Actinic Flux Research Articles

A comprehensive analysis of new particle formation across the northwest Atlantic: Analysis of ACTIVATE airborne data

New particle formation (NPF) is a critical source of particles and cloud condensation nuclei, yet there are scarce vertically-resolved measurements addressing NPF across different seasons in marine regions. This study leverages a multi-season set of airborne data from the NASA ACTIVATE mission between 2020 and 2022 to examine NPF characteristics over the northwest Atlantic ranging from the polluted U.S. East Coast to as far downwind (>1000 km) as Bermuda. Using the number concentration ratio above 3 and 10 nm (N3:N10) as a NPF indicator, we observe the highest ratios in the coldest months and comparable ratios over Bermuda relative to the U.S. East Coast. Within seasons, the highest and lowest ratios are found immediately above cloud tops and at the lowest possible flight altitudes (∼150 m above sea level), respectively. The ratio of (N3-N10)/N3 ranges from 0.16 to 0.29 depending on altitude, proximity to clouds, and season. The N3:N10 and (N3-N10)/N3 ratios increase with altitude up to as high as 9 km, with a case study showing favorable conditions around relatively thicker and precipitating cloud systems presumably due to high actinic fluxes and reduced aerosol surface area. Regression modeling reveals that increased N3:N10 is influenced most by reductions in temperature, relative humidity, and aerosol surface area. This work emphasizes the importance of both NPF in remote marine regions like Bermuda and vertical heterogeneity that exists in its contribution to aerosol and cloud condensation nuclei number budgets.

The Association Between Cloud Droplet Number over the Summer Southern Ocean and Air Mass History

AbstractThe cloud properties and governing processes in Southern Ocean marine boundary layer clouds have emerged as a central issue in understanding the Earth's climate sensitivity. While our understanding of Southern Ocean cloud feedbacks have evolved in the most recent climate model intercomparison, the background properties of simulated summertime clouds in the Southern Ocean are not consistent with measurements due to known biases in simulating cloud condensation nuclei concentrations. This paper presents several case studies collected during the Capricorn 2 and Marcus campaigns held aboard Australian research vessels in the Austral Summer of 2018. Combining the surface‐observed cases with MODIS data along forward and backward air mass trajectories, we demonstrate the evolution of cloud properties with time. These cases are consistent with multi‐year statistics showing that long trajectories of air masses over the Antarctic ice sheet are critical to creating high droplet number clouds in the high latitude summer Southern Ocean. We speculate that secondary aerosol production via the oxidation of biogenically derived aerosol precursor gasses over the high actinic flux region of the high latitude ice sheets is fundamental to maintaining relatively high droplet numbers in Southern Ocean clouds during Summer.

High Accuracy Photodissociation Rates in VULCAN with MCRT

Photochemical processing is a key influence on the chemical compositions of exoplanet atmospheres. We develop a 1D plane-parallel Monte Carlo radiative-transfer (MCRT) path length method to calculate actinic fluxes for photochemical modeling, which we couple to the VULCAN photochemical model. Due to the flexible nature of MCRT methods, this enables accurate calculation of photodissociation rates for complex multiple scattering scenarios encountered in exoplanet atmospheres such as high altitude haze layers.

An observation-constrained estimation of brown carbon aerosol direct radiative effects

Abstract. Brown carbon (BrC) is an organic carbon component with noticeable absorption in the ultraviolet and short visible wavelengths, which influences the global radiative balance. However, assessing BrC radiative effects remains a challenging task owing to the scarcity of direct BrC observations and the uncertainties regarding their chemical and optical properties. This study proposes an efficient method for estimating BrC radiative effects based on the available observational data. The light-absorbing properties of BrC obtained from aethalometer measurements and an optical separation method were combined with simulated BrC optical properties to determine mass concentrations. An optical closure study was conducted to constrain the total and other aerosol contents. Subsequently, we estimated the aerosol optical properties and concentrations. Such a state-of-the-art combination of measurements and numerical models provides primary variables for simulating radiative transfer to estimate BrC radiative effects. We used observations conducted over 4 months (from 1 July to 18 November 2021) in Nanjing (a megacity in east China) as an example. During the observational period, BrC absorption constituted 8.7 %–34.1 % of the total aerosol absorption at 370 nm. In the atmosphere, BrC plays a warming role, with its average instantaneous radiative forcing (RF) and standard deviation of 4.0 ± 2.3 W m−2 corresponding to 15 ± 4.2 % of the black carbon (BC) RF. At the surface, the BrC-induced actinic flux (AF) attenuation is comparable to that caused by BC, accounting for over 55 % of the BC effects in the UV range and almost 20 % in the visible range. The photosynthetically active radiation (PAR) attenuated by BrC is approximately 33.5 ± 9.4 % of that attenuated by BC. Furthermore, we quantified the influences of several BC and BrC microphysical and optical properties on their radiative effects. These findings provide valuable insights for understanding BrC radiative effects. Moreover, they highlight the importance of and necessity for improved observation and modeling of BrC properties.

