A Novel Abiotic Pathway for Phosphine Synthesis over Acidic Dust in Venus' Atmosphere.

Recent ground-based observations of Venus have detected a single spectral feature consistent with phosphine (PH3) in the middle atmosphere, a gas which has been suggested as a biosignature on rocky planets. The presence of PH3 in the oxidized atmosphere of Venus has not yet been explained by any abiotic process. However, state-of-the-art experimental and theoretical research published in previous works demonstrated a photochemical origin of another potential biosignature-the hydride methane-from carbon dioxide over acidic mineral surfaces on Mars. The production of methane includes formation of the HC · O radical. Our density functional theory (DFT) calculations predict an energetically plausible reaction network leading to PH3, involving either HC · O or H· radicals. We suggest that, similarly to the photochemical formation of methane over acidic minerals already discussed for Mars, the origin of PH3 in Venus' atmosphere could be explained by radical chemistry starting with the reaction of ·PO with HC·O, the latter being produced by reduction of CO2 over acidic dust in upper atmospheric layers of Venus by ultraviolet radiation. HPO, H2P·O, and H3P·OH have been identified as key intermediate species in our model pathway for phosphine synthesis.

Effects of Nanobubbles on Photochemical Processes of Levofloxacin Photosensitizer.

Photodynamic therapy (PDT) stands as an efficacious modality for the treatment of cancer and various diseases, in which optimization of the electron transfer and augmentation of the production of lethal reactive oxygen species (ROS) represent pivotal challenges to enhance its therapeutic efficacy. Empirical investigations have established that the spontaneous initiation of redox reactions associated with electron transfer is feasible and is located in the gas-liquid interfaces. Meanwhile, nanobubbles (NBs) are emerging as entities capable of furnishing a plethora of such interfaces, attributed to their stability and large surface/volume ratio in bulk water. Thus, NBs provide a chance to expedite the electron-transfer kinetics within the context of PDT in an ambient environment. In this paper, we present a pioneering exploration into the impact of nitrogen nanobubbles (N2-NBs) on the electron transfer of the photosensitizer levofloxacin (LEV). Transient absorption spectra and time-resolved decay spectra, as determined through laser flash photolysis, unequivocally reveal that N2-NBs exhibit a mitigating effect on the decay of the LEV excitation triplet state, thereby facilitating subsequent processes. Of paramount significance is the observation that the presence of N2-NBs markedly accelerates the electron transfer of LEV, albeit with a marginal inhibitory influence on its energy-transfer reaction. This observation is corroborated through absorbance measurements and offers compelling evidence substantiating the role of NBs in expediting electron transfer within the ambit of PDT. The mechanism elucidated herein sheds light on how N2-NBs intricately influence both electron-transfer and energy-transfer reactions in the photosensitizer LEV. These findings not only contribute to a nuanced understanding of the underlying processes but also furnish novel insights that may inform the application of NBs in the realm of photodynamic therapy.

Reassessing the Quantum Yield and Reactivity of Triplet-State Dissolved Organic Matter via Global Kinetic Modeling.

Measuring the quantum yield and reactivity of triplet-state dissolved organic matter (3DOM*) is essential for assessing the impact of DOM on aquatic photochemical processes. However, current 3DOM* quantification methods require multiple fitting steps and rely on steady-state approximations under stringent application criteria, which may introduce certain inaccuracies in the estimation of DOM photoreactivity parameters. Here, we developed a global kinetic model to simulate the reaction kinetics of the hv/DOM system using four DOM types and 2,4,6-trimethylphenol as the probe for 3DOM*. Analyses of residuals and the root-mean-square error validated the exceptional precision of the new model compared to conventional methods. 3DOM* in the global kinetic model consistently displayed a lower quantum yield and higher reactivity than those in local regression models, indicating that the generation and reactivity of 3DOM* have often been overestimated and underestimated, respectively. The global kinetic model derives parameters by simultaneously fitting probe degradation kinetics under different conditions and considers the temporally increasing concentrations of the involved reactive species. It minimizes error propagation and offers insights into the interactions of different species, thereby providing advantages in accuracy, robustness, and interpretability. This study significantly advances the understanding of 3DOM* behavior and provides a valuable kinetic model for aquatic photochemistry research.

