Photochemical Oxidation Processes Research Articles

Photocatalysis by Mixed Oxides Containing Niobium, Vanadium, Silica, or Tin

Nb-Sn, V-Sn mixed-metal oxides and Nb-Si, V-Si metal oxide–silicas were successfully synthesized through a “soft” templating method, in which appropriate amounts of metal salts (either niobium(V) chloride, or vanadium(IV) oxide sulfate hydrate or tin(II) chloride dihydrate) or tetraethyl orthosilicate (TEOS) were mixed with hexadecyltrimethylammonium chloride (HDTA) or sodium dodecyl sulfate (SDS) solutions to obtain a new series of mesoporous oxides, followed by calcination at different temperatures. As-obtained samples were characterized by SEM, TEM, XRD, and UV-Vis spectra techniques. The photocatalytic activities of the samples were evaluated by degradation of methyl orange II (MO) under simulated sunlight irradiation. The effects of metal species and calcination temperature on the physicochemical characteristic and photocatalytic activity of the samples were investigated in detail. The results indicated that, compared to pure oxides, mixed-metal oxide showed superior photocatalytic performance for the degradation of MO. A maximum photocatalytic discoloration rate of 97.3% (with MO initial concentration of 0.6·10−4 mol/dm3) was achieved in 300 min with the NbSiOx material, which was much higher than that of Degussa P25 under the same conditions. Additionally, the samples were tested in the photochemical oxidation process, i.e., advanced oxidation processes (AOPs) to treat the commercial non-ionic surfactant: propylene oxide ethylene oxide polymer mono(nonylphenyl) ether (N8P7, PCC Rokita). A maximum of 99.9% photochemical degradation was achieved in 30 min with the NbSiOx material.

Transformation of persistent organic micropollutants by UV and UV/H2O2 in wastewater treatment plant effluent

ABSTRACT Photochemical and advanced oxidation processes (AOPs) are promising options to simultaneously disinfect wastewater treatment plant (WWTP) effluent and degrade organic micropollutants (OMPs). In the present study, kinetic experiments with UV alone and the combination of UV and hydrogen peroxide (H2O2) as an AOP were conducted in WWTP effluent (with and without ultrafiltration) to assess the degradation of 24 OMP, 13 of which were examined for the first time, in a flow-through batch reactor setup. Four parameters were systematically varied to quantify their impacts on OMP degradation: H2O2 concentrations, UV source, water matrix, and flow rate. Most of the studied OMPs (e.g., trimethylammonium, 1,3-di-o-tolylguanidine, carbamazepine) were only significantly degraded in the presence of UV radiation and H2O2. The highest pseudo-first-order rate constants were found for diclofenac, acesulfame, diatrizoate, and sulfamethoxazole. The experiment with the highest degradation also showed the strongest abatement of UV absorbance at 254 nm. Only three of the 24 substances (cyanoguanidine, melamine, and oxipurinol) were not degraded; UV alone even increased their concentrations. Overall, upgrading a UV disinfection to an AOP using H2O2 allows the degradation of a wide range of OMP, making it an interesting process for water reuse.

Investigating vertical distributions and photochemical indications of formaldehyde, glyoxal, and NO2 from MAX-DOAS observations in four typical cities of China