Photodissociation of the CH2Br radical: A theoretical study.

Bromine atom (Br) reactions lead to ozone depletion in the troposphere and stratosphere. Photodegradation of bromocarbons is one of the main sources of bromine atoms in the atmosphere. Here, we use high-level abinitio methods, including spin-orbit effects, to study the photodissociation of the CH2Br radical. All possible fragmentation pathways, namely CH2Br + hν → CH2 + Br, HCBr + H, and CBr + H2, have been analyzed. Potential-energy curves of the ground and several excited electronic states along the corresponding dissociating bond distance of each pathway have been calculated. Considering the actinic fluxes of solar irradiation in the troposphere and in the stratosphere in the relevant range of frequencies, it is found that the first five excited states of CH2Br can be accessed from the ground state. Analysis of the potential curves shows that the pathways producing CH2 + Br and HCBr + H can proceed through a fast direct dissociation mechanism, while the pathway leading to CBr + H2 involves much slower dissociation mechanisms like internal conversion between electronic states, predissociation, or tunneling through exit barriers. The main implications are that the two faster channels are predicted to be dominant, and the slower pathway is expected to be less relevant. The tropospheric and stratospheric solar actinic fluxes also allow for further dissociation of the HCBr and CBr fragments, generating additional Br atoms, provided that they survive possible collisions with other atmospheric reagents. Finally, we discuss the possible effect of each of the three CH2Br dissociation pathways on the depletion of atmospheric ozone.

New particle formation in the tropical free troposphere during CAMP2Ex: statistics and impact of emission sources, convective activity, and synoptic conditions

Abstract. Nucleation in the free troposphere (FT) and subsequent growth of new particles represent a globally important source of cloud condensation nuclei (CCN). Whereas new particle formation (NPF) has been shown to occur frequently in the upper troposphere over tropical oceans, there have been few studies of NPF at lower altitudes. In addition, the impact of urban emissions and biomass burning on the NPF in tropical marine FT remains poorly understood. In this study, we examine NPF in the lower and mid-troposphere (3–8.5 km) over the tropical ocean and coastal region using airborne measurements during the recent Cloud, Aerosol and Monsoon Processes Philippines Experiment (CAMP2Ex). NPF was mostly observed above 5.5 km and coincided with elevated relative humidity (RH) and reduced condensation sink (CS), suggesting that NPF occurs in convective cloud outflow. The frequency of NPF increases with altitude, reaching ∼ 50 % above 8 km. An abrupt decrease in NPF frequency coincides with early monsoon transition and is attributed to increased CS resulting from reduced convective activity and more frequent transport of aged urban plumes. Surprisingly, a large fraction of NPF events in background air were observed in the early morning, and the NPF is likely made possible by very low CS despite low actinic flux. Convectively detrained biomass-burning plumes and fresh urban emissions enhance NPF as a result of elevated precursor concentrations and scavenging of pre-existing particles. In contrast, NPF is suppressed in aged urban plumes where the reactive precursors are mostly consumed, while CS remains relatively high. This study shows a strong impact of urban and biomass-burning emissions on the NPF in tropical marine FT. The results also illustrate the competing influences of different variables and interactions among anthropogenic emissions, convective clouds, and meteorology, which lead to NPF under a variety of conditions in tropical marine environments.