Enhanced split-type photoelectrochemical aptasensor incorporating a robust antifouling coating derived from four-armed polyethylene glycol.

Antifouling biosensors capable of preventing protein nonspecific adhesion in real human bodily fluids are highly sought-after for precise disease diagnosis and treatment. In this context, an enhanced split-type photoelectrochemical (PEC) aptasensor was developed incorporating a four-armed polyethylene glycol (4A-PEG) to construct a robust antifouling coating, enabling accurate and sensitive bioanalysis. The split-type PEC system involved the photoelectrode and the biocathode, effectively separating signal converter with biorecogniton events. Specifically, the TiO2 electrode underwent sequential modification with ZnIn2S4 (ZIS) and polydopamine (PDA) to form the PDA/ZIS/TiO2 photoelectrode. The cathode substrate was synthesized as a hybrid of N-doped graphene loaded with Pt nanoparticles (NG-Pt), and subsequently modified with 4A-PEG to establish a robust antifouling coating. Following the anchoring of probe DNA (pDNA) on the 4A-PEG-grafted antifouling coating, the biocathode for model target of cancer antigen 125 (CA125) was obtained. Leveraging pronounced photocurrent output of the photoelectrode and commendable antifouling characteristics of the biocathode, the split-type PEC aptasensor showcased exceptional detection performances with high sensitivity, good selectivity, antifouling ability, and potential feasibility.

Near UV Photodegradation Mechanisms of Amino Acid Excipients: Formation of the Carbon Dioxide Radical Anion from Aspartate and Fe(III).

Carbon dioxide radical anion (•CO2-) is a powerful reducing agent that can reduce protein disulfide bonds and convert molecular oxygen to superoxide. Therefore, the generation of •CO2- can be detrimental to pharmaceutical formulations. Iron is among the most prevalent impurities in formulations, where Fe(III) chelates of histidine (His) can produce •CO2- upon exposure to near-UV light (Zhang and Schöneich, Eur. J. Pharm. Biopharm. 2023, 190, 231-241). Here, we monitor by spin-trapping in combination with electron paramagnetic resonance spectroscopy and/or high-performance liquid chromatography-mass spectrometry analysis the photochemical formation of •CO2- for a series of common amino acid excipients, including arginine (Arg), methionine (Met), proline (Pro), glutamic acid (Glu), glycine (Gly), aspartic acid (Asp), and lysine (Lys). Our results indicate that in the presence of Fe(III), Asp, and Glu produce significant yields of •CO2- under photoirradiation with near-UV light. Notably, Asp demonstrates the highest efficiency of •CO2- generation compared with that of the other amino acid excipients. Stable isotope labeling indicates that •CO2- exclusively originates from the α-carboxyl group of Asp. Mechanistic studies reveal two possible pathways for •CO2- formation, which involve either a ß-carboxyl radical or an amino radical cation intermediate.

Pollution characteristics, source appointment and environmental effect of oxygenated volatile organic compounds in Guangdong-Hong Kong-Macao Greater Bay Area: Implication for air quality management.

