Photolysis Rates Research Articles

Photocatalytic degradation of microcystins from a field-collected cyanobacterial assemblage by 3D printed TiO2 structures using artificial versus solar irradiation

Microcystins (MCs) from freshwater cyanobacteria cause adverse effects to humans and ecological receptors through multiple exposure routes requiring adaptable and diverse treatment technologies. Photocatalysis of MCs using TiO2 is a promising technology; however, TiO2 photocatalysts as unbound nanoparticles in suspension are impractical to deploy. 3D Printing (3DP) provides a means to immobilize TiO2, producing deployable photocatalyst structures with extensive geometric freedom. The objective of this proof-of-concept experiment was to incrementally increase the environmental complexity (e.g., broad-spectrum fluorescent lamps and outdoor solar; filtered cell lysate and algal assemblage as the source of MCs) while comparing photocatalysis rates of MCs by 3DP TiO2 structures using polylactic acid (PLA) as the binder. Degradation half-lives of MCs were shorter in TiO2 embedded in 3DP PLA relative to PLA-only controls with differences in half-lives ranging from 3.6 to 10h. The one exception was the outdoor solar and an algal assemblage, where significant differences could not be discerned due to the already rapid photolysis rates. Ultimately, photocatalysis rates (half-life = 1.9–11.6h) were comparable to those previously published for TiO2 3DP structures in a laboratory environment and TiO2 fixed-films (half-life = 2–13h) demonstrating feasibility of 3DP to immobilize TiO2 photocatalysts under a range of conditions. This is the first time that MC concentrations from a field-collected HAB were photocatalytically degraded in both solar simulated light and sunlight using a custom-made advanced photocatalytic nano-composite with enhanced performance through high surface area design enabled by 3D printing. These data inform future development of scalable, retrievable, and operationally flexible structures with immobilized TiO2.

The effects of physical form, moisture, humic acids, and mixtures on the photolysis of insensitive munitions compounds

The explosive formulations IMX-101 and IMX-104 are replacing conventional explosives in munitions, making them safer to transport and handle. However, munitions manufacturing and military training can lead to the environmental release of constituent insensitive munitions compounds (IMCs) such as 2,4-dinitroanisole (DNAN), 3-nitro-1,2,4-triazol-5-one (NTO), and nitroguanidine (NQ). These IMCs absorb ultraviolet light and transform photochemically into products with potentially greater toxicity. This study explores the effects of physical form, moisture, humic acids, and compound mixtures on the photolysis of solid and dissolved IMCs under UV-A (350 nm) and UV-B (300 nm) light. Irradiation of dry vs. moist solid IMC crystals yielded few measured products, and while photolysis rates were not significantly different, they were orders of magnitude slower than for aqueous IMCs. There was no significant difference in photolysis rates for aqueous IMCs irradiated with 0, 0.4, and 4 mg L-1 humic acids, but 40 and 400 mg L-1 humic acids inhibited NTO and enhanced NQ photolysis. In two- and three-component aqueous mixtures, DNAN photolysis was enhanced by NQ (at 300 and 350 nm) and NTO (at 350 nm); NTO photolysis was inhibited by DNAN and enhanced by NQ (both at 300 nm); and NQ photolysis was inhibited by both DNAN and NTO (both at 300 and 350 nm). The average quantum yields of the IMCs irradiated alone in solution were: 8.29 × 10–5 (300 nm) and 6.26 × 10–5 (350 nm) for DNAN; 5.76 × 10–4 (300 nm) and 1.74 × 10–4 (350 nm) for NTO; and 1.01 × 10–2 (300 nm) and 1.14 × 10–4 (350 nm) for NQ. Although organic and inorganic products were detected in the mixtures, an average of 15–35 % of the theoretical starting IMC masses (as nitrogen) was not accounted for. Overall, aqueous IMCs transformed 4–48 times faster than the solid IMCs, but the environmentally-relevant conditions tested were found to play a minor role in IMC photolysis.