Study on the characteristics of actinic radiation and direct aerosol radiation effects in the Pearl River Delta region

Combined air pollution prevails in the Pearl River Delta (PRD) region in recent years; large amounts of aerosols have caused a significant attenuation of actinic radiation. Solar radiation is the driving energy for photochemical reactions and plays an important role in the ozone formation. In this study, characteristics of actinic radiation and atmospheric composition in the PRD region have been analyzed based on long-term observation. The radiation transfer model (SBDART) is used to quantitatively estimate the direct radiation effect and actinic radiation effect of aerosol. Results indicate that PM2.5 concentration and atmospheric extinction coefficient have shown a downward trend. Meanwhile, ozone and Single Scattering Albedo (SSA) have increased. The average value of SSA is 0.914 ± 0.041, attaining the highest level in spring, followed by autumn and summer, and the lowest is found in winter. A linear relationship between UVA/UVB of actinic radiation flux and solar shortwave radiation has been revealed. Through the conversion formula proposed in the article, conventional radiation data can be converted into actinic radiation flux and species photolysis rate. The actinic radiation and radiation attenuation caused by aerosols shows an overall downward trend at the surface. In the ultraviolet to visible wavelength range (280–670 nm), the annual average attenuation of aerosol direct radiation and actinic radiation is 61.6 ± 31.8 W/m2 and 120.1 ± 59.7 W/m2, respectively. The radiation attenuation caused by aerosols is the largest in spring, with little difference in summer, autumn and winter, which are 92.9 ± 42.1 W/m2, 53.7 ± 21.3 W/m2, 48.0 ± 13.7 W/m2 and 52.1 ± 15.8 W/m2, respectively. The attenuation of actinic radiation caused by aerosol is the largest in spring, followed by winter, and there is little difference between summer and autumn, which are 174.8 ± 78.4 W/m2, 111.1 ± 33.1 W/m2, 98.3 ± 38.4 W/m2 and 96.7 ± 26.9 W/m2, respectively. The direct radiation effect of aerosol and the actinic radiation effect have opposite trends with increasing height. Below the aerosol scale height, the larger SSA is corresponding with greater radiant flux, and it is opposite above the aerosol scale height. SSA has the same effect on the actinic radiant flux of the entire layer: The larger SSA is in accordance with greater actinic radiant flux.

Optical receiver characterizations and corrections for ground-based and airborne measurements of spectral actinic flux densities

Abstract. Solar actinic radiation in the ultraviolet and visible range (UV/VIS) perpetuates atmospheric photochemistry by inducing photolysis processes which form reactive radical species. Photolysis frequencies are rate constants that quantify the rates of photolysis reactions and therefore constitute important parameters for quantitative analyses. Photolysis frequencies are usually calculated from modelled or measured solar spectral actinic flux densities. Suitable measurement techniques are available, but measurement accuracy can suffer from non-ideal 2π or 4π solid-angle reception characteristics of the usually employed 2π optical receivers or receiver combinations. These imperfections, i.e. deviations from an angle-independent response, should be compensated for by corrections of the measured data. In this work, the relative angular sensitivities of four commonly used 2π quartz receivers were determined in the laboratory in a range 280–660 nm. Based on this information, the influence of the non-ideal responses on measured spectral actinic flux densities for ground-based and airborne applications was investigated for a wide range of atmospheric conditions. Spectral radiance distributions and contributions of direct, diffuse downward and diffuse upward spectral actinic flux densities were calculated with a radiative transfer model to derive the corrections. The intention was to determine the ranges of possible corrections under realistic measurement conditions and to derive simple parametrizations with reasonable uncertainties. For ground-based 2π measurements of downward spectral actinic flux densities, corrections typically range <10 % dependent on wavelength and solar zenith angle, with 2 %–8 % uncertainties covering all atmospheric conditions. Corrections for 4π airborne measurements were determined for the platforms Zeppelin NT (New Technology) and HALO (High Altitude and Long Range Research Aircraft) in altitude ranges 0.05–2 and 0.2–15 km, respectively. Total, downward and upward spectral actinic flux densities were treated separately. In addition to various atmospheric conditions, different ground albedos and small (<5∘) aircraft attitude variations were considered in the uncertainties, as well as aircraft headings with respect to the sun in the case of HALO. Corrections for total and downward spectral actinic flux densities again typically range <10 % dependent on wavelength, solar zenith angle and altitude, with 2 %–10 % uncertainties covering all atmospheric conditions for solar zenith angles below 80∘. For upward spectral actinic flux densities, corrections were more variable and significantly greater, up to about −50 % at low altitudes and low ground albedos. A parametrization for corrections and uncertainties was derived using uncorrected ratios of upward / downward spectral actinic flux densities as input, applicable independent of atmospheric conditions for a given wavelength, solar zenith angle and altitude. The use was limited to conditions with solar zenith angles <80∘ when direct sun radiation cannot strike upward- and downward-looking receivers simultaneously. Examples of research flights with the Zeppelin and HALO are discussed, as well as other approaches described in the literature.