Same as other bay areas, the Guangdong-Hong Kong-Macao Greater Bay Area (GBA) is also suffering atmospheric composite pollution. Even a series of atmospheric environment management policies have been conducted to win the "blue sky defense battle", the atmospheric secondary pollutants (e.g., O3) originated from oxygenated volatile organic compounds (OVOCs) still threaten the air quality in GBA. However, there lacks a systematic summary on the emission, formation, pollution and environmental effects of OVOCs in this region for further air quality management. This review focused on the researches related to OVOCs in GBA, including their pollution characteristics, detection methods, source distributions, secondary formations, and impacts on the atmosphere. Pollution profile of OVOCs in GBA revealed that the concentration percentage among total VOCs from Guangzhou and Dongguan cities exceeded 50 %, while methanol, formaldehyde, acetone, and acetaldehyde were the top four highest concentrated OVOCs. The detection technique on regional atmospheric OVOCs (e.g., oxygenated organic molecules (OOMs)) underwent an evolution of off-line derivatization method, on-line spectroscopic method and on-line mass spectrometry method. The OVOCs in GBA were mainly from primary emissions (up to 80 %), including vehicle emissions and biomass combustion. The anthropogenic alkenes and aromatics in urban area, and natural isoprene in rural area also made a significant contribution to the secondary emission (e.g., photochemical formation) of OVOCs. About 20 % in average of ROx radicals was produced from photolysis of formaldehyde in comparison with O3, nitrous acid and rest OVOCs, while the reaction between OVOCs and free radical accelerated the NOx-O3 cycle, contributing to 15 %-60 % cumulative formation of O3 in GBA. Besides, the heterogeneous reactions of dicarbonyls generated 21 %-53 % of SOA. This review also provided suggestions for future research on OVOCs in terms of regional observation, analytical method and mechanistic study to support the development of a control and management strategy on OVOCs in GBA and China.

Photochemical Synthesis of Noble Metal Nanoparticles: Influence of Metal Salt Concentration on Size and Distribution.

This paper explores the photochemical synthesis of noble metal nanoparticles, specifically gold (Au) and silver (Ag) nanoparticles, using a one-component photoinitiator system. The synthesis process involves visible light irradiation at a wavelength of 419 nm and an intensity of 250 mW/cm2. The radical-generating capabilities of the photoinitiators were evaluated using electron spin resonance (ESR) spectroscopy. The main objective of this study was to investigate how the concentration of metal salts influences the size and distribution of the nanoparticles. Proposed mechanisms for the photochemical formation of nanoparticles through photoinitiated radicals were validated using cyclic voltammetry. The results showed that the concentration of AgNO3 significantly impacted the size of silver nanoparticles, with diameters ranging from 1 to 5 nm at 1 wt% and 3 wt% concentrations, while increasing the concentration to 5 wt% led to an increase in the diameter of silver nanoparticles to 16 nm. When HAuCl4 was used instead of AgNO3, it was found that the average diameters of gold nanoparticles synthesized using both photoinitiators at different concentrations ranged between 1 and 4 nm. The findings suggest that variations in HAuCl4 concentration have minimal impact on the size of gold nanoparticles. The photoproduction of AuNPs was shown to be thermodynamically favorable, with the reduction of HAuCl4 to Au0 having ∆G values of approximately -3.51 and -2.96 eV for photoinitiators A and B, respectively. Furthermore, the photoreduction of Ag+1 to Ag0 was demonstrated to be thermodynamically feasible, with ∆G values of approximately -3.459 and -2.91 eV for photoinitiators A and B, respectively, confirming the effectiveness of the new photoinitiators on the production of nanoparticles. The synthesis of nanoparticles was monitored using UV-vis absorption spectroscopy, and their sizes were determined through particle size analysis of transmission electron microscopy (TEM) images.

Thermal/Blue Light Induced Cross-Linking of Acrylic Coatings with Diazo Compounds.

The thermal curing of industrial coatings (e.g., car painting and metal coil coatings) is accompanied by a substantial energy consumption due to the intrinsically high temperatures required during the curing process. Therefore, the development of new photochemical curing processes-preferably using visible light-is in high demand. This work describes new diazo-based cross-linkers that can be used to photocure acrylic coatings using blue light. This work demonstrates that the structure of the tethered diazo compounds influences the cross-linking efficiency, finding that side reactions are suppressed upon engineering greater molecular flexibility. Importantly, this work shows that these diazo compounds can be employed as either thermal or photochemical cross-linkers, exhibiting identical crosslinking performances. The performance of diazo-cross-linked coatings is evaluated to reveal excellent water resistance and demonstrably similar material properties to UV-cured acrylates. These studies pave the way for further usage of diazo-functionalized cross-linkers in the curing of paints and coatings.

