The photocatalytic degradation of the insecticide fenitrothion was performed in the water solution in the presence of TiO2 by UV illumination. NMR spectrocopy showed that the decomposition of the initial substrate and all intermediates formed to the mineralization end products is completed in 66.3 hours. This fact was used to establish the possible mechanisms of the degradation process. The obtained results show that this method may have an important application in the removal of fenitrothion from water.

Organic aerosol (OA) emitted from biomass burning (BB) impacts air quality and global radiation balance. However, the comprehensive characterization of OA remains poorly understood because of the complex evolutionary behavior of OA in atmospheric processes. In this work, smoke particles were generated from rice straw combustion. The effect of OH radicals photooxidation on size distribution, light absorption, and molecular compositions of smoke particles was systematically investigated. The results showed that the median diameters of smoke particles increased by a factor of approximately 1.2 after photooxidation. In the particle compositions, although both non-polar fractions (n-hexane-soluble organic carbon, HSOC) and polar fractions (water-soluble organic carbon, WSOC) underwent photobleaching after aging, the photobleaching properties of HSOC (1.87–2.19) was always higher than that of WSOC (1.52–1.33). Besides, the light-absorbing properties of HSOC were higher than that of WSOC, showing a factor of approximately 1.75 times for mass absorption efficiency at 365 nm (MAE₃₆₅). Consequently, the simple forcing efficiency (SFE) caused by absorption showed that HSOC has higher radiation effects than WSOC. After photooxidation, the concentration of 16 PAHs in HSOC fractions significantly decreased by 15.3%–72.5%. In WSOC fractions, the content of CHO, CHONS, and CHOS compounds decreased slightly, while the content of CHON compounds increased. Meantime, the variations in molecular properties supported the decrease in light absorption of WSOC fractions. These results reveal the aging behavior of smoke particles, then stress the importance of non-polar organic fractions in particles, providing new insights into understanding the atmospheric pollution caused by BB smoke particles.

The plastic debris that washes ashore and litters the shoreline often undergoes weathering under sunlight exposure, such that it fragments to form nanoplastics and microplastics, but the fragmentation rate for many thermoplastics is unknown. In this study, three major thermoplastics were exposed to simulated sunlight in an accelerated weathering chamber to evaluate the speed of photooxidation-induced fragmentation. The initiation of photooxidation-induced fragmentation extrapolated from the accelerated weathering chamber to real sunlight exposure in South Korea followed the order of PS (< 1 year) > PP (< 2 years) > LDPE (> 3 years). The surface cracks created by photooxidation were not directly reflected in the initiation of fragmentation of thermoplastics. The initiation of fragmentation was faster in PS than other polymers, but the total abundance of particles produced, and increasing ratio (exposure/non-exposure) were comparable or lower than those of PP. The increasing ratio pattern between nanoplastics and small microplastics of PP differed noticeably from other polymers. The initiation of nanoplastic and small-microplastic fragmentation determined in this study will be useful for the further estimation of secondary microplastic production by weathering and thus for decision-making regarding methods for the timely removal of plastic litter in the environment.

Disastrous oil spills cause severe environmental issues. The shortcomings of current cleaning methods for remediating oil have prompted the latest research drive to create intelligent nanoparticles that absorb oil. We, therefore, synthesized 197 ± 50 nm floatable photoreactive hybrid nanoparticles with Ag–TiO₂ plasmonic photocatalyst (Eg = 3.08 eV) content to eliminate interfacial water pollutants, especially toluene-based artificial oil spill. We found that the composite particles have non-wetting properties in the aqueous media and float easily on the surface of the water due to the moderate hydrophobic nature (Θ = 113°) of the matrix of polystyrene, and these properties lead to elevated absorption of the interfacial organic pollutants (e.g., mineral oil). We showed that (28.5 mol%) divinylbenzene cross-linker content was required for adequate swelling capacity (2.15 g/g), whereas incorporated 15.8% Ag–TiO₂ content in the swollen particles was enough for efficient photodegradation of the artificial oil spill under 150 min LED light (λₘₐₓ = 405 nm) irradiation. The swollen polymer particles with embedded 32 ± 7 nm Ag–TiO₂ content increase the efficiency of photooxidation by increased the direct contact between both the photocatalysts and the artificial oil spill. Finally, it was also presented that the composite particles destroy themselves: after approximately one and a half months of continuous LED light irradiation, the organic polymer component of the composite was almost completely (88.5%) photodegraded by the incorporated inorganic photocatalyst particles.