Formaldehyde (HCHO), glyoxal (CHOCHO), and nitrogen dioxide (NO2) are crucial in atmospheric photochemical processes at both surface and elevated altitudes. This study presents synchronous multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of the vertical distributions of summertime HCHO, CHOCHO and NO2 in four representative megacities within the Beijing-Tianjin-Hebei (BTH), Yangtze River Delta (YRD), Sichuan Basin (SB), and Pearl River Delta (PRD) regions of China. The vertical distributions of HCHO and CHOCHO tended to occur at higher altitudes compared to NO2, influenced by both primary emissions near the ground and photochemical oxidation processes at elevated altitudes. Source separation regression analysis using the CO-CHOCHO trace pair identified secondary formation as the predominant source of ambient HCHO. In urban areas, the ratio of CHOCHO to secondary HCHO (RGFsec) serves as a more reliable metric at ground level for diagnosing VOC precursor sources, excluding the interference of primary and background HCHO. The increase in RGF values at higher altitudes highlights the relative contribution of VOCs favoring CHOCHO production. Moreover, four indicators (e.g. FNR, FNRsec, GNR, and MNR) were utilized to characterize O3 formation sensitivity at different altitudes. The range of FNR, FNRsec, GNR, and MNR marking the O3 formation sensitivity regime varies regionally, highlighting the need for localized assessments. The VOC-limited regime dominated at the ground level, whereas the contribution of the NOx-limited regime increased with altitude. Therefore, a comprehensive control strategy addressing both VOC and NOx emissions across different altitudes is essential for effectively mitigating photochemical pollution in urban areas of China.

Chemical composition, source characteristics, and hygroscopic properties of organic-enriched aerosols in the high Arctic during summer

Arctic regions are extremely sensitive to global warming. Aerosols are one of the most important short-lived climate-forcing agents affecting the Arctic climate. The present study examines the summertime chemical characteristics and potential sources of various organic and inorganic aerosols at a Norwegian Arctic site, Ny-Ålesund (79°N). The results show that organic matter (OM) accounts for 60 % of the total PM10 mass, followed by sulfate (SO42−). Water-soluble organic carbon (WSOC) contributes 62 % of OC. Photochemical processes involving diverse anthropogenic and biogenic precursor compounds are identified as the major sources of WSOC, while water-insoluble organic carbon (WIOC) aerosols are predominantly linked to primary marine emissions. Despite being a remote pristine site, the aerosols show a sign of chemical aging, evidenced by a significant chloride depletion, which was about 82 % on average during the study period. Nitrogen-containing aerosols are likely stemming from migratory seabird colonies and local dust sources around the sampling site. While biogenic, crustal, and sea salt-derived SO42- account for 37%, 8%, and 5% respectively, the remaining 50% is attributed to anthropogenic SO42-. Through chemical tracers, Pearson correlation coefficient matrix, and Hierarchical Cluster Analysis (HCA), the present study identifies soil biota (terrestrial biogenic) and marine emissions, along with their photochemical oxidation processes, as potential sources of Arctic aerosols during summer, while biomass burning and combustion-related sources have a minor contribution. The chemical closure of hygroscopicity highlights that while organics predominantly control aerosol hygroscopicity in the Arctic summer, specific inorganic components like (NH4)2SO4 can significantly increase it on certain days, affecting aerosol-cloud interactions and climate processes over the Arctic during summer. The present study highlights the high abundance of organics and their vital role in the Arctic climate during summer when natural aerosols are conquered.

A Low-Cost Ecofriendly Oxidation Process to Manufacture High-Performance Polymeric Biosurfactants Derived from Municipal Biowaste.

Biosurfactants account for about 12% of the global value of the surfactant market, which is currently dominated by synthetic surfactants obtained from fossil sources. Yet, the production of biosurfactants from renewable feedstock is bound to increase, driven by the increasing pressure from both society and governments for chemistry-based industries to become more ecofriendly and economically sustainable. A photo-chemical oxidation process is reported here, yielding new biosurfactants from urban biowaste in water that perform as a solvent and terminal oxidant reagent at room temperature without the addition of conventional oxidants and catalysts. Products with 200-500 kDa molecular weight are obtained. They lower the surface tension of water down to 34 mN/m at 0.5-2 g/L concentration. The estimated cost is rather low (0.1-1.5 EUR/kg), which is competitive with the cost of synthetic surfactants but much lower than the cost of the best-performing bacterial surfactants. For the implementation of the photo-chemical oxidation process at the industrial level, the results suggest that the new biosurfactants obtained in the present work may not reach the performance level of the best-performing bacterial surfactants capable of lowering the surface tension of water down to 28 mN/m. Yet, the biosurfactants produced by the photo-chemical process have a greater chance of being marketed on large scales.