Upper bound for broadband radiofrequency field disruption of magnetic compass orientation in night-migratory songbirds.

Night-migratory songbirds have a light-dependent magnetic compass sense, the mechanism of which is thought to depend on the photochemical formation of radical pairs in cryptochrome (Cry) proteins located in the retina. The finding that weak radiofrequency (RF) electromagnetic fields can prevent birds from orienting in the Earth's magnetic field has been regarded as a diagnostic test for this mechanism and as a potential source of information on the identities of the radicals. The maximum frequency that could cause such disorientation has been predicted to lie between 120 and 220 MHz for a flavin-tryptophan radical pair in Cry. Here we show that the magnetic orientation capabilities of Eurasian blackcaps (Sylvia atricapilla) are not affected by RF noise in the frequency bands 140 to 150 MHz and 235 to 245 MHz. From a consideration of its internal magnetic interactions, we argue that RF field effects on a flavin-containing radical-pair sensor should be approximately independent of frequency up to 116 MHz and that birds' sensitivity to RF disorientation should fall by about two orders of magnitude when the frequency exceeds 116 MHz. Taken together with our earlier finding that 75 to 85 MHz RF fields disrupt the magnetic orientation of blackcaps, these results provide compelling evidence that the magnetic compass of migratory birds operates by a radical pair mechanism.

Emerging investigator series: aqueous photooxidation of live bacteria with hydroxyl radicals under cloud-like conditions: insights into the production and transformation of biological and organic matter originating from bioaerosols.

Live bacteria in clouds are exposed to free radicals such as the hydroxyl radical (˙OH), which is the main driver of many photochemical processes. While the ˙OH photooxidation of organic matter in clouds has been widely studied, equivalent investigations on the ˙OH photooxidation of bioaerosols are limited. Little is known about the daytime encounters between ˙OH and live bacteria in clouds. Here we investigated the aqueous ˙OH photooxidation of four bacterial strains, B. subtilis, P. putida, E. hormaechei B0910, and E. hormaechei pf0910, in microcosms composed of artificial cloud water that mimicked the chemical composition of cloud water in Hong Kong. The survival rates for the four bacterial strains decreased to zero within 6 hours during exposure to 1 × 10-16 M of ˙OH under artificial sunlight. Bacterial cell damage and lysis released biological and organic compounds, which were subsequently oxidized by ˙OH. The molecular weights of some of these biological and organic compounds were >50 kDa. The O/C, H/C, and N/C ratios increased at the initial onset of photooxidation. As the photooxidation progressed, there were few changes in the H/C and N/C, whereas the O/C continued to increase for hours after all the bacterial cells had died. The increase in the O/C was due to functionalization and fragmentation reactions, which increased the O content and decreased the C content, respectively. In particular, fragmentation reactions played key roles in transforming biological and organic compounds. Fragmentation reactions cleaved the C-C bonds of carbon backbones of higher molecular weight proteinaceous-like matter to form a variety of lower molecular weight compounds, including HULIS of molecular weight <3 kDa and highly oxygenated organic compounds of molecular weight <1.2 kDa. Overall, our results provided new insights at the process level into how daytime reactive interactions between live bacteria and ˙OH in clouds contribute to the formation and transformation of organic matter.

Transient chiral dynamics revealed by two-dimensional circular dichroism spectroscopy.