Solvent-Mediated Charge Transfer Dynamics of a Model Brown Carbon Aerosol Chromophore: Photophysics of 1-Phenylpyrrole Induced by Water Solvation.

Nitrogen heterocycles are known to be important light-absorbing chromophores in a newly discovered class of aerosols, commonly referred to as "brown carbon" (BrC) aerosols. Due to their significant absorption and spectral overlap with the solar actinic flux, these BrC chromophores steer the physical and optical properties of aerosols. To model the local aqueous solvation environment surrounding BrC chromophores, we generated cold molecular complexes with water and a prototypical BrC chromophore, 1-phenylpyrrole (1PhPy), using supersonic jet-cooling and explored their intermolecular interactions using single-conformation spectroscopy. Herein, we utilized resonant two-photon ionization (R2PI) and UV holeburning (UV HB) double-resonance spectroscopies to obtain a molecular-level understanding of the role of water microsolvation in charge transfer upon photoexcitation of 1PhPy. Quantum chemical calculations and one-dimensional discrete variable representation simulations revealed insights into the charge transfer efficacy of 1PhPy with and without addition of a single water molecule. Taken together, our results indicate that the intermolecular interactions with water guide the geometry of 1PhPy to adopt a more twisted intramolecular charge transfer (TICT) configuration, thus facilitating charge transfer from the pyrrole donor to the phenyl ring acceptor. Furthermore, the water network surrounding 1PhPy reports on the charge transfer such that the H2O solvent primarily interacts with the pyrrole ring donor in the ground state, whereas it preferentially interacts with the phenyl ring acceptor in the excited state. Large Franck-Condon activity is evident in the 1PhPy + 1H2O excitation spectrum for the water-migration vibronic bands, supporting H2O solvent reorganization upon excitation of the 1PhPy chromophore. Fluorescence measurements with increasing H2O % volume corroborated our gas-phase studies by indicating that a polar water solvation environment stabilizes the TICT configuration of 1PhPy in the excited electronic state, from which emission is observed at a lower energy compared to the locally excited configuration.

The pathway of impacts of aerosol direct effects on secondary inorganic aerosol formation.

Airborne aerosols reduce surface solar radiation through light scattering and absorption (aerosol direct effects, ADEs), influence regional meteorology, and further affect atmospheric chemical reactions and aerosol concentrations. The inhibition of turbulence and the strengthened atmospheric stability induced by ADEs increases surface primary aerosol concentration, but the pathway of ADE impacts on secondary aerosol is still unclear. In this study, the online coupled meteorological and chemistry model (WRF-CMAQ; Weather Research and Forecasting-Community Multiscale Air Quality) with integrated process analysis was applied to explore how ADEs affect secondary aerosol formation through changes in atmospheric dynamics and photolysis processes. The meteorological condition and air quality in the Jing-Jin-Ji area (denoted JJJ, including Beijing, Tianjin, and Hebei Province in China) in January and July 2013 were simulated to represent winter and summer conditions, respectively. Our results show that ADEs through the photolysis pathway inhibit sulfate formation during winter in the JJJ region and promote sulfate formation in July. The differences are attributed to the alteration of effective actinic flux affected by single-scattering albedo (SSA). ADEs through the dynamics pathway act as an equally or even more important route compared with the photolysis pathway in affecting secondary aerosol concentration in both summer and winter. ADEs through dynamics traps formed sulfate within the planetary boundary layer (PBL) which increases sulfate concentration in winter. Meanwhile, the impact of ADEs through dynamics is mainly reflected in the increase of gaseous-precursor concentrations within the PBL which enhances secondary aerosol formation in summer. For nitrate, reduced upward transport of precursors restrains the formation at high altitude and eventually lowers the nitrate concentration within the PBL in winter, while such weakened vertical transport of precursors increases nitrate concentration within the PBL in summer, since nitrate is mainly formed near the surface ground.

