Photolysis Rates Research Articles

Direct and indirect photodegradation of bisphenol A in the presence of natural water components.

The impacts and mechanisms of natural water constituents, such as humic acid (HA), nitrates, iron and chloride ions, to the photodegradation of bisphenol A (BPA) were investigated in aqueous media under UV light irradiation. Due to the contributions of ·OH, 1O2, O2- and BPA* to BPA photodegradation in pure water in 13.4, 7.7, 22.9 and 47.9%, respectively, BPA was attenuated through the reaction pathway of direct photodegradation more than self-sensitized photodegradation. About indirect photodegradation, BPA photolysis through inhibitory effect from HA was mainly by light screening effect and quenching effect was insignificant. NO- 3 and NO- 2 both showed inhibitory effect but due to different reactive oxidization species (ROS). The photodegradation of BPA was significantly enhanced by the addition of iron from the formation of ·OH and H2O2, due to iron-assisted indirect photolysis for the degradation process. A dual effect of chloride depending on the different concentration levels involved quenching and promotion effect on reactive photo-induced species (RPS). A simple linear model revealed that BPA photodegradation was significantly impacted by the interaction of the above factors. In natural water, the decreased photolytic rate of BPA was mainly attributed to triple-excited dissolved organic matter (3DOM*), indicating that indirect photolysis was the primary transformation pathway of BPA. The detected photolysis products, such as nitrate and chlorinated products, suggest that there might be potential ecological risk of BPA photodegradation.

Implementation and evaluation of updated photolysis rates in the EMEP MSC-W chemistry-transport model using Cloud-J v7.3e

Abstract. The present work describes the implementation of the state of the art Cloud-J v7.3 photolysis rate calculation code in the EMEP MSC-W chemistry-transport model. Cloud-J calculates photolysis rates and accounts for cloud and aerosol optical properties at model run time, replacing the old system based on tabulated values. The performance of Cloud-J is evaluated against aerial photolysis rate observations made over the Pacific Ocean and against surface observations from three measurement sites in Europe. Numerical experiments are performed to investigate the sensitivity of the calculated photolysis rates to the spatial and temporal model resolution, input meteorology model, simulated ozone column, and cloud effect parameterization. These experiments indicate that the calculated photolysis rates are most sensitive to the choice of input meteorology model and cloud effect parameterization while also showing that surface ozone photolysis rates can vary by up to 20 % due to daily variations in total ozone column. Further analysis investigates the impact of Cloud-J on the oxidizing capacity of the troposphere, aerosol–photolysis interactions, and surface air quality predictions. Results find that the annual mean mass-weighted tropospheric hydroxyl concentration is increased by 26 %, while the photolytic impact of aerosols is mostly limited to large tropical biomass-burning regions. Overall, Cloud-J represents a major improvement over the tabulated system, leading to improved model performance for predicting carbon monoxide and daily maximum ozone surface concentrations.

Kinetic modeling and mechanisms of parahalogenated phenols degradation by UV222/H2O2

Advanced oxidation technology of KrCl excimer lamp activated H2O2 (UV222/H2O2) have been received widespread attention in the field of water treatment recently, due to the higher radical yield and environmentally friendly nature compared to UV254/H2O2. In this investigation, four representative parahalogenated phenols (HPs) degradation kinetic and mechanisms by UV222 alone and UV222/H2O2 were studied, respectively. The results showed that the photolysis rate constants (kobs) under UV222 followed the order of p-Chlorophenol (p-CP) > p-Fluorophenol (p-FP) > p-Bromophenol (p-BP) > p-Iodophenol (p-IP), and the degradation rate constants (kobs) by UV222/H2O2 followed the order of p-FP > p-CP > p-BP > p-IP. The molar absorption coefficient (ε222nm) and quantum yield (Φ222nm) of HPs photolysis were measured. Kinetic model simulating results are in fair agreement with the experimental results. Through HPLC-MS analysis and DFT calculation, the impact of halogen ions on the degradation kinetics of HPS by UV222 and UV222/H2O2 was found, the possible reaction pathways and mechanisms were proposed. Compared with UV254/H2O2 for removing p-CP, UV222/H2O2 was much more energy efficient.

Boosting the Release of Leaving Group from Blebbistatin Derivative Photocages via Enhancing Intramolecular Charge Transfer and Stabilizing Cationic Intermediate.