Differences in aerosol chemistry at a regional background site in Hong Kong before and during the COVID-19 pandemic

Restrictions on human-related activities implemented in Hong Kong to curb the spread of the coronavirus disease 2019 (COVID-19) pandemic provided an opportunity to investigate the anthropogenic impact on organic aerosols (OA) composition. In this study, we conducted a comparative analysis of online measurements of non-refractory submicron particulate matters (NR-PM1) at a regional background site in Hong Kong, covering the periods before the COVID-19 control (November 2018) and during the COVID-19 control (October to November 2020), to investigate changes in OA sources and formation mechanisms. Among the measured NR-PM1 components, organics were the most dominant species with an average percentage of 51.0 ± 0.5 %, exceeding pre-control levels of 44.0 ± 0.7 %. Moreover, 88 % of the organics were attributed to oxygenated OA (OOA). Diurnal variations of all bulk components in NR-PM1 consistently showed afternoon peaks, indicating photochemical processes during COVID-19 control. Similar to the pre-restriction period, the positive matrix factorization (PMF) model showed that OOA was composed of three factors, including two less-oxidized oxygenated factors (LO-OOA1 and LO-OOA2) and one more-oxidized oxygenated factor (MO-OOA). The contribution of the LO-OOA2 factor remained small and stable during both sampling campaigns, which might imply background levels of OOA at this site. The formation of the two predominant components of organics (e.g., LO-OOA1 and MO-OOA) was further discussed. Compared with before control, observational evidence showed that the levels of MO-OOA exceeded LO-OOA1 during the control period, and the average concentration of odd oxygen (Ox = ozone + nitrogen dioxide) increased by 53 % during the COVID-19 control. Besides, the results showed that both LO-OOA1 and MO-OOA exhibited similar diurnal variations to Ox, and their concentrations generally enhanced with increasing Ox levels. This suggested that the formation of OOA was closely related to the photochemical oxidation processes when anthropogenic emissions were reduced. By correlating LO-OOA1 and MO-OOA with speciated OA markers, we found that the formation of LO-OOA1 remained associated with anthropogenic sources, while biogenic emissions contributed to the formation of MO-OOA during the COVID-19 control. Our findings highlight the interplay between emissions, atmospheric conditions, and aerosol composition, providing valuable insights to guide strategic decisions for future air quality improvement.

Algal Extracellular Organic Matter Induced Photochemical Oxidation of Mn(II) to Solid Mn Oxide: Role of Mn(III)-EOM Complex and Its Ability to Remove 17α-Ethinylestradiol.

Photosensitizer-mediated abiotic oxidation of Mn(II) can yield soluble reactive Mn(III) and solid Mn oxides. In eutrophic water systems, the ubiquitous algal extracellular organic matter (EOM) is a potential photosensitizer and may have a substantial impact on the oxidation of Mn(II). Herein, we focused on investigating the photochemical oxidation process from Mn(II) to solid Mn oxide driven by EOM. The results of irradiation experiments demonstrated that the generation of Mn(III) intermediate was crucial for the successful photo oxidization of Mn(II) to solid Mn oxide mediated by EOM. EOM can serve as both a photosensitizer and a ligand, facilitating the formation of the Mn(III)-EOM complex. The complex exhibited excellent efficiency in removing 17α-ethinylestradiol. Furthermore, the complex underwent decomposition as a result of reactions with reactive intermediates, forming a solid Mn oxide. The presence of nitrate can enhance the photochemical oxidation process, facilitating the conversion of Mn(II) to Mn(III) and then to solid Mn oxide. This study deepens our grasp of Mn(II) geochemical processes in eutrophic water and its impact on organic micropollutant fate.

Strategies in photochemical alcohol oxidation on noble-metal free nanomaterials as heterogeneous catalysts.

