Photochemical Model Research Articles

The transition from a nitrogen oxides-limited regime to a volatile organic compounds-limited regime in the petrochemical industrialized Lanzhou City, China

Heavy ozone (O3) pollution is often observed in the petrochemical industrial city of Lanzhou, located in the semi-arid and mountainous northwest China. The mountain-valley topography, special meteorological conditions, and high precursor emissions from the petrochemical industry across the city caused significantly increasing surface ozone concentrations in recent years. We investigated temporal distributions of O3 and its precursors and explored volatile organic compounds (VOCs) ‘composition and its contribution to O3 formation. The Ozone Isopleth Plotting Research (OZIPR) model was used to illustrate the ozone isoconcentration curves and assess the responses and sensitivity of O3 concentrations to its precursors. The results show that, in summer 2018, the VOCs/ nitrogen oxides (NOx) ratio defined in the ridgeline of the Empirical Kinetic Modeling Approach (EKMA) curve was about 13.8:1, indicating that ozone was formed in the NOx-limited regime, whereas in summer 2019, this ratio was 15:1, indicating that ozone was formed in the VOCs-limited regime, featuring a transition from a NOx-limited regime in summer 2018 to a VOCs-limited regime in summer 2019. We explored potential causes of this transition and attributed it to a large-scale instrument overhaul that resulted in significantly lower OH radical concentrations in summer 2019 and lower VOC emission after the overhaul. The modeling results using the Regional Atmospheric Chemical Mechanism version 2 (RACM2) photochemical box model show that the peak OH radical concentration in the summer of 2018 was much higher than that of 2019, reaching 12.38 × 106 molecules·cm−3. The result was confirmed by the Community Multiscale Air Quality (CMAQ) modeling system.

An evaluation of the photochemical air quality modeling using CMAQ in the industrial area of Quintero-Puchuncavi-Concon, Chile

The air pollution has impacted for years the population and the ecosystem in the industrial area located in Quintero, Puchuncavi, and Concon counties, the coastal area of Central Chile. In this study, we used the WRF-SMOKE-CMAQ model system to evaluate the photochemical modeling of PM10, PM2.5, and O3. The industrial and the residential wood combustion sources were the main contributors of particulate matter, sulfur dioxide and volatile organic compounds. The small diurnal temperature cycle, the high relative humidity and the low wind speed profiles exposed the meteorological condition of the coastal lows during the period of analysis. The daily average concentrations for PM10 and PM2.5 ranged from 24.03 to 50.10 μg/m3 and 15.60–21.95 μg/m3 for observed registries; meanwhile, the simulated results were in the range of 22.71–40.62 μg/m3 and 5.49–17.29 μg/m3, respectively. The omission of missing sources in the emission inventory and the default values in the boundary condition could be one of the reasons on the underprediction obtained. The best performance for O3 occurred in the Quintero and Sur stations, located near industrial sources with high NOx and VOC emissions. In the industrial complex, PM10 and PM2.5 concentrations were 10–30 μg/m3 lower when the industrial emissions were shut down and a negligible difference was observed when the residential wood combustion emissions were not considered. Future air quality modeling must be performed in the same region for other periods like the Summer season. Also, the emission inventory from all sources needs to be accurate with more accurate temporal profiles.

Maternal High-Fat Diet Alters the Characteristics of Astrocytes and Worsens the Outcome of Stroke in Rat Offspring, Which Improves After FGF21 Administration.

Background: Maternal high-fat diet (MHFD) has been shown to increase susceptibility to neurological disease in later offspring, but the underlying mechanism is not clear. Fibroblast growth factor 21 (FGF21) has been reported to have a neuroprotective effect in stroke, but its mechanism of action remains unknown. In this study, we investigated the mechanism of the effect of MHFD on stroke in offspring in adulthood and the mechanism by which FGF21 acts on stroke and restores neurological function. Methods: We performed transcriptome sequencing analysis on D21 neonatal rats. Bodyweight and blood indicators were recorded in the adult rats after MHFD. FGF21 was administered 7 h after photochemical modeling twice a day for three consecutive days. Results: We found numerous mRNA changes between the MHFD group and a normal maternal normal diet (MND) group at D21, including genes related to astrocyte and PI3K/Akt pathways. The body weight, blood glucose, and triglycerides of the MHFD offspring were higher, ischemic lesions were larger, the number of activated astrocytes was lower, and the neurological function score was worse than that of the MND group. After FGF21 administration, WB and qPCR analyses showed that astrocytes and the PI3K/Akt pathway were upregulated, while NF-κB and inflammatory cytokines expression were inhibited in stroke and peri-stroke regions. Conclusion: Taken together, we conclude that MHFD alters the characteristics of astrocytes and other transcriptome changes in their offspring, leading to a worse prognosis of stroke, while FGF21 plays a neuroprotective role by inhibiting NF-κB and inflammatory factors and activating the PI3K/Akt pathway and activating more astrocytes in the MND group than the MHFD group.