Blebbistatin (Bleb) derivatives are a visible light photocage platform. During the photocleavage process, intramolecular charge transfer (ICT) and cationic intermediates play a decisive role. However, slow photolysis rate and low photolysis quantum yield are the main problems for Bleb's derivatives. Herein, by introducing a substituted OCH3 group at the para-position of the D ring, Bleb and Bleb derivatives with various leaving groups were synthesized and studied, and the photolysis performance was unveiled by steady-state spectra, photolysis rate experiments, photolysis quantum yield, and density functional theory calculations. Substituted OCH3 derivatives of Bleb may enhance the photolysis rate and increase the photolysis quantum yield because the electron-donating group can promote the ICT process and stabilize the cationic intermediate during the photolytic reaction. More generally, the insights gained from this structure-reactivity relationship may provide theoretical guidance and aid in the development of new highly efficient photoreactions.

Some features of trichlorobiphenyls photolysis

The photolytic decomposition of the Trikhlorbifenil mixture, 2,4,5- and 2,4,6-trichlorobiphenyls under an influence of ultraviolet radiation in presence of tungsten oxide as a catalyst in a methanol medium was studied. A higher rate of photolysis of individual congeners of polychlorbiphenyls was established compared to the congeners of the Trikhlorbifenil mixture. The influence of structural features of polychlorarenes on a depth of photodecomposition and a routes of formation of photodestruction products was considered.

Heterogeneous Processes in the Atmosphere of Mars and Impact on H2O2 and O3 Abundances

AbstractCurrent models underestimate the highest observed ozone (O3) column densities on Mars. These estimates could be improved by including the uptake of odd hydrogen species (HOx) on water ice clouds, but the reported uptake coefficient of HO2 is likely overestimated for atmospheric conditions. This leaves a fundamental problem in Mars' atmospheric chemistry unsolved. Here, using the GEM‐Mars general circulation model, we explore a range of processes involving multiple phases (gas, adsorbed and solid) that may contribute to an alternative solution. First, we focus on hydrogen peroxide (H2O2) and discuss its physical states on Mars and its chemical impact. We also conjecture its photolytic destruction in ices with model simulations and Compact Reconnaissance Imaging Spectrometer for Mars observations. Then, we include in the model all relevant (for Mars) heterogeneous reactions, both on dust and water ice, recommended by the International Union of Pure and Applied Chemistry for terrestrial atmospheric studies. We find that only the uptake of HO2 and H2O2 on dust are efficient on Mars. Finally, we find that attenuation of sunlight by water ice clouds in the calculation of photolysis rates leads to increased O3 and H2O2 abundances below the ice clouds. The combination of the proposed processes leads to O3 increases without the need for strong uptake of HO2 on ice, but it remains difficult to find a good agreement with O3 and H2O2 observations on the global scale. We provide specific recommendations for future work in observations, laboratory experiments and modeling to advance our understanding of fundamental chemistry on Mars.

Atmospheric impact of 2-methylpentanal emissions: kinetics, photochemistry, and formation of secondary pollutants

Abstract. The tropospheric fate of 2-methylpentanal (2MP) has been investigated in this work. First, the photochemistry of 2MP under simulated solar conditions was investigated by determining the UV absorption cross sections (220–360 nm) and the effective photolysis quantum yield in the UV solar actinic region (λ > 290 nm). The photolysis rate coefficient in that region was estimated using a radiative transfer model. Photolysis products were identified by Fourier transform infrared (FTIR) spectroscopy. Secondly, a kinetic study of the chlorine (Cl) and hydroxyl (OH) reactions of 2MP was also performed at 298 K and as a function of temperature (263–353 K), respectively. For the Cl reaction, a relative kinetic method was used in a smog chamber coupled to FTIR spectroscopy, whereas for the OH reaction, the pulsed laser photolysis (PLP) with laser-induced fluorescence (LIF) technique was employed. The estimated lifetime of 2MP depends on the location, the season, and the time of the day. Under mild–strong irradiation conditions, UV photolysis of 2MP may compete with its OH reaction in a mid-latitude inland urban atmosphere, while Cl reaction dominates in mid-latitude coastal urban areas at dawn. Finally, the gaseous product distribution of the Cl and OH reactions was measured in a smog chamber as well as the formation of secondary organic aerosols (SOAs) in the Cl reaction and its size distribution (diameter between 5.6 and 560 nm). The implications for air quality are discussed based on the observed products.

