Photochemical Oxidation Research Articles

Severe level of photochemical oxidants (Ox) over the western coast of Japan during autumn after typhoon passing

Photochemical oxidants (Ox; mainly O3) are a concern in East Asia. Because of the prevailing westerly wind in the midlatitudes, O3 concentration generally shows a high in spring over Kyushu Island, western Japan, and Ox warnings have been issued in spring. However, the record from 2000 to 2021 of Ox warning days in Kyushu Island contains one warning case in autumn 2020. Interestingly, a typhoon had passed the day before this Ox warning. To relate these events, a modelling simulation was conducted and it showed the transboundary O3 transport from the Asian continent to the western coast of Japan due to the strong wind field determined by the location of Typhoon Haishen (2020). The sensitivity simulations for changing Chinese anthropogenic sources suggested that both nitrogen oxides (NOx) and volatile organic compound (VOC) emission regulations in China could decrease high O3 over the downwind region of Japan. Furthermore, VOC emission regulation in China led to an overall O3 decrease in East Asia, whereas NOx emission regulation in China had complex effects of decreasing (increasing) O3 during the daytime (nighttime) over China. The association between air quality and meteorology related to typhoons should be considered along with global warming in the future.

Life-Cycle Assessment of a Combined-Cycle Power Plant for Electricity Generation

Background: Life-cycle assessment (LCA) is a comprehensive method used to evaluate the environmental effects throughout the entire lifespan (from creation to disposal) of a product or process. In this study, we conducted an analysis of the environmental impact associated with generating 1 kilowatt-hour of electricity in a combined-cycle power plant located in the southwest region of Iran. Methods: An LCA following ISO 14044 standards was conducted via the ReCiPe method evaluating 10 impact categories at the midpoint level, and covering the entire life cycle. This method was selected for its comprehensive modeling of potential impacts from numerous chemicals and its practicality at both midpoint and endpoint levels. Results: The study found that resource availability (RA) has the highest impact at 53% in endpoint categories, mainly due to natural land transformation (NLT) and fuel depletion (FD). Human health (HH) contributes 43%, while ecosystem diversity (ED) has a minor 4% role. In midpoint categories, over 99% of global warming potential (GWP) and climate change (CC) are from CO2 emissions due to fossil fuel combustion. Conclusion: Midpoint analysis identified NLT, FD, CC, freshwater ecotoxicity, terrestrial ecotoxicity, human toxicity, photochemical oxidant formation, terrestrial acidification, freshwater eutrophication, and water depletion as the most impacted categories by the power plant. However, at the endpoint level, RA, HH, and ED were the primary concerns. Fossil fuel use significantly shaped the environmental impact throughout the power plant’s life cycle.

Oxidation Chemistry of Bicarbonate and Peroxybicarbonate: Implications for Carbonate Management in Energy Storage.

Carbonate formation presents a major challenge to energy storage applications based on low-temperature CO2 electrolysis and recyclable metal-air batteries. While direct electrochemical oxidation of (bi)carbonate represents a straightforward route for carbonate management, knowledge of the feasibility and mechanisms of direct oxidation is presently lacking. Herein, we report the isolation and characterization of the bis(triphenylphosphine)iminium salts of bicarbonate and peroxybicarbonate, thus enabling the examination of their oxidation chemistry. Infrared spectroelectrochemistry combined with time-resolved infrared spectroscopy reveals that the photoinduced oxidation of HCO3- by an Ir(III) photoreagent results in the generation of the short-lived bicarbonate radical in less than 50 ns. The highly acidic bicarbonate radical undergoes proton transfer with HCO3- to furnish the carbonate radical anion and H2CO3, leading to the eventual release of CO2 and H2O, thus accounting for the appearance of H2O and CO2 in both electrochemical and photochemical oxidation experiments. The back reaction of the carbonate radical subsequently oxidizes the Ir(II) photoreagent, leading to carbonate. In the absence of this back reaction, dimerization of the carbonate radical provides entry into peroxybicarbonate, which we show undergoes facile oxidation to O2 and CO2. Together, the results reported identify tangible pathways for the design of catalysts for the management of carbonate in energy storage applications.

Distribution and 13C Signature of Dicarboxylic Acids and Related Compounds in Fine Aerosols Near Underground Coal Fires in North China: Implications for Fossil Origin of Azelaic Acid