Design and Characterization of a New Quartz Smog Chamber System for Studying the Atmospheric Effects of Vehicle Emissions on Plateaus

Since the 1960s, smog chambers have been an important tool for studying air pollution, and many indoor and outdoor smog chambers have been developed both domestically and internationally. However, all of these chambers are located at altitudes below 1500 meters, only simulating atmospheric conditions in low-altitude plains. Moreover, most are made of polytetrafluoroethylene (PTFE), resulting in a higher wall deposition effect. To simulate the evolution of atmospheric pollution in high-altitude regions, we developed the world's highest-altitude quartz smog chamber, located in Kunming at an elevation of 1900 meters. The chamber is a 3.375m³ cube constructed from 5mm quartz glass and features controlled temperature (0°C to 40°C) and relative humidity (2%-95%). We conducted a comprehensive characterization of the chamber, including tests for temperature and humidity stability, mixing stability, pressure resistance and sealing, light intensity measurement and environmental light matching, and background pollutant and wall loss assessments. The characterization results indicate excellent performance in simulating sunlight and controlling background pollutants. The NO2 photolysis rate is adjustable, ranging from 2.03×10⁻³s⁻1 to 5.87×10⁻³s⁻1. Under dry conditions, after 6 hours of photooxidation, the detected O3 formation rate was approximately 1.05 ppb/h, with a particulate mass concentration around 0.12 μg/m³. The reactor withstands pressures exceeding 1.5 bar, and at this pressure, the leak rate was measured at 1.1‰. Validation using the toluene-NO₂ system showed that indoor mixing reached equilibrium in about four minutes. The wall loss rate for SWFU-HAP particles at 25°C and RH <10% was 0.066 h⁻1, which is 70% lower compared to other chambers, while at RH = 50%, the wall loss rate was 0.137 h⁻1. These results demonstrate the superior performance of our system, meeting the high standards required for high-altitude vehicle exhaust aerosol emissions research and the investigation of the formation mechanisms of vehicle exhaust in high-altitude atmospheric environments.

Black Carbon Radiative Impacts on Surface Atmospheric Oxidants in China with WRF-Chem Simulation

Black carbon (BC) changes the radiative flux in the atmosphere by absorbing solar radiation, influencing photochemistry in the troposphere. To evaluate the seasonal direct radiative effects (DREs) of BC and its influence on surface atmospheric oxidants in China, the WRF-Chem model was utilized in this study. The simulation results suggested that the average annual mean values of the clear-sky DREs of BC at the top of the atmosphere, in the atmosphere and at the surface over China are +2.61, +6.27 and −3.66 W m−2, respectively. Corresponding to the seasonal variations of BC concentrations, the relative changes of the mean surface photolysis rates (J[O1D], J[NO2] and J[HCHO]) in the four seasons range between −3.47% and −6.18% after turning off the BC absorption, which further leads to relative changes from −4.27% to −6.82%, −2.14% to −4.40% and −0.47% to −2.73% in hydroxyl (OH) radicals, hydroperoxyl (HO2) radicals and ozone (O3), respectively. However, different from the relative changes, the absolute changes in OH and HO2 radicals and O3 after turning off BC absorption show discrepancies among the different seasons. In the North China Plain (NCP) region, O3 concentration decreases by 1.79 ppb in the summer, which is higher than the magnitudes of 0.24–0.88 ppb in the other seasons. In southern China, the concentrations of OH and HO2 radicals reach the maximum decreases in the spring and autumn, followed by those in the summer and winter, which is due to the enhancement of solar radiation and the summer monsoon. Thus, BC inhibits the formation of atmospheric oxidants, which further weakens the atmospheric oxidative capacity.

Kinetic modelling of ozonation and photolytic ozonation of metronidazole removal from water

This work addresses the ozonation, photolysis, and photolytic ozonation of metronidazole (MTZ), a widely used antibiotic frequently detected in urban wastewater. A UVA source emitting radiation between 300 and 400 nm was utilized. The presence of scavengers such as t-butanol and sodium azide confirmed the role of hydroxyl radicals in both ozonation and photolysis processes. Conversely, singlet oxygen did not influence the photolytic processes. The average quantum yields of MTZ and ozone were determined to be 1.2 × 10−3 and 0.72 mol/Einstein, respectively, for the 300–400 nm wavelength range. In direct MTZ photolysis, a stoichiometric ratio of 0.34 mol of hydroxyl radicals formed per mol of photolyzed MTZ was observed. However, the effects of hydroxyl radicals on the MTZ photolytic rate were only significant after 45 min of reaction time. Using rate constant data from literature and quantum yields calculated in this study, a kinetic model for both MTZ ozonation and photolytic ozonation was proposed, enabling the prediction of MTZ conversion and degradation rates. This model includes three intermediate compounds that also consume ozone and hydroxyl radicals. The results show that experimental and calculated concentrations of MTZ are within an error margin of less than 14 % in all cases.