Chirality has been considered as one of the key factors in the evolution of life in nature. It is important to uncover how chiral potentials of molecular systems play vital role in fundamental photochemical processes. Here, we investigate the role of chirality in photoinduced energy transfer in a model dimeric system, where the monomers are excitonically coupled. To observe transient chiral dynamics and energy transfer, we employ circularly polarized laser pulses in two-dimensional electronic spectroscopy to construct the two-dimensional circular dichroism (2DCD) spectral maps. Tracking time-resolved peak magnitudes in 2DCD spectra allows one to identify chirality induced population dynamics. The dynamics of energy transfer is revealed by the time-resolved kinetics of cross peaks. However, the differential signal of 2DCD spectra shows the magnitude of cross peaks is dramatically reduced at initial waiting time, which indicates the weak chiral interactions between two monomers. The downhill energy transfer is resolved by presenting a strong magnitude of cross peak in 2DCD spectra after long waiting time. The chiral contribution towards coherent and incoherent energy-transfer pathways in the model dimer system is further examined via control of excitonic couplings between two monomers. Applications are made to study the energy-transfer process in the Fenna-Matthews-Olson complex. Our work uncovers the potential of 2DCD spectroscopy to resolve the chiral-induced interactions and population transfers in excitonically coupled systems.

A vehicle-mounted dual-smog chamber: Characterization and its preliminary application to evolutionary simulation of photochemical processes in a quasi-realistic atmosphere.

Smog chambers are the effective tools for studying formation mechanisms of air pollution. Simulations by traditional smog chambers differ to a large extent from real atmospheric conditions, including light, temperature and atmospheric composition. However, the existing parameters for mechanism interpretation are derived from the traditional smog chambers. To address the gap between the traditional laboratory simulations and the photochemistry in the real atmosphere, a vehicle-mounted indoor-outdoor dual-smog chamber (JNU-VMDSC) was developed, which can be quickly transferred to the desired sites to simulate quasi-realistic atmosphere simultaneously in both chambers using "local air". Multiple key parameters of the smog chamber were characterized in the study, demonstrating that JNU-VMDSC meets the requirements of general atmospheric chemistry simulation studies. Additionally, the preliminary results for the photochemical simulations of quasi-realistic atmospheres in Pearl River Delta region and Nanling Mountains are consistent with literature reports on the photochemistry in this region. JNU-VMDSC provides a convenient and reliable experimental device and means to study the mechanism of atmospheric photochemical reactions to obtain near-real results, and will make a great contribution to the control of composite air pollution.

Investigating the Physiological and Molecular Responses of Solanum lycopersicum hp Mutants to Light of Different Quality for Biotechnological Applications.

The effect of the light of different spectral compositions, white fluorescent light (WFL), red light (RL, 660 nm), blue light (BL, 450 nm), green light (GL, 525 nm), and white LED light (WL, 450 + 580 nm), on the physiological parameters of Solanum lycopersicum 3005 hp-2 (defective for a DET1 gene) and 4012 hp-1w; 3538 hp-1; 0279 hp-1.2 (defective for a DDB1a gene) photomorphogenetic mutants was studied. The parameters of the primary photochemical processes of photosynthesis, photosynthetic and transpiration rates, the antioxidant capacity of low-molecular weight antioxidants, the content of the total phenolic compounds, including flavonoids, and the expression of the genes involved in light signaling and biosynthesis of secondary metabolites were determined. Under BL, the 3005 hp-2 mutant showed the highest nonenzymatic antioxidant activity, which occurred to a greater extent due to the increase in flavonoid content. At the same time, under BL, the number of secretory trichomes on the surface of the leaves of all mutants increased equally. This suggests the accumulation of flavonoids inside leaf cells rather than in trichomes on the leaf surface. The data obtained indicate the possibility of using the hp-2 mutant for biotechnology to increase its nutritional value by enhancing the content of flavonoids and other antioxidants by modulating the spectral composition of light.

Photo-produced aromatic compounds stimulate microbial degradation of dissolved organic carbon in thermokarst lakes.