Impact of wildfires on regional ozone and PM2.5: Considering the light absorption of Brown carbon

The influence of wildfire brown carbon (BrC) in moderating the formation of O3 and fine particulate matter (PM2.5) due to its absorption of ultraviolet (UV) radiation is, for the first time, investigated using a modified community multiscale air quality (CMAQ) model. The wavelength-dependent imaginary refractive index of the organic carbon from wildfires, which are needed by the CMAQ model for its inline photolysis rate calculation, are generated experimentally from wood burning aerosols from a combustion chamber. On high emission days of the Bastrop County Complex fire in Texas in early September 2011, BrC UV absorption reduces the daytime average NO2 photolysis rate by up to 38% in the core region of the wildfire plume compared to the base scenario that does not consider BrC absorption. Consequently, O3 production in the smoke plume is suppressed compared to the base scenario due to reduced HOx radical concentrations. In the core region, the predicted O3 increase due to wildfire reaches as high as 47–123 ppb without considering BrC absorption, the predicted increase of O3 is 5–15% lower when BrC absorption is considered. Similarly, considering the BrC UV absorption leads to approximately 1% (or ∼2–3 μg m−3) lower estimation of the wildfire emissions’ impact on total PM2.5. This change is small because secondary aerosols, which are the components affected by BrC absorption, only account for a small fraction of the total PM2.5 in wildfire impacted regions in this study. In addition, our study shows that assumptions about aerosol mixing state (core-shell vs. homogeneous) in the inline photolysis rate calculation would not significantly affect out assessment of the impact of wildfire BrC light absorption on O3 and PM2.5.

Assessing the Influence of Polymer-Based Anti-Drift Adjuvants on the Photolysis, Volatilization, and Secondary Drift of Pesticides after Application

One practice to reduce spray drift during pesticide application is the addition of certain chemical adjuvants to spraying solutions, which change their physicochemical properties and result in larger droplets. The environmental impact of these agrochemicals continues however also after application, depending on surface processes occurring upon treated surfaces. While the impact of anti-drift adjuvants has been studied regarding spray drift, their impact on the fate of deposited pesticides has received little attention. Here, the effect of a polymer-based adjuvant (polyacrylamide) on the photolysis and evaporation rates of pyrimethanil (common fungicide) from dry films were investigated under controlled laboratory conditions and during two field studies. The laboratory results indicate that the adjuvant enhances the volatilization and photolysis rate both on hydrophobic lemon leaves and hydrophilic glass substrates. These results can be attributed to an increase in the geometrical area of residual film and a widening of its circumference rim, where solutes are likely to concentrate, when generated from adjuvant-containing droplets. Such morphological differences may enhance the exposure of deposited pesticides to interact with the overlaying atmosphere and incident radiation. The field data was less conclusive, suggesting a small impact of the anti-drift adjuvant on the fungicide’s secondary drift from crops and an even lower effect on volatilization from bare soil.

Visible Light Photoiniferter Polymerization for Dispersity Control in High Molecular Weight Polymers

AbstractThe synthesis of polymers with high molecular weights, controlled sequence, and tunable dispersities remains a challenge. A simple and effective visible‐light controlled photoiniferter reversible addition‐fragmentation chain transfer (RAFT) polymerization is reported here to realize this goal. Key to this strategy is the use of switchable RAFT agents (SRAs) to tune polymerization activities coupled with the inherent highly living nature of photoiniferter RAFT polymerization. The polymerization activities of SRAs were in situ adjusted by the addition of acid. In addition to a switchable chain‐transfer coefficient, photolysis and polymerization kinetic studies revealed that neutral and protonated SRAs showed different photolysis and polymerization rates, which is unique to photoiniferter RAFT polymerization in terms of dispersity control. This strategy features no catalyst, no exogenous radical source, temporal regulation by visible light, and tunable dispersities in the unprecedented high molecular weight regime (up to 500 kg mol−1). Pentablock copolymers with three different dispersity combinations were also synthesized, highlighting that the highly living nature was maintained even for blocks with large dispersities. Tg was lowered for high‐dispersity polymers of similar MWs due to the existence of more low‐MW polymers. This strategy holds great potential for the synthesis of advanced materials with controlled molecular weight, dispersity and sequence.