Effect of Aerosol Vertical Distribution on the Modeling of Solar Radiation

Default aerosol extinction coefficient profiles are commonly used instead of measured profiles in radiative transfer modeling, increasing the uncertainties in the simulations. The present study aimed to determine the magnitude of these uncertainties and contribute towards the understanding of the complex interactions between aerosols and solar radiation. Default, artificial and measured profiles of the aerosol extinction coefficient were used to simulate the profiles of different radiometric quantities in the atmosphere for different surface, atmospheric, and aerosol properties and for four spectral bands: ultraviolet-B, ultraviolet-A, visible, and near-infrared. Case studies were performed over different areas in Europe and North Africa. Analysis of the results showed that under cloudless skies, changing the altitude of an artificial aerosol layer has minor impact on the levels of shortwave radiation at the top and bottom of the atmosphere, even for high aerosol loads. Differences of up to 30% were, however, detected for individual spectral bands. Using measured instead of default profiles for the simulations led to more significant differences in the atmosphere, which became very large during dust episodes (10–60% for actinic flux at altitudes between 1 and 2 km, and up to 15 K/day for heating rates depending on the site and solar elevation).

Ab Initio and RRKM/Master Equation Analysis of the Photolysis and Thermal Unimolecular Decomposition of Bromoacetaldehyde

Bromoacetaldehyde (BrCH2CHO) is a major stable brominated organic intermediate of the bromine-ethylene addition reaction during the arctic bromine explosion events. Similar to acetaldehyde, which has been recently identified as a source of organic acids in the troposphere, it may be subjected to photo-tautomerization initially forming brominated vinyl compounds. In this study, we investigate the unimolecular reactions of BrCH2CHO under both photolytic and thermal conditions using high-level quantum chemical calculations and Rice-Ramsperger-Kassel-Marcus (RRKM)/master equation analysis. The unimolecular decomposition of BrCH2CHO takes place through 14 dissociation and isomerization channels along a potential energy surface involving eight wells. Under the assumption of singlet ground-state potential energy surface-dominated photodynamics, the primary photodissociation yields of BrCH2CHO are investigated under both collision-free and collision energy transfer conditions. At atmospheric pressure and under tropospheric actinic flux conditions at ground level, depending on the assumed collisional energy transfer parameter, 150 cm-1 < ⟨ΔEdown⟩ < 450 cm-1, 78-33% of BrCH2CHO undergoes direct photodissociation instead of collisional deactivation at an excitation wavelength of 320 nm. This is significantly higher than the 14% reported for acetaldehyde, hence indicating a strong effect of bromine substitution on the product photolysis yield that is related to additional favorable Br and HBr forming dissociation channels. In contrast to the overall photodissociation quantum yield, the relative branching fractions of the photodissociation products are less dependent on the collisional energy transfer parameter. For a representative value of ⟨ΔEdown⟩ = 300 cm-1 and an excitation wavelength of 320 nm, with 27% for C-C bond fission, 11% for C-Br bond fission, 7% for HBr elimination, and only below 2% each for a consecutive O-Br fission reaction and the photo-tautomerization channel yielding brominated vinyl alcohol, the photodissociation is markedly different from the acetaldehyde case. Finally, as brominated halogenated compounds are of interest for flame inhibition purposes, thermal multichannel unimolecular rate constants were calculated for temperatures in the range from 500 to 2000 K. At a temperature of 2000 K and ambient pressure, the two main reaction channels are the C-Br and C-C bond fissions, contributing 35 and 43% to the total reaction flux, respectively.

Atmospheric photooxidation and ozonolysis of Δ&amp;lt;sup&amp;gt;3&amp;lt;/sup&amp;gt;-carene and 3-caronaldehyde: rate constants and product yields