Photochemical and biological degradation of dissolved organic carbon (DOC) and their interactions jointly contribute to the carbon dioxide released from surface waters in permafrost regions. However, the mechanisms that govern the coupled photochemical and biological degradation of DOC are still poorly understood in thermokarst lakes. Here, by combining Fourier transform ion cyclotron resonance mass spectrometry and microbial high-throughput sequencing, we conducted a sunlight and microbial degradation experiment using water samples collected from 10 thermokarst lakes along a 1100-km permafrost transect. We demonstrate that the enhancement of sunlight on DOC biodegradation is not associated with the low molecular weight aliphatics produced by sunlight, but driven by the photo-produced aromatics. This aromatic compound-driven acceleration of biodegradation may be attributed to the potential high abilities of the microbes to decompose complex compounds in thermokarst lakes. These findings highlight the importance of aromatics in regulating the sunlight effects on DOC biodegradation in permafrost-affected lakes.

Visible-light photocatalytic degradation of water-soluble polyvinyl alcohol in aqueous solution by Cu2O@TiO2: Optimization of conditions, mechanisms and toxicity analysis.

Polyvinyl alcohol (PVA), a water-soluble synthetic polymer, is one of the most prevalent non-native polyvinyl alcohols found in the environment. Due to its inherent invisibility, its potential for causing severe environmental pollution is often underestimated. To achieve efficient degradation of PVA in wastewater, a Cu2O@TiO2 composite was synthesized through the modification of titanium dioxide with cuprous oxide, and its photocatalytic degradation of PVA was investigated. The Cu2O@TiO2 composite, supported by titanium dioxide, facilitated photocarrier separation and demonstrated high photocatalytic efficiency. Under alkaline conditions, the composite exhibited a 98% degradation efficiency for PVA solutions and a 58.7% PVA mineralization efficiency. Radical capture experiments and electron paramagnetic resonance (EPR) analyses revealed that superoxide radicals primarily drive the degradation process within the reaction system. Throughout the degradation process, PVA macromolecules are broken down into smaller molecules, including ethanol, and compounds containing aldehyde, ketone, and carboxylic acid functional groups. Although the intermediate products exhibit reduced toxicity compared to PVA, they still pose certain toxic hazards. Consequently, further research is necessary to minimize the environmental impact of these degradation products.

The study on the effect of hydrodynamic flow on the photocatalytic performance of photocatalytic reactors.

The scalability of photocatalytic reactor is the major challenge due to the inability of the light penetration when the laboratory scale reactors are ascended. It is well known that the characteristic length of photocatalytic reactor is one of the influential parameters determining the efficiency of light penetration and also affects the hydrodynamic fluid flow behaviour inside the reactor. This study visualizes hydrodynamic flow behaviour of three differently configured photocatalytic reactors through numerical simulation of the fluid mass transport inside the reactors. The three photocatalytic reactors are (1) concentric cylindrical glass tube micro-reactor (CGTR), (2) UV-LED strip photocatalytic reactor (STR) and (3) classical annular reactor (CAR) from our previous work. The simulations of flow behaviour confirmed that CGTR exhibited plug flow regime, STR exhibited arbitrary flow (in-between continuously stirred tank reactor and plug flow reactor) and CAR behaved like continuously stirred tank reactor. Also, interpretations of numerical modelling were validated through plotting experimental residence time distribution curve. Furthermore, the comparison of performance parameters revealed that the highest modified space time yield (STYmodified) 225 s-1and highest modified photocatalytic space time yield (PSTYmodified) 9.375 s-1/kW/m3 was obtained for plug flow reactor when compared to continuously stirred tank reactor (CAR) and arbitrary flow reactor (STR). The study confirms that decrease in characteristic length of photocatalytic reactor onsets plug flow regime, which has highest photocatalytic performance efficiency.