Visible Light Photoiniferter Polymerization for Dispersity Control in High Molecular Weight Polymers.

The synthesis of polymers with high molecular weights, controlled sequence, and tunable dispersities remains a challenge. A simple and effective visible-light controlled photoiniferter reversible addition-fragmentation chain transfer (RAFT) polymerization is reported here to realize this goal. Key to this strategy is the use of switchable RAFT agents (SRAs) to tune polymerization activities coupled with the inherent highly living nature of photoiniferter RAFT polymerization. The polymerization activities of SRAs were in situ adjusted by the addition of acid. In addition to a switchable chain-transfer coefficient, photolysis and polymerization kinetic studies revealed that neutral and protonated SRAs showed different photolysis and polymerization rates, which is unique to photoiniferter RAFT polymerization in terms of dispersity control. This strategy features no catalyst, no exogenous radical source, temporal regulation by visible light, and tunable dispersities in the unprecedented high molecular weight regime (up to 500 kg mol-1 ). Pentablock copolymers with three different dispersity combinations were also synthesized, highlighting that the highly living nature was maintained even for blocks with large dispersities. Tg was lowered for high-dispersity polymers of similar MWs due to the existence of more low-MW polymers. This strategy holds great potential for the synthesis of advanced materials with controlled molecular weight, dispersity and sequence.

Sunlight-induced degradation of COVID-19 antivirals arbidol in natural aquatic environments: Mechanisms, pathways and toxicity

Insights into COVID-19 antivirals’ environmental fate and ecological risk are urgently required due to their increasing concentrations in aquatic environments, which have rarely been studied. Herein, we first investigated the photochemical transformation and the resulting alterations in toxicity of arbidol, an antiviral drug with relatively higher toxicity. The photolysis of arbidol was rapid with a rate constant of 0.106 min−1 due to its superior ultraviolet light absorption, in which the direct photolysis was predominated with a contribution of 91.5%. Despite its substantial photolysis, only 14.45% of arbidol was mineralized after 100 min, implying that arbidol and its products might have a long-term impact on aquatic environment. It was inferred that arbidol was photolyzed mainly via the loss of thiophenol, bromine, and alkylamine, based on twelve photolytic products identified. Notably, the experimental results demonstrated that the photolysis process increased the acute toxicity of arbidol, and the toxicity prediction indicated that the ecotoxicity of two photolytic products was very high with LC50 values below 0.1 mg/L. Due to the co-effect of multiple constituents, the photolytic rate observed in wastewater treatment plant effluent and in river water was comparable to that in ultra-pure water, while it was slightly enhanced in lake water. The presence of dissolved organic matter suppressed arbidol photolysis, while NO3− exhibited a promotion effect. These results would be of great significance to assess the fate and risk of COVID-19 antivirals in natural aquatic environments.

Impurity contribution to ultraviolet absorption of saturated fatty acids.

Saturated fatty acids are abundant organic compounds in oceans and sea sprays. Their photochemical reactions induced by solar radiation have recently been found as an abiotic source of volatile organic compounds, which serve as precursors of secondary organic aerosols. However, photoabsorption of wavelengths longer than 250 nanometers in liquid saturated fatty acids remains unexplained, despite being first reported in 1931. Here, we demonstrate that the previously reported absorption of wavelengths longer than 250 nanometers by liquid nonanoic acid [CH3(CH2)7COOH)] originates from traces of impurities (0.1% at most) intrinsically contained in nonanoic acid reagents. Absorption cross sections of nonanoic acid newly obtained here indicate that the upper limit of its photolysis rate is three to five orders of magnitude smaller than those for atmospherically relevant carbonyl compounds.

Inferring the photolysis rate of NO2 in the stratosphere based on satellite observations

Abstract. NO and NO2 (NOx) play major roles in both tropospheric and stratospheric chemistry. This paper provides a novel method to obtain a global and accurate photolysis rate for NO2 based on satellite data. The photolysis rate J(NO2) dominates the daytime diurnal variation of NOx photochemistry. Here the spatial variation of J(NO2) at 50–90∘ S in December from 20–40 km is obtained using data from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) experiment. Because NO and NO2 rapidly exchange with one another in the daytime, J(NO2) can be attained assuming steady state, and the results are shown to be consistent with model results. The J(NO2) value decreases as the solar zenith angle increases and has a weak altitude dependence. A key finding is that satellite-derived J(NO2) increases in the polar regions, in good agreement with model predictions, due to the effects of ice and snow on surface albedo. Thus, the method presented here provides an observation-based check on the role of albedo in driving polar photochemistry.