Using light absorbing semiconductors to harvest solar energy has long been considered as a promising approach for driving chemical reactions. Photochemical oxidation of alcohols catalyzed by noble-metal free nanomaterials is particularly attractive due to the bio-derivable nature of the substrate and the wide availability of such catalysts. Here, a number of strategies that could facilitate the progress are discussed, where it is concluded that the photochemical alcohol oxidation process can benefit from both mechanistic optimization of the electron-transfer steps and structural engineering of the light-absorbing nanomaterials.

Degradation of Pesticides Using Semiconducting and Tetrapyrrolic Macrocyclic Photocatalysts-A Concise Review.

Exposure to pesticides is inevitable in modern times, and their environmental presence is strongly associated to the development of various malignancies. This challenge has prompted an increased interest in finding more sustainable ways of degrading pesticides. Advanced oxidation processes in particular appear as highly advantageous, due to their ability of selectively removing chemical entities form wastewaters. This review provides a concise introduction to the mechanisms of photochemical advanced oxidation processes with an objective perspective, followed by a succinct literature review on the photodegradation of pesticides utilizing metal oxide-based semiconductors as photosensitizing catalysts. The selection of reports discussed here is based on relevance and impact, which are recognized globally, ensuring rigorous scrutiny. Finally, this literature review explores the use of tetrapyrrolic macrocyclic photosensitizers in pesticide photodegradation, analyzing their benefits and limitations and providing insights into future directions.

Process analysis of microplastic aging during the photochemical oxidation process and its effect on the adsorption behavior of dissolved organic matter

Information on microplastics (MPs) interactions with dissolved organic matter (DOM) is essential for understanding their environmental impacts. However, research is scarce regarding the adsorption behavior of DOM with different characteristics onto pristine and aged MPs. This research thus investigates MPs aging behavior accelerated by UV/Persulfate and UV/chlorine oxidation processes and the adsorption behavior of organic matter with low-specific ultraviolet absorbance (L-SUVA) and high-SUVA (H-SUVA) characteristics. MPs were degraded by UV/Cl and UV/Persulfate for 30 days. Changes in thermal properties, surface morphology, and chemistry were studied using different analytical techniques. The adsorption behavior was assessed by adsorption kinetic and isotherm study. After oxidation, the surface of the MPs showed a significant increase in the oxygen-containing functional groups, contact angle, surface roughness, and surface energy, and a decrease in crystallinity. The oxidation effect follows the order of UV/Cl > UV/Persulfate. The kinetic and equilibrium data of H-SUVA adsorption on pristine and aged MPs well-fitted the pseudo-second-order and Langmuir model. In contrast, L-SUVA well-fitted the pseudo-first-order and Freundlich model. The adsorption capacity (qm) increased in the following orders: 8.11 > 5.87>4.29 mg g−1 for H-SUVA and 19.81 > 6.662>5.315 mg g−1 for L-SUVA by MPs aged with UV/Cl, UV/Persulfate and pristine MPs, respectively. The larger the surface damage of MPs, the greater the adsorption affinity of DOM. The result was attributed to the physical adsorption process, hydrophobic interactions, electrostatic, hydrogen, and halogen bonding. These findings are beneficial to provide new insights involving the adsorption behavior and interaction mechanisms of DOM onto MPs for the environmental risk assessment.

Oxidative and Photochemical Processes for Soft Drink–Industry Wastewater Treatment