Disentangling the effects of meteorology and emissions from anthropogenic and biogenic sources on the increased surface ozone in Eastern China

China's Clean Air Actions have substantially improved ambient PM2.5 air quality since 2013. However, ozone (O3) pollution in urban areas has worsened in recent years, particularly in the eastern region. The formation of O3 in these high emission areas is highly complex and regulated by numerous factors. Utilizing the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem), this study conducted a comprehensive analysis through nine sensitivity experiments for the years 2013 and 2017, aimed at disentangling the relative contributions of major factors (e.g., meteorological factors, anthropogenic emissions, biogenic emissions, and aerosol feedback mechanisms) to the observed O3 concentration trends in Jiangsu, a developed region of China with increasing trend of O3 level. Our findings indicate a pronounced increase in mean daily maximum 8-h average (MDA8) O3 levels in the economically vibrant southern Jiangsu, contrasted with a decrease in the less developed northern regions. The study identifies anthropogenic emissions change as the primary driver of O3 variations, with significant impacts also attributed to meteorological conditions and aerosol feedback effects, while biogenic emission shifts play a lesser role. In terms of meteorological factors, we discovered that the alteration in meteorological thermal factors (enhanced solar radiation and temperatures) in 2017, compared to 2013, exerted a more pronounced influence on the formation of O3 than the change in thermally driven dynamic factors (boundary layer height and wind speed). Moreover, the study observes a shift in O3 formation sensitivity from VOC-sensitive to transitional or NOX-sensitive regimes, signifying a notable transformation in the regional atmospheric chemistry conducive to O3 generation. Aerosol feedback effects, through complex pathways including photolysis rate alterations and modifications in the vertical O3 distribution, further compound the challenge of mitigating O3 levels. Our research underscores the necessity for adaptive, region-specific strategies to mitigate O3 pollution, providing potential insights for policymakers to formulate effective control measures.

Photolysis of p-phenylenediamine rubber antioxidants in aqueous environment: Kinetics, pathways and their photo-induced toxicity

The widespread use of rubber antioxidants, especially p-phenylenediamines (PPDs), has raised increasing concerns about their risk assessment. However, there is a notable lack of research on their transformation products (TPs). Photolysis, influenced by active components, plays a significant role in the environmental fates of PPDs. This study investigated four emerging PPDs (N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine (6PPD), N, N′-diphenyl-p-phenylenediamine (DPPD), N-isopropyl-N′-phenyl-p-phenylenediamine (IPPD), and N-cyclohexyl-N′-phenyl-p-phenylenediamine (CPPD)) through a combination of experiments (photolysis kinetics, quenching experiments, acute toxicity test to Vibrio Fischeri (V. fischeri) and identification of photolytic products) and theoretical calculations. The results revealed different pathways for indirect photolysis mediated by the hydroxyl radicals (•OH) and singlet oxygen (1O2) of DPPD and IPPD under simulated sunlight irradiation. The effects of dissolved organic matter (DOM) and fulvic acid (FA) on the rates of photolysis of PPDs highlighted the complex interactions among the molecular structure, light absorption properties, and environmental variables. Quenching for reactive oxygen species (ROS) reduced photo-induced toxicity, whereas the addition of DOM and FA increased it, suggesting the crucial role of ROS in the formation of more toxic photolytic products. The study of photolysis pathways and the evaluation of the health risks provide a comprehensive understanding of the environmental effects of these pollutants.