Generalized Oscillator Strengths for the Valence Shell Excitations in Carbon Tetrachloride Studied by Fast Electron Impact.

A joint experimental and theoretical investigation of the valence shell excitations of carbon tetrachloride has been performed by fast electron scattering and time dependent density functional theory calculations. At a collision energy of 1.5 keV and an energy resolution of about 70 meV, the dipole-forbidden transition of a1σ* ← 2t1 has been clearly observed at large momentum transfers, and its excitation energy of 6.15 eV and line width of 0.72 eV have been determined. Two new features are also recognized at 9.97 and 10.26 eV. The generalized oscillator strengths of the excited states at 5-11.3 eV have been determined from the measured spectra. The calculated generalized oscillator strength of the a1σ* ← 2t1 transition with the vibronic effect shows better agreement with the experiment, and the vibronic effect also accounts for its nonzero intensity at zero squared momentum transfer. The optical oscillator strengths of the valence shell excitations have also been obtained by extrapolating the generalized oscillator strengths to the limit of zero squared momentum transfer. The integral cross sections have been systematically determined from the threshold to 5000 eV by means of the BE-scaling method. The present oscillator strengths and cross sections provide the fundamental data of carbon tetrachloride and have important applications in photochemical modeling for atmospheric physics.

Investigating the Understanding of Oxidation Chemistry Using 20 Years of Airborne OH and HO2 Observations

AbstractHydroxyl (OH) and hydroperoxyl (HO2) strongly influence the atmosphere's oxidation of gases emitted from Earth's surface and the formation and aging of aerosol particles. Thus, understanding OH and HO2 chemistry is essential for examining the impact of human activity on future atmospheric composition and climate. Using the OH and HO2 data set collected with the Penn State Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) during nine aircraft missions over the past 20 years, we compare observed OH and HO2 to that modeled using the same near‐explicit photochemical box model. In general, the agreement is well within the combined uncertainties of the observations and models, even when the model is constrained only with a common data set of simultaneous measurements. However, in environments such as cities, forests, and pollution plumes, the model chemical mechanism and size of the data set of constraining measurements do matter. The model constrained by the full set of measurements better simulates OH loss and OH in these regions than the model constrained by the common set of measurements. In cleaner regions, the differences between observed and modeled OH and HO2 found in previous studies generally remain and do not appear to be systematic, indicating that the differences are driven by measurement issues for ATHOS and/or other instruments. Thus, these comparisons indicate that the oxidation chemistry in most of the free troposphere is understood to as well as current measurements can determine. The focus of future research needs to be on regions rich in volatile organic compounds, where observed‐to‐modeled differences are more persistent, and on improving measurement consistency.

Empirical Models of Ion Density Distribution in the Dayside Martian Ionosphere

AbstractWith the aid of the recent Neutral Gas and Ion Mass Spectrometer (NGIMS) measurements made onboard the Mars Atmosphere and Volatile Evolution spacecraft, we construct empirical models for the vertical density distributions of 12 species in the dayside Martian ionosphere over the altitude range of 150–450 km, from abundant species such as , , and O+ to trace species such as and OCOH+. Two different sets of formulism are proposed to parameterize the ion density distribution characterized either by a distinctive layer structure or by a near exponential decay above 150 km. Both the solar control and magnetic control of ion distribution are taken into account in our modelings. In general, our empirical models are in good agreement with the NGIMS measurements. The full set of parameters constrained by data‐model comparison is tabulated for reference. This allows the easy computation of any individual ion density profile for a unique combination of solar zenith angle, solar extreme ultraviolet flux, and ambient magnetic elevation, which in turn facilitates comparisons with photochemical model results. The empirical models reported in this study are an extension of previous empirical models constructed for the electron distribution in the dayside Martian ionosphere using both radar sounding and radio occultation data.

