warming potential of hydrogen

Hydrogen (H2) is considered a promising fuel to contribute to net-zero carbon emission goals. While hydrogen itself is not a greenhouse gas, leakage of hydrogen fuels causes indirect warming due to hydrogen’s influence on methane, tropospheric ozone, and stratospheric water vapor, with the methane term dominating the impact. Some studies consider a simple four-equation box model to explore the climate consequences of leakage from hydrogen fuel use relative to methane, while others have employed much more detailed global photochemical models. Here we use a comprehensive photochemical box model including 66 reactions to show and quantify how the analogous four-equation system is missing a critical OH feedback, leading it to overestimate the time-integrated methane response to a pulse of hydrogen by over 100%. We estimate a hydrogen global warming potential (GWP) relative to carbon dioxide of 28−11+18 on the 20-year time horizon and 10−4+7 on the 100-year time horizon based on the 66-reaction model and information from the literature. GWPs provide a measure of the relative global warming impact of emission of one gas compared to a selected reference gas per unit mass emitted. While CO2 is generally chosen for the reference, any gas can be used. We present the GWP of H2 using CH4 as the reference, as this choice cancels out some uncertainties that are common to both H2 and CH4. The GWP for H2 relative to CH4 from fossil fuel sources is 0.35−0.06+0.13 on time horizons beyond 15 years; put differently, we find that relative to an equivalent mass of emission of fossil CH4, hydrogen emission has a climate impact about three times smaller. These global warming potentials underscore that hydrogen leakage does contribute to climate change, emphasizing the importance of limiting both hydrogen and methane leakage if global net-zero greenhouse gas emissions are to be achieved by 2050.

Loss of endogenous Nox2-NADPH oxidase does not prevent age-induced platelet activation and arterial thrombosis in mice

BackgroundReactive oxygen species are known to contribute to platelet hyperactivation and thrombosis during aging; however, the mechanistic contribution of the specific oxidative pathway remains elusive. ObjectivesWe hypothesized that during aging, endogenous Nox2-NADPH oxidase contributes to platelet reactive oxygen species accumulation and that loss of Nox2 will protect from platelet activation and thrombosis. MethodsWe studied littermates of Nox2 knockout (Nox2-KO) and -wild-type (Nox2-WT) mice at young (3-4 months) and old (18-20 months) age. Within platelets, we examined the expression of subunits of NADPH oxidase and enzyme activity, oxidant levels, activation markers, aggregation, and secretion. We also assessed susceptibility to in vivo thrombosis in 2 experimental models. ResultsWhile aged Nox2-WT mice displayed increased mRNA levels for Nox2, aged Nox2-KO mice showed an increase in Nox4 mRNA. However, neither the protein levels of several subunits nor the activity of NADPH oxidase were found to be altered by age or genotype. Both aged Nox2-WT and aged Nox2-KO mice exhibited similar enhancement in levels of platelet oxidants, granule release, αIIbβ3 activation, annexin V binding, aggregation and secretion, and a greater susceptibility to platelet-induced pulmonary thrombosis compared with young mice. In a photochemical injury model, adoptive transfer of platelets from aged Nox2-WT or Nox2-KO mice to the aged host mice resulted in a similar time to develop occlusive thrombus in the carotid artery. These findings suggest that loss of endogenous Nox2 does not protect against age-related platelet activation and arterial thrombosis in mice. ConclusionWe conclude that Nox2 is not an essential mediator of prothrombotic effects associated with aging.

Source apportionment of Volatile Organic Compounds (VOCs) in the South Coast Air Basin (SoCAB) During RECAP-CA

Ozone (O3) concentrations in the South Coast Air Basin (SoCAB) surrounding Los Angeles remain at unhealthy levels despite multiple decades of control programs designed to reduce emissions of precursor Volatile Organic Compounds (VOCs). Here we report on comprehensive VOC measurements made at Redlands, which has the highest measured O3 concentrations in SoCAB, as part of the Re-Evaluating the Chemistry of Air Pollutants in California (RECAP-CA) field campaign (July–October 2021). Positive matrix factorization (PMF) analysis was applied to identify nine VOC factors. A photochemical chamber model initialized by field measurements was configured with a tagging technique to quantify the VOC factor contributions to O3 formation in Redlands. Biogenic VOCs (BVOCs) made the largest contribution (26.6%) to O3 formation, followed by traffic VOCs (21.2%), volatile chemical products (VCPs) (19%), and plant decomposition (14.9%). High O3 episodes were not driven by increased VOC emissions from any single source, but rather were associated with stagnation events that concentrated VOCs from all sources and high temperature days that enhanced O3 formation efficiency. This implies that VOC controls optimized to reduce O3 concentrations would look similar in both the NOx-limited and VOC-limited regimes that can occur at Redlands. These results suggest that control strategies that reduce VOC and NOx emissions from the on-road vehicle fleet, such as increasing electrification, may yield O3 reductions on days in both the NOx-limited and VOC-limited chemical regimes at Redlands.