Photolysis of dinotefuran and nitenpyram in water and ice phase: Influence mechanism of temperature over photolysis

Neonicotinoids are widely used pesticides around the world, but the photolysis of neonicotinoids in cold agricultural region are still in blank. This paper aimed to study the influence of cold temperature over photolysis of neonicotinoids. To this end, the photolysis rates and photoproducts of dinotefuran and nitenpyram in water, ice and freeze-thawing condition were determined. Coupled with quantum chemistry calculation, the influence mechanisms of temperature and medium were investigated. The results showed the photolysis rates of neonicotinoids in water condition slightly declined with the lowered temperature due to the photolysis reactions were endothermic reactions. However, the photolysis rates increased by 89.8 %, 59.2 %, 49.4 % and 9.5 % for dinotefuran and nitenpyram in ice and thawing condition, respectively. This phenomenon was posed by the concentration-enhancing effect and change of photo-chemical properties of neonicotinoids in ice condition, which included lowered bond cleavage energy, lowered first excited singlet state energy and expanded light absorption range. The photolysis pathways of the two neonicotinoids did not change in different medium, but the concentration of carboxyl products was relatively higher than that of water condition due to the more amounts of reactive oxygen species in ice medium, which might increase the secondary pollution risk after ice-off in spring due to the higher ecotoxicity to nontarget organism of these photoproducts. The influence of cold temperature and medium change should be considered for the environmental fate and risk assessment of neonicotinoids in cold agricultural region.

Photolytic Mass Loss of Humic Substances Measured with a Quartz Crystal Microbalance.

Laboratory studies have shown that photolytic mass loss can be a significant sink for secondary organic aerosol (SOA). Here, we use a quartz crystal microbalance to measure mass loss of Suwannee River Humic Acid (SRHA) and Suwannee River Fulvic Acid (SRFA), surrogates for SOA, exposed to 254, 300, and 405 nm radiation over the course of 24 h. We find that the photolytic mass loss rates of these materials are comparable to those for laboratory-generated limonene and toluene SOA material from the study of Baboomian et al, ACS Earth Space Chem. 2020, 4, 1078. Scaling our results to ambient conditions, we estimate that humic substances in aerosols can lose as much as 8% by mass in the first day of exposure in the atmosphere, equivalent to 0.025% of J NO2 , the photolysis rate of nitrogen dioxide. By using zero air instead of nitrogen, we also find that the presence of oxygen accelerates the photolytic mass loss rate by a factor of 2 to 4 at all wavelengths suggesting a potential role for reactive oxygen species. UV photolysis of an aqueous SRFA solution demonstrated both photobleaching at UV wavelengths and photoenhancement at visible wavelengths. Ultrahigh-resolution mass spectrometric analysis showed that condensed-phase SRFA photolysis led to decreased intensity in the 100-300 m/z range while aqueous SRFA photolysis resulted in an increase in intensity in the same range. This work reaffirms that photolytic mass loss is a potentially significant sink for SOA, but only on the time scale of a day or two and demonstrates that SRHA and SRFA are suitable surrogates for atmospheric SOA with respect to photolytic mass loss.

Quantifying HONO Production from Nitrate Photolysis in a Polluted Atmosphere.

The photolysis of particulate nitrate (pNO3-) has been suggested to be an important source of nitrous acid (HONO) in the troposphere. However, determining the photolysis rate constant of pNO3- (jpNO3-) suffers from high uncertainty. Prior laboratory measurements of jpNO3- using aerosol filters have been complicated by the "shadow effect"─a phenomenon of light extinction within aerosol layers that potentially skews these measurements. We developed a method to correct the shadow effect on the photolysis rate constant of pNO3- for HONO production (jpNO3-→HONO) using aerosol filters with identical chemical compositions but different aerosol loadings. We applied the method to quantify jpNO3-→HONO over the North China Plain (NCP) during the winter haze period. After correcting for the shadow effect, the normalized average jpNO3-→HONO at 5 °C increased from 5.89 × 10-6 s-1 to 1.72 × 10-5 s-1. The jpNO3-→HONO decreased with increasing pH and nitrate proportions in PM2.5 and had no correlation with nitrate concentrations. A parametrization for jpNO3-→HONO was developed for model simulation of HONO production in NCP and similar environments.