The Role of Temperature in Modifying the Risk of Ozone-Attributable Mortality under Future Changes in Climate: A Proof-of-Concept Analysis.

Air pollution risk assessments typically estimate ozone-attributable mortality counts using concentration-response (C-R) parameters from epidemiologic studies that treat temperature as a potential confounder. However, some recent epidemiologic studies have indicated that temperature can modify the relationship between short-term ozone exposure and mortality, which has potentially important implications when considering the impacts of climate change on public health. This proof-of-concept analysis quantifies counts of temperature-modified ozone-attributable mortality using temperature-stratified C-R parameters from a multicity study in which the pooled ozone-mortality effect coefficients change in concert with daily temperature. Meteorology downscaled from two global climate models is used with a photochemical transport model to simulate ozone concentrations over the 21st century using two emission inventories: one holding air pollutant emissions constant at 2011 levels and another accounting for reduced emissions through the year 2040. The late century climate models project increased summer season temperatures, which in turn yields larger total counts of ozone-attributable deaths in analyses using temperature-stratified C-R parameters compared to the traditional temperature confounder approach. This analysis reveals substantial heterogeneity in the magnitude and distribution of the temperature-stratified ozone-attributable mortality results, which is a function of regional variability in both the C-R relationship and the model-predicted temperature and ozone.

Three-dimensional distribution of ions and electrons in the lunar ionosphere originated from the photochemical reactions

ABSTRACT Using a fluid-based time-dependent numerical photochemical model, the three-dimensional distribution of ions and electrons in the lunar ionosphere, originated purely from photochemical reactions, is investigated. The photochemical model includes the production and recombination of 16 ions, namely CO$_2^+$, H2O+, H3O+, OH+, O$_2^+$, O+, Ar+, Ne+, He+, H+, H$_2^+$, CH$_3^+$, CH$_4^+$, and CH$_5^+$. The model also includes the interaction of solar wind with lunar plasma and calculates electron density profiles from the surface to 200 km altitude for the entire latitudes and longitudes. Model runs suggest that the surface electron density at the Moon could be as high as 1.2 × 105 cm−3 over the mid-latitudes if dynamical interaction between the solar wind and lunar plasma is not accounted for. The dominant ions, in this case, would be Ar+, Ne+, and He+. The absence of any intrinsic magnetic field however leads the ionosphere at the Moon to interact continuously with the solar wind and result in the removal of positive ions. This, in turn, leads to a negligible presence of plasma in the lunar ionosphere with a maximum electron density of ∼1600 cm−3. The electron density is maximum during the midnight and post-midnight periods at all the latitudes, and the maximum is centred around the polar region. Though solar wind acts as a strong removal agent, the electron density distribution is controlled by photochemistry, and ions are molecular in origin.

Assessment of summertime O3 formation and the O3-NOX-VOC sensitivity in Zhengzhou, China using an observation-based model

Zhengzhou, the provincial capital of Henan province in Central China and a major hub of the country's transportation network, has been suffering from severe summertime ozone (O3) pollution. Simultaneous field measurements of O3 and its precursors, including NOx, CO, HONO, and 106 volatile organic compounds (VOCs), were conducted at an urban site (the municipal environmental monitoring station, MEM) in Zhengzhou in July 2019. The Community Multiscale Air Quality (CMAQ) model, which incorporates the Master Chemical Mechanism (MCMv3.3.1), was modified to work as a 0-D observation-based photochemical box model to assess the sources and sinks of HOx radicals and O3, and the OH reactivity (KOH) and ozone formation potential (OFP) of major VOC groups. In addition, the O3-NOx-VOC sensitivity was evaluated using the relative incremental reactivity (RIR) and O3 formation isopleth techniques. The OH radicals were mainly generated from the propagation reaction of HO2 + NO (91–95%). The daily average mixing ratios of OH and HO2 radicals were significantly higher during high O3 days, reaching as high as 4.8 × 106 and 7.7 × 108 molecules cm−3, respectively. Photochemical O3 formation was mostly due to the conversion of NO to NO2 by HO2 radicals (52–54%), while the NO2 + OH reaction was the main contributor to O3 destruction (70– 76%). Alkenes and aromatics were the main anthropogenic VOC contributors to KOH and OFP. Contributions of biogenic VOCs became much more important on high O3 days, correlating with the increase in temperature and solar radiation. RIR analysis showed that the O3 formation was under the VOC-limited on low O3 days but was in the transition regime during the O3 pollution buildup and persisting days. These results are generally consistent with those based on the O3 formation isopleth. This paper provides important corroborative scientific evidence urgently needed by local governments to formulate O3 pollution control strategies.