Exploring the long-term variations and high concentration episodes of peroxyacetyl nitrate in Megacity Seoul

Over the past few years, peroxyacetyl nitrate (PAN) has drawn significant attention as a key indicator of photochemical pollution owing to its intimate relationship with ozone and associated health effects. This study presents measurements conducted at the Korea University campus in Seoul during the high-ozone seasons from 2018 to 2021. PAN concentration was measured using fast gas chromatography with luminol chemiluminescence detection (GC-LCD), alongside measurements of O3, volatile organic compounds (VOCs), NO, NO2, and meteorological variables, including boundary layer height (BLH).The mean concentrations of PAN and O3 over the years were 0.56 ppbv and 35 ppbv in 2018, 1.29 ppbv and 58 ppbv in 2019, 0.21 ppbv and 50 ppbv 2020, and 0.53 ppbv and 46 ppbv in 2021, respectively. The annual variation observed in Seoul is consistent with trends seen in major cities worldwide during the COVID19 pandemic, reflecting a substantial reduction in urban emissions. Notably, the mean concentration of NOx and VOCs decreased significantly by more than 50 % and 25%, respectively, from 2019 to 2021.At temperatures above 30 °C, PAN decomposition was accelerated, decoupling a consistent positive relationship between PAN and O3 in 2020 and 2021. The results of a 0-D photochemical model (F0AM) calculation demonstrated that PAN formation primarily stems from anthropogenic VOCs, particularly > C2 alkenes. Elevated PAN concentrations during nighttime were attributed to boundary layer expansion and upper-air entrainment. Instances where PAN concentrations surged to at least 3 ppbv or higher in 2019 were attributed to biomass burning impacted air, as evidenced by concurrent elevations in K+ and OC in PM2.5, and O3.This study underscores the complex interplay of factors influencing PAN and ozone enhancements under decreased precursor levels, with an emphasis on dynamic change in the boundary layer, and long-distance transport of non-fossil sources during agricultural burning seasons.

The chemical characteristics and sources of formaldehyde on O3 and non-O3 polluted days in Wuhan, central China

In August 2023, a detailed investigation of formaldehyde (HCHO) chemical characteristics on ozone (O3) polluted days and non-O3 polluted days in Wuhan was undertaken. The mean value of HCHO on O3 polluted days (3.02 ± 1.15 ppbv) was 122% higher than that on non-O3 polluted days (1.35 ± 0.41 ppbv). Utilizing Positive Matrix Factorization (PMF) model revealed secondary formation as the dominant HCHO source (58.3% on non-O3 polluted days and 66.2% on O3 polluted days). On O3 polluted days, the contribution of liquefied petroleum gas (LPG)/solvent usage and industrial emissions to HCHO were 13.7% and 8.2%, respectively, whereas on non-O3 polluted days, LPG/solvent use and diesel exhaust contributed 15.4% and 14.7%, respectively. The top ten species, with the highest Relative Incremental Reactivity (RIR) to HCHO, were mainly alkenes and aromatics, which remained consistent on both O3 and non-O3 polluted days. It is noteworthy that the RIR of isobutane to HCHO is significant in this study. Further reapportionment of secondary HCHO by a photochemical box model indicated that LPG/solvent usage (33.2%) contributed the most to HCHO on O3 polluted days, while diesel exhaust (31.9%) dominated on non-O3 polluted days. This research enhances understanding of HCHO in Wuhan, providing a theoretical basis for targeted pollution reduction and supporting efforts to improve air quality and public health.