Isoprene, formaldehyde and acetaldehyde are important reactive organic compounds which strongly impact atmospheric oxidation processes and formation of tropospheric ozone. Monsoon meteorology and the topography of Himalayan foothills cause surface emissions to get rapidly transported both horizontally and vertically, thereby influencing atmospheric processes in distant regions. Further in monsoon, Indo-Gangetic Plain is a major rice growing region of the world and daytime hourly ozone can frequently exceed phytotoxic dose of 40 ppb O₃. However, the sources and ambient variability of these compounds which are potent ozone precursors are unknown. Here, we investigate the sources and photochemical processes driving their emission/formation during monsoon season from a sub-urban site at the foothills of the Himalayas. The measurements were performed in July, August and September using a high sensitivity mass spectrometer. Average ambient mixing ratios (±1σ variability) of isoprene, formaldehyde, acetaldehyde, and the sum of methyl vinyl ketone and methacrolein (MVK+MACR), were 1.4 ± 0.3 ppb, 5.7 ± 0.9 ppb, 4.5 ± 2.0 ppb, 0.75 ± 0.3 ppb, respectively, and much higher than summertime values in May. For isoprene these values were comparable to mixing ratios observed over tropical forests. Surprisingly, despite occurrence of anthropogenic emissions, biogenic emissions were found to be the major source of isoprene with peak daytime isoprene driven by temperature (r ≥ 0.8) and solar radiation. Photo-oxidation of precursor hydrocarbons were the main sources of acetaldehyde, formaldehyde and MVK+MACR. Ambient mixing ratios of all the compounds correlated poorly with acetonitrile (r ≤ 0.2), a chemical tracer for biomass burning suggesting negligible influence of biomass burning during monsoon season. Our results suggest that during monsoon season when radiation and rain are no longer limiting factors and convective activity causes surface emissions to be transported to upper atmosphere, biogenic emissions can significantly impact the remote upper atmosphere, climate and ozone affecting rice yields.

The co-existence of heavy metals and organic compounds including Cr(VI) and p-cresol (pC) in water environment becoming a challenge in the treatment processes. Herein, the synchronous photocatalytic reduction of Cr(VI) and oxidation of pC by silver oxide decorated on fibrous silica zirconia (AgO/FSZr) was reported. In this study, the catalysts were successfully developed using microemulsion and electrochemical techniques with various AgO loading (1, 5 and 10 wt%) and presented as 1, 5 and 10-AgO/FSZr. Catalytic activity was tested towards simultaneous photoredox of hexavalent chromium and p-cresol (Cr(VI)/pC) and was ranked as followed: 5-AgO/FSZr (96/78%) > 10-AgO/FSZr (87/61%) > 1-AgO/FSZr (47/24%) > FSZr (34/20%). The highest photocatalytic activity of 5-AgO/FSZr was established due to the strong interaction between FSZr and AgO and the lowest band gap energy, which resulted in less electron-hole recombination and further enhanced the photoredox activity. Cr(VI) ions act as a bridge between the positive charge of catalyst and cationic pC in pH 1 solution which can improve the photocatalytic reduction and oxidation of Cr(VI) and pC, respectively. The scavenger experiments further confirmed that the photogenerated electrons (e⁻) act as the main species for Cr(VI) to be reduced to Cr(III) while holes (h⁺) and hydroxyl radicals are domain for photooxidation of pC. The 5-AgO/FSZr was stable after 5 cycles of reaction, suggesting its potential for removal of Cr(VI) and pC simultaneously in the chemical industries.

Microplastics (MPs) pollution has become a global environmental concern. MPs alone and in combination with pollutants can potentially cause significant harm to organisms and human beings. Weathering of MPs under various environmental stresses increases the uncertainty of their environmental fates. Compared with field surveys, laboratory simulation experiments are appropriate to simplify the research procedures and investigate the mechanisms. In this review, the effects of abrasion, solar radiation, chemical and thermal oxidation, microbial adhesion and colonization, and other environmental factors on the MPs and the relative laboratory simulation methods were summarized and discussed. Photo-oxidation and abrasion are the most appliable methods due to easy operation and adjustable weathering degree. Furthermore, the structural and components changes in weathering process and the applied characterization methods were generalized. In addition, one of important environmental behaviors, adsorption of the weathered MPs towards two typical pollutants was analyzed. Finally, three priorities for research were proposed. This paper conducts systematic summarized of the MPs weathering process and provides a reference for future studies to accurately determine the environmental risks of weathering MPs.