Triple oxygen isotope constraints on atmospheric O2 and biological productivity during the mid-Proterozoic

Reconstructing the history of biological productivity and atmospheric oxygen partial pressure (pO2) is a fundamental goal of geobiology. Recently, the mass-independent fractionation of oxygen isotopes (O-MIF) has been used as a tool for estimating pO2 and productivity during the Proterozoic. O-MIF, reported as Δ'17O, is produced during the formation of ozone and destroyed by isotopic exchange with water by biological and chemical processes. Atmospheric O-MIF can be preserved in the geologic record when pyrite (FeS2) is oxidized during weathering, and the sulfur is redeposited as sulfate. Here, sedimentary sulfates from the ∼1.4-Ga Sibley Formation are reanalyzed using a detailed one-dimensional photochemical model that includes physical constraints on air-sea gas exchange. Previous analyses of these data concluded that pO2 at that time was <1% PAL (times the present atmospheric level). Our model shows that the upper limit on pO2 is essentially unconstrained by these data. Indeed, pO2 levels below 0.8% PAL are possible only if atmospheric methane was more abundant than today (so that pCO2 could have been lower) or if the Sibley O-MIF data were diluted by reprocessing before the sulfates were deposited. Our model also shows that, contrary to previous assertions, marine productivity cannot be reliably constrained by the O-MIF data because the exchange of molecular oxygen (O2) between the atmosphere and surface ocean is controlled more by air-sea gas transfer rates than by biological productivity. Improved estimates of pCO2 and/or improved proxies for Δ'17O of atmospheric O2 would allow tighter constraints to be placed on mid-Proterozoic pO2.

Contributions of Ammonia to High Concentrations of PM2.5 in an Urban Area

Atmospheric ammonia (NH3) plays a critical role in PM2.5 pollution. Data on atmospheric NH3 are scanty; thus, the role of NH3 in the formation of ammonium ions (NH4+) in various environments is understudied. Herein, we measured concentrations of NH3, PM2.5, and its water-soluble SO42−, NO3−, and NH4+ ions (SNA) at an urban site in Jeonju, South Korea from May 2019 to April 2020. During the measurement period, the average concentrations of NH3 and PM2.5 were 10.5 ± 4.8 ppb and 24.0 ± 12.8 μg/m3, respectively, and SNA amounted to 4.3 ± 3.1, 4.4 ± 4.9, and 1.6 ± 1.8 μg/m3, respectively. A three-dimensional photochemical model analysis revealed that a major portion of NH3, more than 88%, originated from Korea. The enhancement of the ammonium-to-total ratio of NH3, NHX (NHR = [NH4+]/[NH4+] + [NH3]) was observed up to ~0.61 during the increase of PM2.5 concentration (PM2.5 ≥ 25 μg/m3) under low temperature and high relative humidity conditions, particularly in winter. The PM2.5 and SNA concentrations increased exponentially as NHR increased, indicating that NH3 contributed significantly to SNA formation by gas-to-particle conversion. Our study provided experimental evidence that atmospheric NH3 in the urban area significantly contributed to SNA formation through gas-to-particle conversion during PM2.5 pollution episodes.

Atmospheric Effects on the Isotopic Composition of Ozone

The delta values of the isotope composition of atmospheric ozone is ~100‰ (referenced to atmospheric O2). Previous photochemical models, which considered the isotope fractionation processes from both formation and photolysis of ozone, predicted δ49O3 and δ50O3 values, in δ49O3 versus δ50O3 space, that are &gt;10‰ larger than the measurements. We propose that the difference between the model and observations could be explained either by the temperature variation, Chappuis band photolysis, or a combination of the two and examine them. The isotopic fractionation associated with ozone formation increases with temperature. Our model shows that a hypothetical reduction of ~20 K in the nominal temperature profile could reproduce the observations. However, this hypothesis is not consistent with temperatures obtained by in situ measurements and NCEP Reanalysis. Photolysis of O3 in the Chappuis band causes O3 to be isotopically depleted, which is supported by laboratory measurements for 18O18O18O but not by recent new laboratory data made at several wavelengths for 49O3 and 50O3. Cloud reflection can significantly enhance the photolysis rate and affect the spectral distribution of photons, which could influence the isotopic composition of ozone. Sensitivity studies that modify the isotopic composition of ozone by the above two mechanisms are presented. We conclude isotopic fractionation occurring in photolysis in the Chappuis band remains the most plausible solution to the model-observation discrepancy. Implications of our results for using the oxygen isotopic signature for constraining atmospheric chemical processes related to ozone, such as CO2, nitrate, and the hydroxyl radical, are discussed.