Photodegradation potential of selected non-steroidal anti-inflammatory drugs in a middle-order Alpine river downstream of a wastewater treatment plant, during a year of enduring water scarcity

The year 2022 was characterised by significant water shortages and droughts in Italy, with the most pronounced impact observed in the North-Western regions, including Piemonte. In conditions of water scarcity, treated wastewater undergoes little dilution by natural flows and this can deeply affect the chemistry of water-poor rivers and streams. However, increased pollution by wastewater would be partially offset by fast photodegradation of pollutants in shallow water and by the longer time allowed to photochemical reactions if water flows more slowly. We assessed the latter phenomena in the Stura di Lanzo, a middle-order Alpine river tributary of the largest Italian river, the Po, and affected by a wastewater treatment plant (WWTP). In 2022, the concentration values of the photochemically significant parameters nitrate, nitrite, and DOC were usually higher downstream of the WWTP outlet, which could slightly favour indirect photodegradation reactions. Direct and indirect photodegradation was assessed for the non-steroidal anti-inflammatory drugs paracetamol, diclofenac, and naproxen, all undergoing rather fast photoreactions. Photochemistry model results show that the three compounds would undergo 10–40 % photodegradation in spring and summer along the stretch separating the wastewater outlet from the confluence of Stura into the Po. Photodegradation would continue in the latter, but other WWTPs might contribute additional pollution in the meanwhile. Albeit significant, photodegradation could only partially promote the elimination of the contaminants.

Electron Transfer Drives the Photosensitized Polymerization of Contrast Agents by Flavoprotein Tags for Correlative Microscopy.

Singlet oxygen generation has long been considered the key feature that allows genetically encoded fluorescent tags to produce polymeric contrast agents for electron microscopy. Optimization of the singlet oxygen sensitization quantum yield has not included the effects of electron-rich monomers on the sensitizer's photocycle. We report that at monomer concentrations employed for staining, quenching by electron transfer is the primary deactivation pathway for photoexcitations. A simple photochemical model including contributions from both processes reproduces the observed reaction rates and indicates that most of the product is driven by pathways that involve electron transfer with monomers─not by the sensitization of singlet oxygen. Realizing the importance of these competing reaction pathways offers a new paradigm to guide the development of genetically encodable tags and suggests opportunities to expand the materials scope and growth conditions for polymeric contrast agents (e.g., biocompatible monomers, O2 poor environments).

Wintertime ozone surges: The critical role of alkene ozonolysis

Ozone (O3) pollution is usually linked to warm weather and strong solar radiation, making it uncommon in cold winters. However, an unusual occurrence of four high O3 episode days (with maximum hourly concentrations exceeding 100 ppbv and peaking at 121 ppbv) was recorded in January 2018 in Lanzhou city, China. During these episodes, the average daytime concentration of total non-methane volatile organic compounds (TVOCs) reached 153.4 ± 19.0 ppbv, with alkenes—largely emitted from the local petrochemical industry—comprising 82.3 ± 13.1 ppbv. Here we show a photochemical box model coupled with a Master Chemical Mechanism to elucidate the mechanisms behind this unusual wintertime O3 pollution. We find that the typically low temperatures (−1.7 ± 1.3 °C) and weak solar radiation (263.6 ± 60.7 W m-2) of those winter episode days had a minimal effect on the reactivity of VOCs with OH radicals. Instead, the ozonolysis of alkenes generated Criegee intermediates, which rapidly decomposed into substantial ROx radicals (OH, HO2, and RO2) without sunlight. This radical production led to the oxidation of VOCs, with alkene ozonolysis ultimately contributing to 89.6 ± 8.7% of the O3 formation during these episodes. This mechanism did not activate at night due to the depletion of O3 by the NO titration effect. Furthermore, the findings indicate that a reduction of alkenes by 28.6% or NOx by 27.7% in the early afternoon could significantly mitigate wintertime O3 pollution. Overall, this study unravels the unique mechanism of alkene-induced winter O3 pollution and offers a reference for winter O3 reduction strategies in the petrochemical industrial regions.

Assimilating Satellite-Derived Snow Cover and Albedo Data to Improve 3-D Weather and Photochemical Models

During wintertime temperature inversion episodes, ozone in the Uinta Basin sometimes exceeds the standard of 70 ppb set by the US Environmental Protection Agency. Since ozone formation depends on sunlight, and less sunlight is available during winter, wintertime ozone can only form if snow cover and albedo are high. Researchers have encountered difficulties replicating high albedo values in 3-D weather and photochemical transport model simulations for winter episodes. In this study, a process to assimilate MODIS satellite data into WRF and CAMx models was developed, streamlined, and tested to demonstrate the impacts of data assimilation on the models’ performance. Improvements to the WRF simulation of surface albedo and snow cover were substantial. However, the impact of MODIS data assimilation on WRF performance for other meteorological quantities was minimal, and it had little impact on ozone concentrations in the CAMx photochemical transport model. The contrast between the data assimilation and reference cases was greater for a period with no new snow since albedo appears to decrease too rapidly in default WRF and CAMx configurations. Overall, the improvement from MODIS data assimilation had an observed enhancement in the spatial distribution and temporal evolution of surface characteristics on meteorological quantities and ozone production.