Characterization of a new Teflon chamber and on-line analysis of isomeric multifunctional photooxidation products

Abstract. The photooxidation of volatile organic compounds (VOCs) in the troposphere has important implications for air quality, weather, and climate. A deeper understanding of the underlying mechanisms can be achieved by studying these reactions under controlled conditions and analysing the emerging photooxidation products. This requires dedicated laboratory infrastructure as well as sensitive and selective analytical techniques. Here, we constructed a new 300 L indoor Teflon atmospheric simulation chamber as part of the Bayreuth ATmospheric simulation CHambers (BATCH) infrastructure. The chamber was irradiated by a bandpass-filtered solar simulator that enabled experiments with realistic photon fluxes and OH radical concentrations. It was coupled to a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) and a solid-phase microextraction–gas chromatography–mass spectrometry (SPME-GC-MS) system for the on-line analysis of the precursor VOC and its oxidation products in the gas phase. As part of the SPME-GC-MS method, multifunctional oxygenated compounds (carbonyls, alcohols, carboxylic acids) were derivatized with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N-trimethylsilyl-N-methyltrifluoroacetamide (MSTFA). We designed a permeation source for the on-line addition of internal standards to improve method reproducibility. The joint setup was tested and validated by studying the OH-radical-induced photooxidation of toluene, one of the most abundant aromatic hydrocarbons in the atmosphere. For chamber characterization, we first derived the photolysis rates for several typical toluene products in the irradiated BATCH Teflon chamber (1.77 × 10−8–3.02 × 10−4 s−1). Additionally, wall loss rates were determined empirically (4.54 × 10−6–8.53 × 10−5 s−1) and then parameterized according to fundamental molecular properties. For the cresols, we compiled a weighted calibration factor for the PTR-ToF-MS, taking into account isomer-specific sensitivities as well as the relative distribution as determined by the SPME-GC-MS. The weighted calibration improved the instrumental agreement to 14 %, whereas the PTR-ToF-MS overestimated the sum of the isomers by 31 % compared to the SPME-GC-MS concentrations when using the averaged calibration factor. Thus, the combined data set offered insight into both temporal trends and the isomeric composition. Finally, we conducted six toluene photooxidation experiments to evaluate the ring-retaining first-generation products. Based on the loss-corrected concentrations, we derived formation yields for o-cresol (8.0 ± 1.8 %), m-cresol (0.4 ± 0.1 %), p-cresol (2.4 ± 0.6 %), benzyl alcohol (0.5 ± 0.1 %), and benzaldehyde (4.6 ± 1.7 %) under NOx-free conditions at T = 298 ± 1 K. These yields are consistent with previous studies and therefore serve as proof of concept for our applied methods.

Photolytic degradation of commonly used pesticides adsorbed on silica particles

The currently used pesticides are mostly semi-volatile organic compounds. As a result, a fraction of them can be adsorbed on atmospheric aerosol surface. Their atmospheric photolysis is poorly documented, and gaps persist in understanding their reactivity in the particle phase. Laboratory experiments were conducted to determine the photolysis rates of eight commonly used pesticides (i.e., cyprodinil, deltamethrin, difenoconazole, fipronil, oxadiazon, pendimethalin, permethrin, and tetraconazole) using a flow reactor. These pesticides were individually adsorbed on hydrophobic silica particles and exposed to a filtered xenon lamp to mimic atmospheric aerosols and sunlight irradiation, respectively.The estimated photolysis rate constants ranged from less than (3.4 ± 0.3) × 10−7 s−1 (permethrin; >47.2 days) to (3.8 ± 0.2) × 10−5 s−1 (Fipronil; 0.4 days), depending on the considered compound. Moreover, this study assessed the influence of pesticide mixtures on their photolysis rates, revealing that certain pesticides can act as photosensitizers, thereby enhancing the reactivity of permethrin and tetraconazole. This study underscores the importance of considering photolysis degradation when evaluating pesticide fate and reactivity, as it can be a predominant degradation pathway for some pesticides. This contributes to an enhanced understanding of their behavior in the atmosphere and their impact on air quality.

Resetting tropospheric OH and CH4 lifetime with ultraviolet H2O absorption.

The decay of methyl chloroform, a banned ozone-depleting substance, has provided a clear observational metric of mean tropospheric hydroxyl radical (OH) abundance. Almost all current global chemistry models calculate about 15% too much OH and thus too rapid methane loss. Methane is a short-lived climate forcer, critical to achieving global warming targets, and this error affects our model projections of climate change. New observations of water vapor absorption in the ultraviolet region (290 to 350 nanometers) imply reductions in sunlight with key photolysis rates decreasing by 8 to 12% in the near-surface tropical atmosphere. Incorporation of this new mechanism in a chemistry-transport model reduces OH and methane loss by only 4%, but combined with other proposed mechanisms, such as tropospheric halogen chemistry (7%), we may be able to resolve this conundrum.