Overview of the Lake Michigan Ozone Study 2017.

The Lake Michigan Ozone Study 2017 (LMOS 2017) was a collaborative multiagency field study targeting ozone chemistry, meteorology, and air quality observations in the southern Lake Michigan area. The primary objective of LMOS 2017 was to provide measurements to improve air quality modeling of the complex meteorological and chemical environment in the region. LMOS 2017 science questions included spatiotemporal assessment of nitrogen oxides (NO x = NO + NO2) and volatile organic compounds (VOC) emission sources and their influence on ozone episodes; the role of lake breezes; contribution of new remote sensing tools such as GeoTASO, Pandora, and TEMPO to air quality management; and evaluation of photochemical grid models. The observing strategy included GeoTASO on board the NASA UC-12 aircraft capturing NO2 and formaldehyde columns, an in situ profiling aircraft, two ground-based coastal enhanced monitoring locations, continuous NO2 columns from coastal Pandora instruments, and an instrumented research vessel. Local photochemical ozone production was observed on 2 June, 9-12 June, and 14-16 June, providing insights on the processes relevant to state and federal air quality management. The LMOS 2017 aircraft mapped significant spatial and temporal variation of NO2 emissions as well as polluted layers with rapid ozone formation occurring in a shallow layer near the Lake Michigan surface. Meteorological characteristics of the lake breeze were observed in detail and measurements of ozone, NOx, nitric acid, hydrogen peroxide, VOC, oxygenated VOC (OVOC), and fine particulate matter (PM2.5) composition were conducted. This article summarizes the study design, directs readers to the campaign data repository, and presents a summary of findings.

A Comparative Study of Atmospheric Chemistry with VULCAN

Abstract We present an update of the open-source photochemical kinetics code VULCAN to include C–H–N–O–S networks and photochemistry. The additional new features are advection transport, condensation, various boundary conditions, and temperature-dependent UV cross sections. First, we validate our photochemical model for hot Jupiter atmospheres by performing an intercomparison of HD 189733b models between Moses et al., Venot et al., and VULCAN, to diagnose possible sources of discrepancy. Second, we set up a model of Jupiter extending from the deep troposphere to upper stratosphere to verify the kinetics for low temperature. Our model reproduces hydrocarbons consistent with observations, and the condensation scheme successfully predicts the locations of water and ammonia ice clouds. We show that vertical advection can regulate the local ammonia distribution in the deep atmosphere. Third, we validate the model for oxidizing atmospheres by simulating Earth and find agreement with observations. Last, VULCAN is applied to four representative cases of extrasolar giant planets: WASP-33b, HD 189733b, GJ 436b, and 51 Eridani b. We look into the effects of the C/O ratio and chemistry of titanium/vanadium species for WASP-33b, we revisit HD 189733b for the effects of sulfur and carbon condensation, the effects of internal heating and vertical mixing (K zz) are explored for GJ 436b, and we test updated planetary properties for 51 Eridani b with S8 condensates. We find that sulfur can couple to carbon or nitrogen and impact other species, such as hydrogen, methane, and ammonia. The observable features of the synthetic spectra and trends in the photochemical haze precursors are discussed for each case.