Abstract. The oxidation of Δ3-carene and one of its main oxidation products, caronaldehyde, by the OH radical and O3 was investigated in the atmospheric simulation chamber SAPHIR under atmospheric conditions for NOx mixing ratios below 2 ppbv. Within this study, the rate constants of the reaction of Δ3-carene with OH and O3 and of the reaction of caronaldehyde with OH were determined to be (8.0±0.5)×10-11 cm3 s−1 at 304 K, (4.4±0.2)×10-17 cm3 s−1 at 300 K and (4.6±1.6)×10-11 cm3 s−1 at 300 K, in agreement with previously published values. The yields of caronaldehyde from the reaction of OH and ozone with Δ3-carene were determined to be 0.30±0.05 and 0.06±0.02, respectively. Both values are in reasonably good agreement with reported literature values. An organic nitrate (RONO2) yield from the reaction of NO with RO2 derived from Δ3-carene of 0.25±0.04 was determined from the analysis of the reactive nitrogen species (NOy) in the SAPHIR chamber. The RONO2 yield of the reaction of NO with RO2 derived from the reaction of caronaldehyde with OH was found to be 0.10±0.02. The organic nitrate yields of Δ3-carene and caronaldehyde oxidation with OH are reported here for the first time in the gas phase. An OH yield of 0.65±0.10 was determined from the ozonolysis of Δ3-carene. Calculations of production and destruction rates of the sum of hydroxyl and peroxy radicals (ROx=OH+HO2+RO2) demonstrated that there were no unaccounted production or loss processes of radicals in the oxidation of Δ3-carene for conditions of the chamber experiments. In an OH-free experiment with added OH scavenger, the photolysis frequency of caronaldehyde was obtained from its photolytical decay. The experimental photolysis frequency was a factor of 7 higher than the value calculated from the measured solar actinic flux density, an absorption cross section from the literature and an assumed effective quantum yield of unity for photodissociation.

One dimension photochemical models in global mean conditions in question: Application to Titan

Observational data of Titan's atmosphere composition, gathered in particular by the Cassini mission, allow accessing latitudinal, longitudinal and temporal variations of the altitudinal profiles of several species. While 1D models are a powerful tool to gain insight into the chemistry occurring in Titan's atmosphere, they cannot capture the four-dimensional nature of these processes at the same time. However, due to the large extent of the atmosphere and the complexity of chemistry, global 2D and 3D models with the chemical complexity of 1D models do not exist yet. On the way of developing a 2D photochemical model of Titan, including the very complex chemical schemes used in 1D models and also taking latitudinal variations into account, we developed an ultraviolet radiative transfer model to compute the actinic flux in a 2D geometry. We found that photolysis rates calculated in classical plane-parallel models to derive the rates in mean conditions give results notably different from a model that calculates the mean rates with a 2D geometry. We demonstrate that the introduction of the 2D geometry affects significantly the density profiles on both neutrals and ions, especially on nitriles. As a consequence, we advocate using radiative transfer model in 2D geometry from now on to interpret the wide diversity of observational data about Titan's atmosphere (pending the emergence of 2D models with complex chemical schemes).

Seasonality of nitrous acid near an industry zone in the Yangtze River Delta region of China: Formation mechanisms and contribution to the atmospheric oxidation capacity

HONO along with other trace gases and actinic flux were continuously measured in selected months from December 2015 to November 2016 near a major industrial zone of the Yangtze River Delta (YRD) region of China. The seasonalities of HONO and its formation mechanisms were explored. A box model was developed to assess the role of HONO chemistry in the atmospheric oxidative capacity in the study area. The model was constrained by in-situ observations to minimize simulation uncertainties. Our measurement results demonstrate that HONO mean concentration and diurnal profile varied noticeably between different seasons with the maximum (1.32 ± 0.92 ppbv) observed in winter, coincided with high mass loading of fine particles (PM2.5 = 114 ± 59.6 μg m−3). The averaged nighttime NO2 to HONO conversion ratios (hr−1) were (1.83 ± 0.73)% in spring, (2.91 ± 1.06)% in summer, (0.72 ± 0.44)% in autumn, and (0.84 ± 0.45)% in winter. The homogeneous reaction of OH + NO was responsible for a large portion of HONO production throughout the year but was relatively weaker compared to other mechanisms in winter. Heterogeneous reactions on ground surfaces were much stronger than those on aerosol surfaces, dominating nighttime HONO production, except in summer. Primary HONO emissions were only responsible for a small portion of the HONO budget. Particulate nitrate photolysis was a significant source of HONO and it showed very little variation in different seasons. OH budget analysis shows that O3 photolysis was a major contributor to the OH production in the study area while HONO photolysis provided an extra boost to the photochemical reactivity in the early morning, particularly during summer. However, HONO chemistry played a more important role in autumn and winter by dominating OH production throughout the day. Accordingly, effective control of NOx emissions dominated by industries can significantly reduce HONO production and thus weaken the atmospheric oxidative capacity in the study area.