Seasonal Variation of Saturn's Lyα Brightness

We examine Saturn’s nonauroral (dayglow) emissions at Lyα observed by the Cassini/Ultraviolet Imaging Spectrograph (UVIS) instrument from 2003 until 2017, to constrain meridional and seasonal trends in the upper atmosphere. We separate viewing geometry effects from trends driven by atmospheric properties, by applying a multivariate regression to the observed emissions. The Lyα dayglow brightnesses depend on the incident solar flux, solar incidence angle, emission angle, and observed latitude. The emissions across latitudes and seasons show a strong dependence with solar incidence angle, typical of resonantly scattered solar flux and consistent with no internal source such as electroglow. We observe a bulge in Lyα brightnesses that shifts with the summer season from the southern to the northern hemisphere. We estimate atomic hydrogen optical depths above the methane homopause level for dayside disk observations (2004–2016) by comparing observed Lyα emissions to a radiative transfer model. We model emissions from resonantly scattered solar flux and a smaller but significant contribution by scattered photons from the interplanetary hydrogen (IPH) background. During the northern summer, inferred hydrogen optical depths steeply decrease with latitude toward the winter hemisphere from a northern hemisphere bulge, as predicted by a 2D seasonal photochemical model. The southern hemisphere mirrors this trend during its summer. However, inferred optical depths show substantially more temporal variation between 2004 and 2016 than predicted by the photochemical model. We benchmark our brightness values by comparing observed IPH Lyα emissions from Cassini/UVIS in 2006 with a model of the IPH emissions. Cassini/UVIS observations agree well with the modeled IPH background.

Chemical Mapping of Temperate Sub-Neptune Atmospheres: Constraining the Deep Interior H2O/H2 Ratio from the Atmospheric CO2/CH4 Ratio

Understanding the planetary envelope composition of sub-Neptune-type exoplanets is challenging due to the inherent degeneracy in their interior composition scenarios. Particularly, the planetary envelope’s H2O/H2 ratio, which can also be expressed as the O/H ratio, provides crucial insights into its original location relative to the ice line during planetary formation. Using self-consistent radiative transfer modeling and a rate-based automatic chemical network generator combined with 1D photochemical kinetic-transport atmospheric modeling, we investigate various atmospheric scenarios of temperate sub-Neptunes, ranging from H2-dominated to H2O-dominated atmospheres with equilibrium temperatures (T eq) of 250—400 K. This study includes examples such as K2-18 b (T eq = 255 K), LP 791-18 c (T eq = 324 K), and TOI-270 d (T eq = 354 K). Our models indicate that the atmospheric CO2/CH4 ratio can be used to infer the deep interior H2O/H2 ratio. Applying this method to recent JWST observations, our findings suggest that K2-18 b likely has an interior that is 50% highly enriched in water, exceeding the water content in a 100 × Z ⊙ scenario and suggesting a planetary formation mechanism involving substantial accretion of ices. In contrast, our model suggests that approximately 25% of TOI-270 d’s interior is composed of H2O, which aligns with the conventional metallicity framework with a metallicity higher than 100 × Z ⊙. Furthermore, our models identify carbonyl sulfide (OCS) and sulfur dioxide (SO2) as strong indicators for temperate sub-Neptunes with at least 10% of their interior composed of water. These results provide a method to delineate the internal composition and formation mechanisms of temperate sub-Neptunes (T eq < ∼ 500 K) via atmospheric characterization through transmission spectroscopy.