Soft drinks–industry wastewater (SDIW) contains high concentrations of sugar (420–487 mg/L) and sodium (320–397 mg/L), has high pH (∼9), and contains biorefractory pollutants. Therefore, rapid and effective techniques are required for its treatment. In the present study, SDIW was subjected to microwave (MW) photocatalysis (PC) using electrodeless discharge lamps, and the outcomes were compared with other oxidative and photochemical advanced oxidation processes, including oxidation, MW oxidation (MWO), and ultraviolet–titanium dioxide PC, in terms of the removal efficiency of organics based on chemical oxygen demand (COD), total phosphate (TP), and total nitrogen (TN). The mineralization of organics was ∼3.5 times higher in the MWPC and MWO systems compared to the oxidation and PC systems. The COD removal efficiency after 60 min using the oxidation, PC, MWO, and MWPC systems was 22.7%, 25.41%, 79.36%, and 87.3%, respectively. Direct photolysis using UV (using 486 kJ/mole of energy) and photocatalytic degradation using increased hydroxyl radicals in the presence of MWs was the primary degradation mechanism in the MWPC system. The TP removal efficiency in the oxidation, PC, MWO, and MWPC systems was 15%, 40%, 50%, and 60%, respectively. The respective TN removal efficiencies for the four systems were 40%, 58%, 82%, and 85%. The main mechanism for organics, TP, and TN removal in the MWPC system involved the direct disruption of the chemical bonds of the organic molecules, photocatalytic phosphate reduction, and breaking of the primary amine bond in the organic nitrogen using the high-energy plasma and hotspots that formed in the MW-based systems. The electrical energy consumed by the systems [electrical energy per order (EEO)] occurred in the order PC > MWO > MWPC, with respective values of 14,614, 6,919, and 4,526 Rs/kg COD removal.

Heterogeneous and Photosensitized Oxidative Degradation Kinetics of the Plastic Additive Bisphenol-A in Sea Spray Aerosol Mimics.

Plastics have become ubiquitous in the world's oceans, and recent work indicates that they can transfer from the ocean to the atmosphere in sea spray aerosol (SSA). Hazardous chemical residues in plastics, including bisphenol-A (BPA), represent a sizable fraction of consumer plastics and have been measured consistently in air over both terrestrial and marine environments. However, the chemical lifetimes of BPA and mechanisms by which plastic residues degrade with respect to photochemical and heterogeneous oxidation processes in aerosols are unknown. Here, we present the photosensitized and OH-initiated heterogeneous oxidation kinetics of BPA in the aerosol phase consisting of pure-component BPA and internal mixtures of BPA, NaCl, and dissolved photosensitizing organic matter. We found that photosensitizers enhanced BPA degradation in binary-component BPA + photosensitizer aerosol mixtures when irradiated in the absence of OH. OH-initiated degradation of BPA was enhanced in the presence of NaCl with and without photosensitizing species. We attribute this enhanced degradation to greater mobility and thus reaction probability between BPA, OH, and reactive chlorine species (RCS) formed through reaction between OH and dissolved Cl- in the more liquid-like aerosol matrix in the presence of NaCl. Addition of the photosensitizers in the ternary-component BPA + NaCl + photosensitizer aerosol led to no enhancement in the degradation of BPA following light exposure compared to the binary-component BPA + NaCl aerosol. This was attributed to quenching of triplet state formation by dissolved Cl- in the less viscous aqueous aerosol mixtures containing NaCl. Based upon measured second-order heterogeneous reaction rates, the estimated lifetime of BPA with respect to heterogeneous oxidation by OH is one week in the presence of NaCl compared to 20 days in the absence of NaCl. This work highlights the important heterogeneous and photosensitized reactions and the role of phase state, which affect the lifetimes of hazardous plastic pollutants in SSA with implications for understanding pollutant transport and exposure risks in coastal marine environments.

Transformation of microplastics by oxidative water and wastewater treatment processes: A critical review.