Photochemical transformation of liquid crystal monomers in simulated environmental media: Kinetics, mechanism, toxicity variation and QSAR modeling

Liquid crystal monomers (LCMs) are a new class of emerging pollutants with high octanol-water partition coefficients; however, their transformation behavior and associated risk to environments with high organic matter content has rarely been reported. In this study, we investigated the photodegradation kinetics, mechanism, and toxicity variation of 23 LCMs on leaf wax models (e.g., organic solvents methanol and n-hexane). The order of the photolysis rates of these LCMs were biphenylethyne LCMs > phenylbenzoate LCMs > diphenyl/terphenyl LCMs under simulated sunlight, while the phenylcyclohexane LCMs were resistant to photodegradation. The phenylbenzoate and biphenylethyne LCMs mainly undergo direct photolysis, while the diphenyl/terphenyl LCMs mainly undergo self-sensitized photolysis. The main photolysis pathways are the cleavage of ester bonds for phenylbenzoate LCMs, the addition, oxidation and cleavage of alkynyl groups for biphenylethyne LCMs, and the cleavage/oxidation of chains attached to phenyls and the benzene ring opening for diphenyl/terphenyls LCMs. Most photolysis products remained toxic to aquatic organisms to some degree. Additionally, two quantitative structure-activity relationship models for predicting kobs of LCMs in methanol and n-hexane were developed, and employed to predict kobs of 93 LCMs to fill the kobs data gap in systems mimicking leaf surfaces. These results can be helpful for evaluating the fate and risk of LCMs in environments with high content of organic phase.

Deciphering the seasonal dynamics of multifaceted aerosol-ozone interplay: Implications for air quality management in Eastern China

We employed an enhanced WRF-Chem to investigate the discrete mechanisms of aerosol-radiation-feedback (ARF), extinction-photochemistry (AEP), and heterogeneous-reactions (AHR) across different seasons in eastern China, aiming to assess the synergistic effects arising from the simultaneous operation of multiple processes on O3 and PM2.5. Our findings demonstrated that ARF fostered the accumulation of pollutants and moisture, initiating two distinct feedback mechanisms concerning O3. The elevation in the NO/NO2 ratio amplified O3 consumption. Increased near-surface moisture diminished upper-level cloud formation, thereby enhancing photolysis rates and O3 photochemical production. The pronounced impact of heightened NO/NO2 on O3 led to a decrease of 0.1–2.7 ppb. When decoupled from ARF, AEP led to a more significant reduction in photolysis rates, resulting in declines in both O3 and PM2.5, except for an anomalous increase observed in summer, with O3 increasing by 1.6 ppb and PM2.5 by 2.5 μg m−3. The heterogeneous absorption of hydroxides in spring, autumn, and winter predominantly governed the AHR-induced variation of O3, leading to a decrease in O3 by 0.7–1 ppb. Conversely, O3 variations in summer were primarily dictated by O3-sensitive chemistry, with heterogeneous absorption of NOy catalyzing a decrease of 2.4 ppb in O3. Furthermore, AHR accentuated PM2.5 by facilitating the formation of fine sulfates and ammonium while impeding nitrate formation. In summer, the collective impact of ARF, AEP, and AHR (ALL) led to a substantial reduction of 6.2 ppb in O3, alleviating the secondary oxidation of PM2.5 and leading to a decrease of 0.3 μg m−3 in PM2.5. Conversely, albeit aerosol substantially depleted O3 by 0.4–4 ppb through their interactions except for summer, aerosol feedback on PM2.5 was more pronounced, resulting in a significant increase of 1.7–6.1 μg m−3 in PM2.5. Our study underscored the seasonal disparities in the ramifications of multifaceted aerosol-ozone interplay on air quality.