Multiphase Volatilization of Halogens at the Soil‐Atmosphere Interface on Mars

AbstractThe Martian critical zone, especially its soil‐atmosphere interface, may host an active halogen cycle affecting habitability, as inferred from halogen trends observed in situ at Gusev and Meridiani, along with oxychlorine species detected in situ. However, the sinks and sources of the Martian halogen cycle remain poorly constrained, especially for Br, including the broader geographic significance of halogen volatility in soils. Here, we statistically analyze Br, Cl, and S distribution and associated cations in the soils of Gale Crater and compare the results with soils of Gusev Crater and Meridiani Planum. We further place the overall in situ soil trends in the framework of terrestrial natural evaporative halides and Mars‐analog evaporative experiments. We observe three lines of evidence that support preferential volatilization of Br versus Cl and S in Martian soils: (a) Unlike Cl and S, Br abundance decreases from subsurface to surface. (b) Br and Cl abundances correlate strongly at the relatively dust‐free and freshly exposed surface of the active Bagnold dunes, but Br‐Cl correlations weaken and Br concentrations decrease in less mobile surface soil. (c) Laboratory experiments show preferential Br loss over Cl and S under ultraviolet (UV) irradiation, consistent with the observed Br loss relative to Cl in Martian soil samples. Overall, these findings generally suggest that soil serves as a source for volatilized halogens. Specifically, soil‐atmosphere multiphase reaction pathways constitute a crucial component missing from purely gas‐phase photochemical models of the halogen cycle.

Aeolian driven silicate comminution unlikely to be responsible for the rapid loss of martian methane

Seasonally varying levels of methane have been measured at parts per billion by volume levels in the lower Martian atmosphere. The source of this methane is not understood, but equally intriguing is its rapid loss, which is higher than the current chemical or photochemical decomposition models suggest. This implies an unknown but efficient sink mechanism. Earlier investigations reported the formation of Si• during the comminution of borosilicate glass and quartz that permitted the uptake of methane. This led to the speculation that an analogous aeolian driven comminution of Si-rich minerals on Mars could similarly sequestrate atmospheric methane. However, borosilicate glass is an artificial material and crystalline quartz is not common on the surface of Mars. To investigate whether this mechanism could take place on materials that were more representative of those on Mars, we comminuted a set of Mars analogue silicate rocks/minerals (basalt, obsidian, feldspar, pyroxene, zeolite, opal) in the presence of 13C-labeled methane. Solid-state Nuclear Magnetic Resonance (NMR) analysis of borosilicate glass and quartz indicated silicon carbide bond formation and this observation was supported by attenuated total reflectance-Fourier transform infra-red spectroscopy and X-ray photoelectron spectroscopy. However, silicon carbide bonds and methane sequestration were not detected in our set of Mars analogue samples. We hypothesise that electron donation by redox-active elements within the analogue materials, such as Fe, may have suppressed Si-methyl bond formation during comminution. Aeolian driven Si radical formation appears unlikely to be responsible for the rapid loss of methane in the Martian atmosphere, and thus the methane sink mechanism(s) require further investigation.

Photochemistry of HCl in the martian atmosphere

The recent discovery of HCl in the martian atmosphere using the ExoMars Trace Gas Orbiter (Korablev et al., 2021, Sci. Adv. 7, eabe4386) during a global dust storm indicates a correlation between the HCl appearance and dust. Here this idea is studied using one-dimensional photochemical modeling on two summer midlatitude sites in the aphelion and perihelion seasons (LS = 70° at 40°N and LS = 250° at 40°S). Dissociation energies of chlorides lead to the conclusion that FeCl3 is the most active chloride that can form gaseous chlorine species in reactions with H and O, while NaCl is probably the most abundant chloride and may contribute to the production of HCl as well. Heterogeneous loss of the atmospheric chlorine is expected by Cl on FeCl2 and by HCl and HOCl on water ice. We have included five heterogeneous reactions that control HCl abundances, and probabilities of four of those are unknown and chosen to fit the observed HCl. The models involve 35 reactions of the standard CO2-H2O-NO chemistry and 38 reactions of chlorine chemistry that determine vertical profiles of nine chlorine species. Along with the five heterogeneous chlorine reactions, three reactions of heterogeneous loss of OH, HO2, and H2O2 on water ice are included in the models. Alternative mechanisms of the production of HCl in the martian atmosphere are related to electric discharges and not considered here because of the lack of observational evidences for those discharges. The background atmospheres at the chosen sites, including vertical profiles of temperature, density, H2O, and dust and water ice aerosol, are calculated using the Thermal Emission Spectrometer database. The calculated abundances of O3, H2O2, and the O2 dayglow at 1.27 μm agree with observations and other models. The predicted HCl at perihelion varies from 2 ppb at the surface to 10 ppb above 55 km, in agreement with the observed 0.5–5 ppb at 5–35 km. The model cannot reproduce the observed cutoff in HCl above 35 km. The lifetime of HCl is 70 days at perihelion, close to some estimates based on the observations. The abundance of HCl in aphelion is ≈1.5 ppt at equilibrium and 60 ppt if the HCl lifetime is constant. The effects of HCl chemistry on major photochemical products are low on Mars. Photolysis of the high-altitude water vapor near perihelion facilitates production of H and hence HCl, and this explains the observed correlation between H2O and HCl.