Microplastics (MPs) are contaminants of emerging concern that accumulate in various environments, where they pose threats to both the ecosystem and public health. Since MPs have been detected in drinking water resources and wastewater effluents, more efficient treatment is needed at wastewater treatment plants (WWTPs) and drinking water treatment plants (DWTPs). This review discusses the potential of biological, photochemical, Fenton (-like) systems, ozonation, and other oxidation processes in the treatment of MPs in terms of their indicators of oxidation such as mass loss and surface oxidation. The oxidation processes were further analyzed in terms of limitations and environmental implications. Most previous studies examining MPs degradation using conventional treatments-such as UV disinfection, ozonation, and chlorination-employed significantly higher doses than the common doses applied in DWTPs and WWTPs. Owing to such dose gaps, the oxidative transformation of MPs observed in many previous studies are not likely to occur under practical conditions. Some novel oxidation processes showed promising MPs treatment efficiencies, while many of them have not yet been applied on a larger scale due to high costs and the lack of extensive basic research. Health and environmental impacts related to the discharge of oxidized MPs in effluents should be considered carefully in different aspects: the role as vectors of external pollutants, release of organic compounds (including organic byproducts from oxidation) and fragmentation into smaller particles as MPs circulate in the ecosystem as well as the possibility of bioaccumulation. Future research should also focus on ways to incorporate developed oxidation processes in DWTPs and WWTPs to mitigate MPs contamination.

Study on the mechanism of the black crust formation on the ancient marble sculptures and the effect of pollution in Beijing area

In Beijing area, the precious stone objects often suffer from the black crusts on the specific parts of the objects, in order to understand the forming mechanism of the black crusts, samples from the stone sculptures in Beijing Stone Carving Art Museum, ZHIHUA Temple and Museum of Western Zhou Yandu Relics were taken and studied. Nondestructive measurement was carried out firstly to acquire main elements of the samples by portable X-ray spectrum (pXRF). Morphology and microstructure of typical black crust samples were examined by ultra-depth of field microscope (UDFM) and scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS). Compositions of black crusts and body rocks were evaluated with X-ray diffraction (XRD), Raman spectra and mapping. Inductively coupled plasma optical emission spectrometry (ICP-OES) and pyrolysis-gas chromatography/mass spectrometry (Py-GCMS) were used to identify the major pollution sources leading to the black crusts.Through this study, the composition of the black crusts was revealed. Different gypsum crystals and carbonaceous species were found. Pollutant elements analysis and pyrolysis products provide indicators of the pollution sources. As consequence of strong photochemical oxidation processes and the high temperature from June to September in Beijing, more acid rain precursors can be formed. Frequent sulphation process occurs on the CaCO3/CaMg(CO3)2 surface. Combining morphology results and atmospheric data, the formation of black crusts in Beijing can be deduced.

Secondary organic aerosol formation at an urban background site on the coastline of South China: Precursors and aging processes

Understanding the formation mechanisms of secondary organic aerosols (SOA) is an arduous task in atmospheric chemistry. In November 2018, a sampling campaign was conducted at an urban background site in Hong Kong for characterization of secondary air pollution. A high-resolution time-of-flight aerosol mass spectrometer was used to monitor the compositions of non-refractory submicron particulate matters (NR-PM1), and multiple online instruments provided us with comprehensive auxiliary data. Organic aerosol (OA) constituted the largest fraction (43.8%) of NR-PM1, and 86.5% of the organics was contributed by the oxygenated OA (OOA, secondary components). Formation mechanisms of a dominant and more variable component of the less-oxidized OOA (labelled as LO-OOA1 in this study) and the more-oxidized OOA (MO-OOA) were explored. Based on the multilinear regression with molecular markers of OA (e.g., hydroxybenzonic acids and 2,3-dihydroxy-4-oxopentanoic acid), we presumed that anthropogenic organic compounds, especially aromatics, were the most likely precursors of LO-OOA1. MO-OOA correlated well with odd oxygen (Ox), and its concentration responded positively to the increase of liquid water content (LWC) in NR-PM1, indicating that the formation of MO-OOA involved photochemical oxidation and aqueous processes. It exhibited the best correlation with malic acid which can be formed through the oxidation of various precursors. Moreover, it was plausible that LO-OOA1 was further oxidized to MO-OOA through aqueous processes, as indicated by the consistent diurnal variations of MO-OOA to LO-OOA1 ratio and LWC. This study highlights the important roles of anthropogenic emissions and aqueous processes in SOA formation in coastal areas downwind of cities.