Inferring the diurnal variability of OH radical concentrations over the Amazon from BVOC measurements

The atmospheric oxidation of biogenic volatile organic compounds (BVOC) by OH radicals over tropical rainforests impacts local particle production and the lifetime of globally distributed chemically and radiatively active gases. For the pristine Amazon rainforest during the dry season, we empirically determined the diurnal OH radical variability at the forest-atmosphere interface region between 80 and 325 m from 07:00 to 15:00 LT using BVOC measurements. A dynamic time warping approach was applied showing that median averaged mixing times between 80 to 325 m decrease from 105 to 15 min over this time period. The inferred OH concentrations show evidence for an early morning OH peak (07:00–08:00 LT) and an OH maximum (14:00 LT) reaching 2.2 (0.2, 3.8) × 106 molecules cm−3 controlled by the coupling between BVOC emission fluxes, nocturnal NOx accumulation, convective turbulence, air chemistry and photolysis rates. The results were evaluated with a turbulence resolving transport (DALES), a regional scale (WRF-Chem) and a global (EMAC) atmospheric chemistry model.

Ozone deterioration over North China plain caused by light absorption of black carbon and organic carbon

Previous studies have revealed that the light absorption effect of black carbon (BC) aerosol could influence ozone concentrations via absorbing sunlight and modulating photolysis rates, the so-called aerosol-photolysis interaction (API). However, few studies have quantified the API effect of organic carbon (OC) aerosol, which has recently been found to contribute to about 10%–40% of the total light absorption at 300 nm wavelength. This study tried to quantify and compare the OC and BC aerosols' influence on ozone concentrations through a case study over North China Plain (NCP) in Oct. 2018. By modulating OC's absorption index based on field measurements, we quantified the OC and BC API effect on surface ozone by the WRF-Chem model. The API effect and its uncertainties of OC aerosols were evaluated using the high and low absorption values that have been reported in previous studies. Results showed that, in terms of the pollution periods in NCP, removing all the OC aerosol from the atmosphere could increase the daytime maximum daily average 8-h (MDA8) O3. In this episode, the average (extreme) MDA8 O3 increased by 0.7–2.4 ppb (1.1–3.7 ppb), accounting for 1.5%–5.3% (2.4%–8.8%) of ozone concentration, comparable to that by BC of 2.0 ppb (3.3 ppb), accounting for 4.4% (7.8%), which means the OC's API effect was 35%–120% of BC's API effect on surface ozone in this case. The results also indicated a fact that, though OC has a lower light absorption rate than BC, the API efficiency of OC on surface ozone when reducing aerosols could be compensated by a higher portion of OC aerosols and higher light absorption efficiency due to much more OC was distributed on higher altitude (especially 1–3 km) than BC aerosols, which result in larger ozone changes in both the low troposphere and surface.

Photochemical degradation in natural attenuation of characteristics of petroleum hydrocarbons (C10-C40) in crude oil polluted soil by simulated long term solar irradiation

Photodegradation process plays an important role in the natural attenuation of petroleum hydrocarbons (PHs) in oil contaminated soil. The photodegradation characteristics of PHs (C10-C40) in topsoil of crude oil contaminated soil irradiated by simulated sunlight in 280 d without microbial action were investigated. The results showed that photodegradation rate of PHs was increased with increasing the light intensity and decreased with increasing the initial concentration of PHs. Moreover, the photodegradation capacity of tested PHs was relevant to the length of carbon chain. The photodegradation rates of C10-C20 were higher than that of C21-C40 in photoperiod. C21-C40 showed an obvious trend of photodegradation after 56 d, although their photodegradation rates were less than 20% at the early stage. And, the redundancy analysis indicated that lighting time was the primary factor for photodegradation of PHs under abiotic conditions. The photodegradation rate was well interpreted by a two-stage, first-order kinetic law with a faster initial photolysis rate. The EPR spectrums showed that simulated solar irradiation accelerated the generation of superoxide radicals, which could react with PHs in soil. Also, the function groups in PHs polluted soil were changed after light exposure, which might imply the possible photodegradation pathway of PHs.