The aim of this study was to chemically characterize the fine particulate matter (PM₂.₅) at a subtropical forest in East Asia under the influences of anthropogenic and biogenic sources and a complex topographic setting. Four seasonal campaigns were conducted at the Xitou Experimental Forest in central Taiwan from the winter of 2013 to the autumn of 2014. The results indicated that the ambient levels and chemical features of PM₂.₅ exhibited pronounced seasonal variations. Non-sea-salt sulfate (nss-SO₄²⁻) constituted the major component of PM₂.₅, followed by ammonium (NH₄⁺) and nitrate (NO₃⁻) during winter, summer and autumn. However, it was revealed that the mass fraction of NO₃⁻ increased to be comparable with that of nss-SO₄²⁻ in springtime. The mass contribution of secondary organic carbon (SOC) to PM₂.₅ peaked in summer (13.2%), inferring the importance of enhanced photo-oxidation reactions in SOC formation. Diurnal variations of O₃ and SO₂ coincided with each other, suggesting the transport of aged pollutants from distant sources, whereas CO and NOₓ were shown to be under the influences of both local and regional sources. Notably high sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR) were observed, which were 0.93 ± 0.05 and 0.39 ± 0.20, respectively. Precursor gases (i.e. SO₂ and NOₓ) could be converted to sulfate and nitrate during the transport by the uphill winds. Furthermore, due to the high relative humidity at Xitou, enhanced aqueous-phase and/or heterogeneous reactions could further contribute to the formation of sulfate and nitrate at the site. This study demonstrated the significant transport of urban pollutants to a subtropical forest by the mountain-valley circulations as well as the long-range transport from regional sources, whereas the implications of which for regional climate change necessitated further investigation.

Photocatalysis was recognised as a suitable process for the photoabatement of atmospheric pollutants. The photooxidation mechanism on TiO2 has been widely studied. However, recent studies demonstrated that the very often-assumed photooxidation intermediated by the hydroxyl radical cannot explain all the experimental observations. Indeed, this study contributes for a new understanding of NO photooxidation. First, the adsorption equilibrium isotherms of NO, NO2 and H2O on the photocatalyst, Aeroxide® P25 from Evonik Industries, were obtained. Also, the concentration of hydroxyl radicals was determined by photoluminescence. A comprehensive design of experiments was then followed; NO conversion and selectivity were obtained as a function of the relative humidity, irradiance, NO inlet concentration and residence time, following a response surface methodology (RSM). These results were then used to discuss the photooxidation mechanism of NO.

To further explore the composition and distribution of secondary organic aerosol (SOA) components from the photo-oxidation of light aromatic precursors (toluene, m-xylene, and 1,3,5-trimethylbenzene (1,3,5-TMB)) and idling gasoline exhaust, a vacuum ultraviolet photoionization mass spectrometer (VUV-PIMS) was employed. Peaks of the molecular ions of the SOA components with minimum molecular fragmentation were clearly observed from the mass spectra of SOA, through the application of soft ionization methods in VUV-PIMS. The experiments comparing the exhaust-SOA and light aromatic mixture-SOA showed that the observed distributions of almost all the predominant cluster ions in the exhaust-SOA were similar to that of the mixture-SOA. Based on the characterization experiments of SOA formed from individual light aromatic precursors, the SOA components with molecular weights of 98 and 110 amu observed in the exhaust-SOA resulted from the photo-oxidation of toluene and m-xylene; the components with a molecular weight of 124 amu were derived mainly from m-xylene; and the components with molecular weights of 100, 112, 128, 138, and 156 amu were mainly derived from 1,3,5-TMB. These results suggest that C7-C9 light aromatic hydrocarbons are significant SOA precursors and that major SOA components originate from gasoline exhaust. Additionally, some new light aromatic hydrocarbon-SOA components were observed for the first time using VUV-PIMS. The corresponding reaction mechanisms were also proposed in this study to enrich the knowledge base of the formation mechanisms of light aromatic hydrocarbon-SOA compounds.