Inferring Shallow Surfaces on Sub-Neptune Exoplanets with JWST

Abstract Planets smaller than Neptune and larger than Earth make up the majority of the discovered exoplanets. Those with H2-rich atmospheres are prime targets for atmospheric characterization. The transition between the two main classes, super-Earths and sub-Neptunes, is not clearly understood as the rocky surface is likely not accessible to observations. Tracking several trace gases (specifically the loss of ammonia (NH3) and hydrogen cyanide (HCN)) has been proposed as a proxy for the presence of a shallow surface. In this work, we revisit the proposed mechanism of nitrogen conversion in detail and find its timescale on the order of a million years. NH3 exhibits dual paths converting to N2 or HCN, depending on the UV radiation of the star and the stage of the system. In addition, methanol (CH3OH) is identified as a robust and complementary proxy for a shallow surface. We follow the fiducial example of K2-18b with a 2D photochemical model on an equatorial plane. We find a fairly uniform composition distribution below 0.1 mbar controlled by the dayside, as a result of slow chemical evolution. NH3 and CH3OH are concluded to be the most unambiguous proxies to infer surfaces on sub-Neptunes in the era of the James Webb Space Telescope.

Mimicking atmospheric photochemical modeling with a deep neural network

Fast and accurate prediction of ambient ozone (O3) formed from atmospheric photochemical processes is crucial for designing effective O3 pollution control strategies in the context of climate change. The chemical transport model (CTM) is the fundamental tool for O3 prediction and policy design, however, existing CTM-based approaches are computationally expensive, and resource burdens limit their usage and effectiveness in air quality management. Here we proposed a novel method (noted as DeepCTM) that using deep learning to mimic CTM simulations to improve the computational efficiency of photochemical modeling. The well-trained DeepCTM successfully reproduces CTM-simulated O3 concentration using input features of precursor emissions, meteorological factors, and initial conditions. The advantage of the DeepCTM is its high efficiency in identifying the dominant contributors to O3 formation and quantifying the O3 response to variations in emissions and meteorology. The emission-meteorology-concentration linkages implied by the DeepCTM are consistent with known mechanisms of atmospheric chemistry, indicating that the DeepCTM is also scientifically reasonable. The DeepCTM application in China suggests that O3 concentrations are strongly influenced by the initialized O3 concentration, as well as emission and meteorological factors during daytime when O3 is formed photochemically. The variation of meteorological factors such as short-wave radiation can also significantly modulate the O3 chemistry. The DeepCTM developed in this study exhibits great potential for efficiently representing the complex atmospheric system and can provide policymakers with urgently needed information for designing effective control strategies to mitigate O3 pollution.

Role of Antioxidant Moieties in the Quenching of a Purine Radical by Dissolved Organic Matter.

Dissolved organic matter (DOM) has been known to inhibit the degradation of trace organic contaminants (TrOCs) in advanced oxidation processes but quantitative understanding is lacking. Adenine (ADN) was selected as a model TrOC due to the wide occurrence of purine groups in TrOCs and the well-documented transient spectra of its intermediate radicals. ADN degradation in the presence of DOM during UV/peroxydisulfate treatment was quantified using steady-state photochemical experiments, time-resolved spectroscopy, and kinetic modeling. The inhibitory effects of DOM were found to include competing for photons, scavenging SO4•- and HO•, and also converting intermediate ADN radicals (ADN(-H)•) back into ADN. Half of the ADN(-H)• were reduced back to ADN in the presence of about 0.2 mgC L-1 of DOM. The quenching rate constants of ADN(-H)• by the 10 tested DOM isolates were in the range of (0.39-1.18) × 107 MC-1 s-1. They showed a positive linear relationship with the total antioxidant capacity of DOM. The laser flash photolysis results of the low-molecular-weight analogues of redox-active moieties further supported the dominant role of antioxidant moieties in DOM in the quenching of ADN(-H)•. The diverse roles of DOM should be considered in predicting the abatement of TrOCs in advanced oxidation processes.