Indirect photolysis of cysteine and thiourea in the aquatic environment

The aim of this research is to study the thiourea (TU) and cysteine (Cys) photochemical transformations in aqueous solutions on model systems in order to estimate their role in the processes arising in the aquatic system. So, both thiols, TU and Cys, have been subjected to indirect photolysis with OH radicals, generated by the photodissociation of hydrogen peroxide on irradiation with different artificial light sources. It has been found that the indirect photolysis rates of TU and Cys depend on the chemical nature and initial concentrations of the substrate as well as H2O2. TU and Cys undergo photochemical transformations via very complex radical mechanisms.

Relationships between ozone and particles during air pollution episodes in arid continental climate

For human health, tropospheric ozone (O3), particles (PM2.5 and PM10, particles with aerodynamic diameter <2.5 and 10 μm), and nitrogen dioxide (NO2) are the most harmful air pollutants. We have investigated the simultaneity of PM2.5, PM10, NO2, and O3 occurrence by using data from 21 ground-based monitoring stations in a megacity of the Middle East, Tehran (Iran), between 2011 and 2022. In Tehran, the daily PM2.5 (21–45 μg m−3), PM10 (52–108 μg m−3) and NO2 (75–146 μg m−3) mean concentrations have largely exceeded the 24-h limit value established by the 2021 World Health Organization for the protection of human health, i.e., 15, 45 and 25 μg m−3, respectively, in particular for NO2. The ground-level daily O3 concentrations ranged from 26 to 47 μg m−3. Changes in aerosols burden (e.g., PM2.5 and PM10) affect surface O3 through changes in aerosol chemistry and photolysis rates. Following the dust events and for the days with PM2.5 and PM10 exceeding 50 and 100 μg m−3, respectively, we observed a reduction of surface O3 levels (- 30.0% and - 13.5%), concurrently to surface NO2 (+27.9% and +16.6%) levels increases compared to the non-dusty clear-sky days over Tehran city. Surface O3 formation is suppressed under high particulate matter (PM) levels in the atmosphere, in particular PM2.5, likely due to weakened photochemical reactions (lower solar radiation and air temperature), dilution effect, and heterogeneous chemical processes occurring onto the PM2.5 surface (reactive uptake of nitrogen oxides, NOx, and hydrogen oxide radicals, HOx). To achieve O3-PM co-improvement in cities, we recommend reductions in NOx emissions concurrently with significant reductions in PM and Volatile Organic Compounds emissions, for instance by suitable greening and re-naturing programs.

Degradation and Defluorination of Per- and Polyfluoroalkyl Substances by Direct Photolysis at 222 nm.

The susceptibility of 19 representative per- and polyfluoroalkyl substances (PFAS) to direct photolysis and defluorination under far-UVC 222 nm irradiation was investigated. Enhanced photolysis occurred for perfluorocarboxylic acids (PFCAs), fluorotelomer unsaturated carboxylic acids (FTUCAs), and GenX, compared to that at conventional 254 nm irradiation on a similar fluence basis, while other PFAS showed minimal decay. For degradable PFAS, up to 81% of parent compound decay (photolysis rate constant (k222nm) = 8.19-34.76 L·Einstein-1; quantum yield (Φ222nm) = 0.031-0.158) and up to 31% of defluorination were achieved within 4 h, and the major transformation products were shorter-chain PFCAs. Solution pH, dissolved oxygen, carbonate, phosphate, chloride, and humic acids had mild impacts, while nitrate significantly affected PFAS photolysis/defluorination at 222 nm. Decarboxylation is a crucial step of photolytic decay. The slower degradation of short-chain PFCAs than long-chain ones is related to molar absorptivity and may also be influenced by chain-length dependent structural factors, such as differences in pKa, conformation, and perfluoroalkyl radical stability. Meanwhile, theoretical calculations indicated that the widely proposed HF elimination from the alcohol intermediate (CnF2n+1OH) of PFCA is an unlikely degradation pathway due to high activation barriers. These new findings are useful for further development of far-UVC technology for PFAS in water treatment.