Photocatalytic degradation of ciprofloxacin by MMT/CuFe2O4 nanocomposite: characteristics, response surface methodology, and toxicity analyses.

The photocatalytic degradation of ciprofloxacin (CIP) was examined by loading spinel ferrite copper (CuFe2O4) nanoparticles onto montmorillonite (MMT) under irradiation using UV light. The laboratory parameters were optimized using response surface methodology (RSM), and maximum efficiency (83.75%) was achieved at a pH of 3, CIP concentration of 32.5 mg/L, MMT/CuFe2O4 dose of 0.78 g/L, and irradiation time of 47.50 min. During the photocatalysis process, the experiments on radical trapping demonstrated the generation of hydroxyls (•OH), superoxide (•O2-) radical, electrons (e-), and holes (h+). A low rate drop (below 10%) in the CIP degradation during the six consecutive reaction cycles corroborated the remarkable recyclability and stability of the MMT/CuFe2O4. The acute toxicity of the treated solution was determined using Daphnia Magna, by applying photocatalysis, which was indicative of a marked decline in the toxicity. Comparing the findings of the degradation using UV and the degradation process using visible light represented results with close resemblance to each other at the end of the reaction time. Besides, under UV and visible light, the particles in reactor are easily activated when the pollutant mineralization exceeded 80%.

Photothermal Catalytic CO2 Conversion: Beyond Catalysis and Photocatalysis.

In recent years, the combination of both thermal and photochemical contributions has provided interesting opportunities for solar upgrading of catalytic processes. Photothermal catalysis works at the interface between purely photochemical processes, which involve the direct conversion of photon energy into chemical energy, and classical thermal catalysis, in which the catalyst is activated by temperature. Thus, photothermal catalysis acts in two different ways on the energy path of the reaction. This combined catalysis, of which the fundamental principles will be reviewed here, is particularly promising for the activation of small reactive molecules at moderate temperatures compared to thermal catalysis and with higher reaction rates than those attained in photocatalysis, and it has gained a great deal of attention in the last years. Among the different applications of photothermal catalysis, CO2 conversion is probably the most studied, although reaction mechanisms and photonic-thermal synergy pathways are still quite unclear and, from the reaction route point of view, it can be said that photothermal-catalytic CO2 reduction processes are still in their infancy. This article intends to provide an overview of the principles underpinning photothermal catalysis and its application to the conversion of CO2 into useful molecules, with application essentially as fuels but also as chemical building blocks. The most relevant specific cases published to date will be also reviewed from the viewpoint of selectivity towards the most frequent target products.

Summertime carbonyl compounds in an urban area in the North China Plain: Identification of sources, key precursors and their contribution to O3 formation.

Carbonyl compounds are critical components of volatile organic compounds, which significantly participate in the photochemical formation of atmospheric ozone and thus threaten human health. Here we measured 15 C1-C8 carbonyl compounds at an urban site in Linyi, a typically industrialised city in the North China Plain (NCP). Formaldehyde (3.89 ppbv), acetaldehyde (1.66 ppbv) and acetone (2.03 ppbv) were found to be the top three carbonyl compounds, accounting for 76.11% of the total concentration of carbonyl compounds. Anthropogenic secondary formation was recognised as the main source of the top five carbonyl compounds, which included formaldehyde, acetaldehyde, acetone, butyraldehyde and benzaldehyde, and accounted for 46-54% of all sources. Alkenes were the most important precursors of formaldehyde and acetaldehyde, suggesting that reducing the emission of alkenes from anthropogenic sources is an effective way to control carbonyl compound pollution in Linyi. Furthermore, the photolysis of carbonyl compounds played a significant role (68-75%) as sources of HO2• and RO2• and thus made a significant contribution (14.6%) to the photochemical formation of O3. This study highlights the importance of anthropogenic secondary formation as a source of carbonyl compounds and provides a scientific basis for O3 pollution control in carbonyl compound-enriched cities in the NCP.