New particle formation in the remote marine boundary layer

Marine low clouds play an important role in the climate system, and their properties are sensitive to cloud condensation nuclei concentrations. While new particle formation represents a major source of cloud condensation nuclei globally, the prevailing view is that new particle formation rarely occurs in remote marine boundary layer over open oceans. Here we present evidence of the regular and frequent occurrence of new particle formation in the upper part of remote marine boundary layer following cold front passages. The new particle formation is facilitated by a combination of efficient removal of existing particles by precipitation, cold air temperatures, vertical transport of reactive gases from the ocean surface, and high actinic fluxes in a broken cloud field. The newly formed particles subsequently grow and contribute substantially to cloud condensation nuclei in the remote marine boundary layer and thereby impact marine low clouds.

Exploring the drivers of the increased ozone production in Beijing in summertime during 2005–2016

Abstract. In the past decade, average PM2.5 concentrations decreased rapidly under the strong pollution control measures in major cities in China; however, ozone (O3) pollution emerged as a significant problem. Here we examine a unique (for China) 12-year data set of ground-level O3 and precursor concentrations collected at an urban site in Beijing (PKUERS, campus of Peking University), where the maximum daily 8 h average (MDA8) O3 concentration and daytime Ox (O3+NO2) concentration in August increased by 2.3±1.2 ppbv (+3.3±1.8 %) yr−1 and 1.4±0.6 (+1.9±0.8 %) yr−1, respectively, from 2005 to 2016. In contrast, daytime concentrations of nitrogen oxides (NOx) and the OH reactivity of volatile organic compounds (VOCs) both decreased significantly. Over this same time, the decrease of particulate matter (and thus the aerosol optical depth) led to enhanced solar radiation and photolysis frequencies, with near-surface J(NO2) increasing at a rate of 3.6±0.8 % yr−1. We use an observation-based box model to analyze the combined effect of solar radiation and ozone precursor changes on ozone production rate, P(O3). The results indicate that the ratio of the rates of decrease of VOCs and NOx (about 1.1) is inefficient in reducing ozone production in Beijing. P(O3) increased during the decade due to more rapid atmospheric oxidation caused to a large extent by the decrease of particulate matter. This elevated ozone production was driven primarily by increased actinic flux due to PM2.5 decrease and to a lesser extent by reduced heterogeneous uptake of HO2. Therefore, the influence of PM2.5 on actinic flux and thus on the rate of oxidation of VOCs and NOx to ozone and to secondary aerosol (i.e., the major contributor to PM2.5) is important for determining the atmospheric effects of controlling the emissions of the common precursors of PM2.5 and ozone when attempting to control these two important air pollutants.

Photooxidation of pinonaldehyde at ambient conditions investigated in the atmospheric simulation chamber SAPHIR

Abstract. The photooxidation of pinonaldehyde, one product of the α-pinene degradation, was investigated in the atmospheric simulation chamber SAPHIR under natural sunlight at low NO concentrations (&lt;0.2 ppbv) with and without an added hydroxyl radical (OH) scavenger. With a scavenger, pinonaldehyde was exclusively removed by photolysis, whereas without a scavenger, the degradation was dominated by reaction with OH. In both cases, the observed rate of pinonaldehyde consumption was faster than predicted by an explicit chemical model, the Master Chemical Mechanism (MCM, version 3.3.1). In the case with an OH scavenger, the observed photolytic decay can be reproduced by the model if an experimentally determined photolysis frequency is used instead of the parameterization in the MCM. A good fit is obtained when the photolysis frequency is calculated from the measured solar actinic flux spectrum, absorption cross sections published by Hallquist et al. (1997), and an effective quantum yield of 0.9. The resulting photolysis frequency is 3.5 times faster than the parameterization in the MCM. When pinonaldehyde is mainly removed by reaction with OH, the observed OH and hydroperoxy radical (HO2) concentrations are underestimated in the model by a factor of 2. Using measured HO2 as a model constraint brings modeled and measured OH concentrations into agreement. This suggests that the chemical mechanism includes all relevant OH-producing reactions but is missing a source for HO2. The missing HO2 source strength of (0.8 to 1.5) ppbv h−1 is similar to the rate of the pinonaldehyde consumption of up to 2.5 ppbv h−1. When the model is constrained by HO2 concentrations and the experimentally derived photolysis frequency, the pinonaldehyde decay is well represented. The photolysis of pinonaldehyde yields 0.18 ± 0.20 formaldehyde molecules at NO concentrations of less than 200 pptv, but no significant acetone formation is observed. When pinonaldehyde is also oxidized by OH under low NO conditions (maximum 80 pptv), yields of acetone and formaldehyde increase over the course of the experiment from 0.2 to 0.3 and from 0.15 to 0.45, respectively. Fantechi et al. (2002) proposed a degradation mechanism based on quantum-chemical calculations, which is considerably more complex than the MCM scheme and contains additional reaction pathways and products. Implementing these modifications results in a closure of the model–measurement discrepancy for the products acetone and formaldehyde, when pinonaldehyde is degraded only by photolysis. In contrast, the underprediction of formed acetone and formaldehyde is worsened compared to model results by the MCM, when pinonaldehyde is mainly degraded in the reaction with OH. This shows that the current mechanisms lack acetone and formaldehyde sources for low NO conditions like in these experiments. Implementing the modifications suggested by Fantechi et al. (2002) does not improve the model–measurement agreement of OH and HO2.