The Relationship of Surface Ozone Pollution with Meteorological Conditions in Determining Episode Periods

Jakarta, the capital city of Indonesia, is located in a tropical region with abundant sunlight and high temperatures year-round. Ozone and particulate matter (PM) are critical parameters causing unhealthy air pollution. Meteorological data were obtained from the NASA Power website. This study aims to explore the relationship between ozone formation and meteorological factors in Jakarta. Ozone air quality data were measured using the Backman model 950A ozone Analyzer, which detects concentrations as low as 0.05 ppm, with measurements taken every 40 seconds. From January to October 2023, ozone concentrations increased during the dry months of May to October, with the highest hourly value recorded at 263 μg/m³. During this period, average temperatures ranged from 27-29°C, rainfall was 0.3-5.6 mm, wind speeds were 3.14-4.64 m/s, wind direction was 92-171 degrees, and air humidity was 74-82%. Significant episodes were identified on (i) May 5-9, (ii) July 12-15, (iii) September 6-7, (iv) September 13-14, (v) September 21-22, and (vi) October 29-30, 2023. Daily, monthly, and seasonal ozone variations aligned with meteorological conditions, showing higher concentrations during the dry months. Further studies, including photochemical modeling, are required to identify dominant factors causing high ozone concentrations during these episodes. Understanding NOx or VOC emission sensitivities is crucial for effective ozone abatement strategies in Jakarta.

Constructing a Transient Ischemia Attack Model Utilizing Flexible Spatial Targeting Photothrombosis with Real-Time Blood Flow Imaging Feedback.

Transient ischemic attack (TIA) is an early warning sign of stroke and death, necessitating suitable animal models due to the associated clinical diagnostic challenges. In this study, we developed a TIA model using flexible spatially targeted photothrombosis combined with real-time blood flow imaging feedback. By modulating the excitation light using wavefront technology, we precisely created a square light spot (50 × 250 µm), targeted at the distal middle cerebral artery (dMCA). The use of laser speckle contrast imaging (LSCI) provided real-time feedback on the ischemia, while the excitation light was ceased upon reaching complete occlusion. Our results demonstrated that the photothrombus formed in the dMCA and spontaneously recanalized within 10 min (416.8 ± 96.4 s), with no sensorimotor deficits or infarction 24 h post-TIA. During the acute phase, ischemic spreading depression occurred in the ipsilateral dorsal cortex, leading to more severe ischemia and collateral circulation establishment synchronized with the onset of dMCA narrowing. Post-reperfusion, the thrombi were primarily in the sensorimotor and visual cortex, disappearing within 24 h. The blood flow changes in the dMCA were more indicative of cortical ischemic conditions than diameter changes. Our method successfully establishes a photochemical TIA model based on the dMCA, allowing for the dynamic observation and control of thrombus formation and recanalization and enabling real-time monitoring of the impacts on cerebral blood flow during the acute phase of TIA.

Controls of Atmospheric Methane on Early Earth and Inhabited Earth-like Terrestrial Exoplanets

Methane (CH4) is a primarily biogenic greenhouse gas. As such, it represents an essential biosignature to search for life on exoplanets. Atmospheric CH4 abundance on Earth-like inhabited exoplanets is likely controlled by marine biogenic production and atmospheric photochemical consumption. Such interactions have been previously examined for the case of the early Earth where primitive marine ecosystems supplied CH4 to the atmosphere, showing that the atmospheric CH4 response to biogenic CH4 flux variations is nonlinear, a critical property when assessing CH4 reliability as a biosignature. However, the contributions of atmospheric photochemistry, metabolic reactions, or solar irradiance to this nonlinear response are not well understood. Using an atmospheric photochemical model and a marine microbial ecosystem model, we show that the production of hydroxyl radicals from water vapor photodissociation is a critical factor controlling the atmospheric CH4 abundance. Consequently, atmospheric CH4 partial pressure (pCH4) on inhabited Earth-like exoplanets orbiting Sun-like stars (F-, G-, and K-type stars) would be controlled primarily by stellar irradiance. Specifically, irradiance at wavelengths of approximately 200–210 nm is a major controlling factor for atmospheric pCH4 when the carbon dioxide partial pressure is sufficiently high to absorb most stellar irradiance at 170–200 nm. Finally, we also demonstrated that inhabited exoplanets orbiting near the outer edge of K-type stars’ habitable zones are better suited for atmospheric pCH4 buildup. Such properties will provide valuable support for future detection of life signatures.