One-step solvothermal synthesis of wood flour carbon fiber/BiOBr composites for photocatalytic activation of peroxymonosulfate towards sulfadiazine degradation: Mechanisms comparison between photo, chemical and photo-chemical oxidation processes

Facile preparation of novel catalysts which can effectively activate peroxymonosulfate (PMS) under visible light is of great significance for rapid degradation of refractory organic chemicals in water. Herein, one-step solvothermal process was introduced to prepare carbon nanofiber incorporated bismuth oxybromide (BiOBr/SCF) composites, in which commercial wood flour was in-situ converted to carbon fiber with graphitic structure and incorporated with BiOBr via the process. At the existence of PMS, the prepared composites exhibited prominent visible-light photocatalytic degradation capability towards sulfadiazine (SDZ) with satisfying adaptability and recyclability. Specifically, the apparent pseudo-first order kinetic constant of BiOBr/SCF-180/PMS/visible light system (0.0724 min−1) exceeded those of both BiOBr/SCF-180/PMS (0.0462 min−1) and BiOBr/SCF-180/visible light (0.0111 min−1) systems. An integrated mechanism in the BiOBr/SCF/PMS/visible light system was elucidated through comparing the mechanisms amongst photo-oxidation, chemical oxidation and photo-chemical oxidation systems, in which photo-induced electron and hole, Bi3+/Bi5+ redox couple, graphitic structure and oxygen functional groups in the SCF all participated in the generation and conversion of the active species. The possible SDZ degradation pathway was also proposed. This work demonstrates a novel strategy to prepare high-efficient catalysts in the field of wastewater treatment.

Oxidation pathways and emission sources of atmospheric particulate nitrate in Seoul: based on δ15N and Δ17O measurements

Abstract. PM2.5 haze pollution driven by secondary inorganic NO3- has been a great concern in East Asia. It is, therefore, imperative to identify its sources and oxidation processes, for which nitrogen and oxygen stable isotopes are powerful tracers. Here, we determined the δ15N (NO3-) and Δ17O (NO3-) of PM2.5 in Seoul during the summer of 2018 and the winter of 2018–2019 and estimated quantitatively the relative contribution of oxidation pathways for particulate NO3- and investigated major NOx emission sources. In the range of PM2.5 mass concentration from 7.5 µg m−3 (summer) to 139.0 µg m−3 (winter), the mean δ15N was −0.7 ‰ ± 3.3 ‰ and 3.8 ‰ ± 3.7 ‰, and the mean Δ17O was 23.2 ‰ ± 2.2 ‰ and 27.7 ‰ ± 2.2 ‰ in the summer and winter, respectively. While OH oxidation was the dominant pathway for NO3- during the summer (87 %), nighttime formation via N2O5 and NO3 was relatively more important (38 %) during the winter, when aerosol liquid water content (ALWC) and nitrogen oxidation ratio (NOR) were higher. Interestingly, the highest Δ17O was coupled with the lowest δ15N and highest NOR during the record-breaking winter PM2.5 episodes, revealing the critical role of photochemical oxidation process in severe winter haze development. For NOx sources, atmospheric δ15N (NOx) estimated from measured δ15N (NO3-) considering isotope fractionation effects indicates vehicle emissions as the most important emission source of NOx in Seoul. The contribution from biogenic soil and coal combustion was slightly increased in summer and winter, respectively. Our results built on a multiple-isotope approach provide the first explicit evidence for NO3- formation processes and major NOx emission sources in the Seoul megacity and suggest an effective mitigation measure to improve PM2.5 pollution.

Aerosol Proteinaceous Matter in Coastal Okinawa, Japan: Influence of Long-Range Transport and Photochemical Degradation.