Net ozone production and its relationship to nitrogen oxides and volatile organic compounds in the marine boundary layer around the Arabian Peninsula

Abstract. Strongly enhanced tropospheric ozone (O3) mixing ratios have been reported in the Arabian Basin, a region with intense solar radiation and high concentrations of O3 precursors such as nitrogen oxides (NOx) and volatile organic compounds (VOCs). To analyze photochemical O3 production in the marine boundary layer (MBL) around the Arabian Peninsula, we use shipborne observations of NO, NO2, O3, OH, HO2, HCHO, the actinic flux, water vapor, pressure and temperature obtained during the summer 2017 Air Quality and Climate in the Arabian Basin (AQABA) campaign, and we compare them to simulation results from the ECHAM-MESSy Atmospheric Chemistry (EMAC) general circulation model. Net O3 production rates (NOPRs) were greatest over both the Gulf of Oman and the northern Red Sea (16 ppbv d−1) and over the Arabian Gulf (32 ppbv d−1). The NOPR over the Mediterranean, the southern Red Sea and the Arabian Sea did not significantly deviate from zero; however, the results for the Arabian Sea indicated weak net O3 production of 5 ppbv d−1 as well as net O3 destruction over the Mediterranean and the southern Red Sea with values of −1 and −4 ppbv d−1, respectively. Constrained by HCHO∕NO2 ratios, our photochemistry calculations show that net O3 production in the MBL around the Arabian Peninsula mostly occurs in NOx-limited regimes with a significant share of O3 production occurring in the transition regime between NOx limitation and VOC limitation over the Mediterranean and more significantly over the northern Red Sea and Oman Gulf.

Impacts of spectrally resolved irradiance on photolysis frequency calculations within a forest canopy

Although photolysis frequencies are wavelength-dependent and the dependence varies among chemical species, previous canopy radiative transfer models did not consider more than three broad bands (ultraviolet, photosynthetically active radiation (PAR), and near-infrared). In this study, high spectral resolution and wavelength-dependent idealized leaf optical properties allow us to determine the disposition of the light spectrum within a mixed deciduous forest canopy. Four radiative transfer approaches of varying complexity are applied to obtain vertical profiles of spectral actinic flux. Broad-band radiation measurements made above and below a mixed deciduous forest provide the necessary information to verify the fidelity of each radiative transfer approach. Model comparison results indicate that the Beer–Lambert scheme gives less total actinic flux, while the other three schemes give similar actinic flux profiles. Spectral actinic flux profiles are used to calculate in-canopy photolysis for different chemical species and to assess the importance of in-canopy photochemistry in modifying biogenic volatile organic compounds transported to the overlying atmospheric boundary layer. We find that, depending on the time of day and chemical species, percent errors in photolysis frequencies incurred by using a common in-canopy approximation based on weighting by relative PAR profiles can be as high as ± 50% in lower regions of the canopy, or 10–20% in daily canopy integrated photolysis frequency. Results obtained using a one-dimensional photochemical model suggest that choice of canopy radiative transfer scheme can have substantial impacts on in-canopy chemical reactions and concentrations in the overlying atmospheric boundary layer air. Such effects caused in-canopy gas concentration differences ranging from 8% for ozone and 35% for hydroxyl radical to 77% for nitrate radical.