Effects of VOC emission reduction on atmospheric photochemistry and ozone concentrations during high-ozone episodes

We studied atmospheric volatile organic compounds (VOCs) characteristics and sources during fifteen high ozone (O3) episodes (daily 1-h maximum >100 ppbv and maximum 8-h average > 80 ppbv) in Nanjing, China, and used a photochemical box model to study the O3 formation sensitivity of VOCs, O3 photochemistry, radical budget, and reactivity for different emission reduction scenarios together with the base case ones. Overall, emission reduction from biogenic sources, followed by combustion sources, multiple sources, and solvent usage, had the major impacts on the O3 concentrations. According to photochemical box model simulations, isoprene was the most sensitive or influential VOC in the formation of O3, followed by ethylene, o-xylene, and cis-2-pentene. A 20.6 ± 11.7% concentration reduction of the sixteen most sensitive VOCs (SV16) for the production of O3 could bring the O3 concentration below the national standard level (daily 1-h maximum <100 ppbv). Besides, a 30% emission reduction from all the anthropogenic sources was more than enough to bring the O3 concentration below the national standard level. The total emission reduction of alkenes was always enough to bring the O3 concentration below the national standard level, which was not the case for aromatics under severe pollution conditions. The simulated OH reactivity analysis illustrates the importance of alkenes and aromatics, which account for about half of the total OH reactivity. The highest OH reactivity decreased due to the emission reduction for biogenic sources, followed by combustion and multiple sources. Alkenes played a major role in the OH, HO2, and RO2 radical's formation in the study area. The biggest drop in OH, HO2, and RO2 radical concentrations was noticed for biogenic emission reduction, followed by combustion and multiple sources. Due to the emission reduction from VOC sources, the highest O3 formation rates decreased for biogenic sources, followed by combustion and multiple sources. The acquired information is valuable to the scientific community and policymakers for formulating and implementing O3 pollution control strategies.

Ozone sensitivity regimes vary at different heights in the planetary boundary layer

The sensitivity of tropospheric ozone (O3) to its precursors volatile organic compounds (VOCs) and nitrogen oxides (NOX) determines the emission reduction strategy for O3 mitigation. Due to the lack of comprehensive vertical measurements of VOCs, the vertical distribution of O3 sensitivity regimes has not been well understood. O3 precursor sensitivity determined by ground-level measurements has been generally used to guide O3 control strategy. Here, to precisely diagnose O3 sensitivity regimes at different heights in the planetary boundary layer (PBL), we developed a vertical measurement system based on an unmanned aerial vehicle platform to conduct comprehensive vertical measurements of VOCs, NOX and other relevant parameters. Our results suggest that the O3 precursor sensitivity shifts from a VOC-limited regime at the ground to a NOX-limited regime at upper layers, indicating that the ground-level O3 sensitivity cannot represent the situation of the whole PBL. We also found that the state-of-the-art photochemical model tends to underestimate oxygenated VOCs at upper layers, resulting in overestimation of the degree of VOCs-limited regime. Therefore, thorough vertical measurements of VOCs to accurately diagnose O3 precursor sensitivity is in urgent need for the development of effective O3 control strategies.

The impact of multi-decadal changes in VOC speciation on urban ozone chemistry: a case study in Birmingham, United Kingdom

Abstract. Anthropogenic non-methane volatile organic compounds (VOCs) in the United Kingdom have been substantially reduced since 1990, which is, in part, attributed to controls on evaporative and vehicle tailpipe emissions. Over time, other sources with a different speciation (for example, alcohols from solvent use and industry processes) have grown in both relative importance and, in some cases, in absolute terms. The impact of this change in speciation and the resulting photochemical reactivities of VOCs are evaluated using a photochemical box model constrained by observational data during a summertime ozone event (Birmingham, UK) and apportionment of sources based on the UK National Atmospheric Emission Inventory (NAEI) data over the period 1990–2019. Despite road transport sources representing only 3.3 % of UK VOC emissions in 2019, road transport continued being the sector with the largest influence on the local O3 production rate (P(O3)). Under case study conditions, the 96 % reduction in road transport VOC emissions that has been achieved between 1990 and 2019 has likely reduced daytime P(O3) by ∼ 1.67 ppbv h−1. Further abatement of fuel fugitive emissions was modeled to have had less impact on P(O3) reduction than abatement of VOCs from industrial processes and solvent use. The long-term trend of increased emissions of ethanol and methanol has somewhat weakened the benefits of reducing road transport emissions, increasing P(O3) by ∼ 0.19 ppbv h−1 in the case study. Abatement of VOC emissions from multiple sources has been a notable technical and policy success in the UK, but some future benefits (from an ozone perspective) of the phase-out of internal combustion engine passenger cars may be offset if domestic and commercial solvent use of VOCs continue to increase.