Elucidating the photodegradation mechanism of octylisothiazolinone and dichlorooctylisothiazolinone in surface water: An in-depth comprehensive analysis

Octylisothiazolinone (OIT) and Dichlorooctylisothiazolinone (DCOIT), widely used antibacterial agents in coatings, have seen a sharp increase in use in response to the Coronavirus disease 2019 (Covid-19) pandemic, ultimately leading to their increase in the aquatic environment. However, their photodegradation process in surface water is still unclear. The purpose of this study is to investigate the photodegradation kinetics and mechanisms of OIT and DCOIT in natural water environments. Under simulated solar irradiation, they undergo direct photolysis in both natural freshwater and seawater mainly via their excited singlet states, while no self-sensitization photolysis was observed. The direct photolysis rate constants of OIT and DCOIT were 1.19 ± 0.07 and 0.57 ± 0.03 h−1, respectively. In addition, dissolved organic matter (DOM), NO3− and Cl− in natural waters did not contribute significantly to the photodegradation, and the light screening effect of DOM was identified as the main inhibiting factor. The photodegradation half-life of OIT was estimated to be 0.66 to 1.69 days, while the half-life of DCOIT was as high as 20.9 days during winter in surface water at 30°N latitude. Ring opening of the N-S bond and covalent bond breaking between CN are the main pathways for the photodegradation of OIT and DCOIT, which is verified by density-functional theory calculations. Ecological Structure Activity Relationships (ECOSAR) results indicate that OIT and DCOIT have “Very Toxic” biological toxicity, and the acute toxicity of their products is significantly reduced. It is noteworthy that the toxicity of the products of DCOIT is generally higher than that of OIT, and the chronic toxicity of most of the products is still above the “Toxic” level. Therefore, an in-depth understanding of the photodegradation mechanisms of OIT and DCOIT in aqueous environments is crucial for accurately assessing their ecological risks in natural water environments.

New insights into the environmental photochemistry of common-use antibiotics in ice and in water: A comparison of kinetics and influencing factors

The photochemistry of organic contaminants present in ice is receiving growing attention, given the wide presence of ice during winter in temperate regions as well as Polar and mountain environments. Differences between ice photochemistry and aqueous photochemistry, however, influence the quantitative fate and transformation of organic chemicals present in freshwater, marine and ice-cap environments and these differences need to be explored. Here we comparatively studied the ice and aqueous photochemistry of three antibiotics [levofloxacin (LVX), sulfamerazine (SM), and chlortetracycline (CTC)] under the same simulated sunlight (λ > 290 nm). Their photodegradation in ice/water followed pseudo-first-order kinetics, whereby the photolytic rates of LVX in ice and water were found to be similar, SM photodegraded faster in ice, while CTC underwent slower photodegradation in ice. Whether individual antibiotics underwent faster photodegradation in ice or not depends on the specific concentration effect and cage effect coexisting in the ice compartment. In most cases, the fastest photodegradation occurred in freshwater ice or in fresh water, and the slowest photolysis occurred in pure-water ice or in pure water. This can be attributed to the effects of key photochemical reactive constituents of Cl−, HA, NO3− and Fe(III), that exist in natural waters. These constituents at certain levels showed significant effects (P < 0.1) on the photolysis, not only in ice but also in water. However, these individual constituents at a given concentration, serve to either enhance or suppress the photoreaction, depending on the specific antibiotic and the matrix type (e.g., ice or aqueous solution). Furthermore, extrapolation of the laboratory findings to cold environments indicate that pharmaceuticals present in ice will have a different photofate compared to water. These results are of particular relevance for those regions that experience seasonal ice cover in fresh water and coastal marine systems.

Photodegradation of the novel herbicide pyraclonil in aqueous solution: Kinetics, identification of photoproducts, mechanism, and toxicity assessment

Pyraclonil is a new type of pyrazole herbicide, whose photochemical fate in aqueous solution has not been reported yet. In this study, effects on the photolysis rate such as light source, pH, NO3−, Fe3+, fulvic acid (FA) and riboflavin (RF) were investigated. Pyraclonil photodegraded in pure water under both UV and simulated sunlight with half-lives of 32.29 min and 42.52 h, respectively. Under UV, the degradation rate of pyraclonil in pH 4 solution (0.0299 ± 0.0033 min−1) was about twice higher than that in pH 9 (0.0160 ± 0.0063 min−1). Under simulated sunlight, low concentration (0.1–1 mg/L) of FA, NO3−, Fe3+ and RF noticeably promoted the photodegradation of pyraclonil. Then, with the combination of experimental UPLC-Q-TOF/MS and computational calculation of density functional theory (DFT), fourteen transformation products (TPs) of pyraclonil were identified with possible mechanism of C–N bond cleavage, photorearrangement, demethylation, hydroxylation and oxidation. Additionally, acute toxicity assessment was conducted through ECOSAR prediction and laboratory bioassays. The prediction results indicated that toxicity of TP157 to daphnid and green algae was 1.3 and 1.4 times higher than that of the parent, respectively. The bioassay results indicated that toxicities of TP157 and TP263 to C. vulgaris were about 1.6 and 5.9 times higher than that of the parent, respectively. The results provided a reference for elucidating the potential hazards of pyraclonil to non-target organisms and promoting its rational use.