The characteristics, sources, and atmospheric oxidation processes of marine aerosol proteinaceous matter (APM), including total proteins and free amino acids (FAAs), were investigated using a set of 1 year total suspended particulate (TSP) samples collected in the coastal area of Okinawa Island in the western North Pacific rim. The concentrations of APM at this site (total proteins: 0.16 ± 0.10 μg m-3 and total FAAs: 9.7 ± 5.6 ng m-3, annual average) are comparable to those of marine APM. The major FAA species of APM are also similar to previously reported marine APM with glycine as the dominant species (31%). Based on the different seasonal trends and weak correlations of total proteins and FAAs, we found that they were contributed by different sources, especially with the influence of long-range transport from the Asian continent of northern China and Mongolia and the oceanic area of the Bohai Sea, Yellow Sea, and East China Sea. The photochemical oxidation processes of high-molecular-weight proteins releasing FAAs (especially glycine) were also considered as an important factor influencing the characteristics of APM at this site. In addition, we propose a degradation process based on the correlation with ozone and ultraviolet radiation, emphasizing their roles in the degradation of proteins. Our findings help to deepen the understanding of atmospheric photochemical reaction processes of organic aerosols.

Degradation of carbendazim in aqueous solution by different settings of photochemical and electrochemical oxidation processes

The present study analyzed the performance of photochemical and electrochemical techniques in the degradation and mineralization of the pesticide carbendazim (CBZ). Direct photolysis (DP), heterogeneous photocatalysis (HP), photoelectrocatalysis (PEC), and electrochemical oxidation (EO) were tested, and the influence of UV radiation, current density (j), and supporting electrolyte concentration were evaluated. The results suggest that CBZ is only degraded by DP when UV-C254nm is used. For HP, the CBZ degradation was observed both when UV-A365nm or UV-C254nm were used, which is related to the reactive oxygen species (ROS) formed by the photocatalytic activity (photon-ROS). Neither DP nor HP were able to mineralize CBZ, demonstrating its resistance to photomediated processes. For EO, regardless of the j, there were higher CBZ degradation and mineralization than those observed when using DP and HP. The increase in the supporting electrolyte concentration (Na2SO4) did not affect the levels of degradation and mineralization of CBZ. Concerning the PEC, a CBZ mineralization of 52.2% was accomplished. These findings demonstrate that the EO is the main pathway for CBZ mineralization, suggesting an additional effect of the electro-ROS on the photon-ROS and UV-C254nm. The values of mineralization, kinetics, and half-life show that PEC UV-C254nm with a j of 15 mA cm−2 was the best setting for the degradation and mineralization of CBZ. However, when the values of specific energy consumption were considered for industrial applications, the use of EO with a j of 3 mA cm−2 and 4 g L−1 of Na2SO2 becomes more attractive. The assessment of by-products formed after this best cost-efficient treatment setting revealed the presence of aromatic and aliphatic compounds from CBZ degradation. Acute phytotoxicity results showed that the presence of sodium sulfate can be a representative factor regarding the toxicity of samples treated in electrochemical systems.

Fully 3D printing of carbon black-thermoplastic hybrid materials and fast activation for development of highly stable electrochemical sensors

3D printing technologies have emerged as powerful tools for the development of electrochemical sensors. However, pre-treatment methods are often required to improve electrochemical properties of 3D printed sensing surface to enable higher electroanalytical performance. Herein, we report a toxic-free method for rapid activation of 3D printed electrochemical sensors. The proposed pre-treatment involves a combination of photochemical and electrochemical oxidation processes to degrade the excess of binder material impregnated on the cell surface. This strategy is simple, fast and exposes the carbon black nanoparticles to facilitate the faradaic reactions. The reported method ensured long-term stability (~2 months) and high heterogeneous rate constants (1.2 ± 0.3 × 10−3 cm s−1). In addition, peak currents were remarkably increased up to 353 ± 13%, clearly highlighting the potential use these 3D electrodes for electroanalytical applications. The treated electrode offered low detection limits (at µmol L−1 levels) for different analytes including metals like Cd(II) (0.009) and Pb(II) (0.006), midazolam maleate (0.54) and uric acid (0.71). Based on the achieved results, the activated, stable, and fully 3D printed electrochemical cell is very promising towards a plethora of high-performance electroanalytical applications.