Deciphering the Role of Microbial Extracellular and Intracellular Organic Matter in Antibiotic Photodissipation: Molecular and Fluorescent Profiling under Natural Radiation.

This study addresses existing gaps in understanding the specific involvement of dissolved organic matter (DOM) fractions in antibiotic photolysis, particularly under natural conditions and during DOM photobleaching. Employing fluorescent, chemical, and molecular analysis techniques, it explores the impact of extracellular and intracellular organic matter (EOM and IOM) on the photodissipation of multiclass antibiotics, coupled with DOM photobleaching under natural solar radiation. Key findings underscore the selective photobleaching of DOM fractions, propelled by distinct chemical profiles, influencing DOM-mediated antibiotic photolysis. Notably, lipid-like substances dominate in the IOM, while lignin-like substances prevail in the EOM, each uniquely responding to sunlight and exhibiting selective photobleaching. Sunlight primarily targets fulvic acid-like lignin components in EOM, contrasting the initial changes observed in tryptophan-like lipid substances in IOM. The lower photolability of EOM, attributed to its rich unsaturated compounds, contributes to an enhanced rate of indirect antibiotic photolysis (0.339-1.402 h-1) through reactive intermediates. Conversely, the abundance of aliphatic compounds in IOM, despite it being highly photolabile, exhibits a lower mediation of antibiotic photolysis (0.067-1.111 h-1). The triplet state excited 3DOM* plays a pivotal role in the phototransformation and toxicity decrease of antibiotics, highlighting microbial EOM's essential role as a natural aquatic photosensitizer for water self-purification. These findings enhance our understanding of DOM dynamics in aquatic systems, particularly in mitigating antibiotic risks, and introduce innovative strategies in environmental management and water treatment technologies.

Interplay of Luminophores and Photoinitiators during Synthesis of Bulk and Patterned Luminescent Photopolymer Blends.

Four-dimensional printing with embedded photoluminescence is emerging as an exciting area in additive manufacturing. Slim polymer films patterned with three-dimensional lattices of multimode cylindrical waveguides (waveguide-encoded lattices, WELs) with enhanced fields of view can be fabricated by localizing light as self-trapped beams within a photopolymerizable formulation. Luminescent WELs have potential applications as solar cell coatings and smart planar optical components. However, as luminophore-photoinitiator interactions are expected to change the photopolymerization kinetics, the design of robust luminescent photopolymer sols is nontrivial. Here, we use model photopolymer systems based on methacrylate-siloxane and epoxide homopolymers and their blends to investigate the influence of the luminophore Lumogen Violet (LV) on the photolysis kinetics of the Omnirad 784 photoinitiator through UV-vis absorbance spectroscopy. Initial rate analysis with different bulk polymers reveals differences in the pseudo-first-order rate constants in the absence and presence of LV, with a notable increase (∼40%) in the photolysis rate for the 1:1 blend. Fluorescence quenching studies, coupled with density functional theory calculations, establish that these differences arise due to electron transfer from the photoexcited LV to the ground-state photoinitiator molecules. We also demonstrate an in situ UV-vis absorbance technique that enables real-time monitoring of both waveguide formation and photoinitiator consumption during the fabrication of WELs. The in situ photolysis kinetics confirm that LV-photoinitiator interactions also influence the photopolymerization process during WEL formation. Our findings show that luminophores play a noninnocent role in photopolymerization and highlight the necessity for both careful consideration of the photopolymer formulation and a real-time monitoring approach to enable the fabrication of high-quality micropatterned luminescent polymeric films.