AbstractTo understand the characteristics of chemical components and dicarboxylic acids, oxocarboxylic acids and α‐dicarbonyls in atmospheric aerosols at underground coal fire environment, we collected fine aerosols (PM2.5) from Wuhai, Inner Mongolia, North China, where the underground coal fire often occurs. PM2.5 samples were analyzed for the measurements of carbonaceous components, stable carbon isotopic composition (δ13C) of total carbon, and molecular distribution and compound‐specific δ13C of diacids, oxoacids and α‐dicarbonyls. Oxalic acid (C2) was the most abundant species, accounting for 43.2%–63.1% (avg. 50.8%) of total diacids, followed by phthalic acid (Ph) (13.7%). Azelaic acid (C9) was the third most (7.4%) abundant, followed by succinic (C4) and malonic (C3) acids. Significant correlations of C2 diacid with glyoxylic (ωC2) and 3‐oxopropanoic (ωC3) acids and C3 diacid and their δ13C implied that diacids and related compounds were mainly derived from the underground coal fire emissions and subsequent in situ secondary formation. Based on molecular distribution, seasonal pattern and linear relations of C9 diacid with C2, C3, ωC2 and ωC3 as well as with Ph acid and total diacids, together with the comparability and similarity of its δ13C (−27.0 ± 0.9‰) with that of Ph acid and organic matter in coals, respectively, we found that the C9 diacid has been mainly derived from its precursors such as unsaturated fatty acids emitted from underground coal fires and their subsequent in situ photochemical oxidation. However, further research is needed to confirm such an importance of coal combustion for azelaic acid loading in atmospheric aerosols.

Photochemical Desaturation and Epoxidation with Oxygen by Sequential Flavin Catalysis.

Catalytic desaturations are important strategies for the functionalization of organic molecules. In nature, flavoenzymes mediate the formation of α,β-unsaturated carbonyl compounds by concomitant cofactor reduction. Contrary to many laboratory methods for these reactions, such as the Saegusa-Ito oxidation, no transition metal reagents or catalysts are required. However, a molecular flavin-mediated variant has not been reported so far. We disclose a photochemical approach for silyl enol ether oxidation, which leads to α,β-unsaturated ketones (13 examples) in very good yields. The flavin catalysts are stable throughout the desaturation reaction, and we successfully applied them in a subsequent aerobic epoxidation by simply changing the reaction conditions. This protocol allowed us to directly convert silyl enol ethers into α,β-epoxyketones in a one-pot fashion (12 examples). Sequential flavin catalysis is not limited to one specific reactivity combination and can, inter alia, couple the photochemical oxidation with radical additions. We anticipate that flavin-catalyzed desaturation will be applicable to other substrate classes and that its sequential catalytic activity will enable rapid substrate diversification.

Photochemical Desaturation and Epoxidation with Oxygen by Sequential Flavin Catalysis

AbstractCatalytic desaturations are important strategies for the functionalization of organic molecules. In nature, flavoenzymes mediate the formation of α,β‐unsaturated carbonyl compounds by concomitant cofactor reduction. Contrary to many laboratory methods for these reactions, such as the Saegusa‐Ito oxidation, no transition metal reagents or catalysts are required. However, a molecular flavin‐mediated variant has not been reported so far. We disclose a photochemical approach for silyl enol ether oxidation, which leads to α,β‐unsaturated ketones (13 examples) in very good yields. The flavin catalysts are stable throughout the desaturation reaction, and we successfully applied them in a subsequent aerobic epoxidation by simply changing the reaction conditions. This protocol allowed us to directly convert silyl enol ethers into α,β‐epoxyketones in a one‐pot fashion (12 examples). Sequential flavin catalysis is not limited to one specific reactivity combination and can, inter alia, couple the photochemical oxidation with radical additions. We anticipate that flavin‐catalyzed desaturation will be applicable to other substrate classes and that its sequential catalytic activity will enable rapid substrate diversification.

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.

Insights Into NOx and HONO Chemistry in the Tropical Marine Boundary Layer at Cape Verde During the MarParCloud Campaign

AbstractChemical processing of reactive nitrogen species, especially of NOx (= NO + NO2) and nitrous acid (HONO), determines the photochemical ozone production and oxidation capacity in the troposphere. However, sources of HONO and NOx in the remote marine atmosphere are still poorly understood. In this work, the multiphase chemistry mechanism CAPRAM in the model framework SPACCIM was used to study HONO formation at Cape Verde (CVAO) in October 2017, adopted with the input of current parameterizations for various HONO sources. Three simulations were performed that adequately reproduced ambient HONO levels and its diurnal pattern. The model performance for NOx and O3 improves significantly when considering dust‐surface‐photocatalytic conversions of reactive nitrogen compounds with high correlation coefficients up to 0.93, 0.56, and 0.89 for NO, NO2, and O3, respectively. Photocatalytic conversion of the adsorbed HNO3 on dust is modeled to be the predominant contributor for daytime HONO at CVAO, that is, accounting for about 62% of the chemical formation rate at noontime. In contrast, the ocean‐surface‐mediated conversion of NO2 to HONO and other discussed pathways are less important. The average OH levels at midday (9:00–16:00) modeled for cluster trajectory 1, 2, and 3 are 5.2, 5.1, and 5.2 × 106 molecules cm−3, respectively. Main OH formation is driven by O3 photolysis with a contribution of 74.6% to the total source rate, while HONO photolysis is negligible (∼1.8%). In summary, this study highlights the key role of dust aerosols for HONO formation and NOx cycling at CVAO and possibly in other dust‐affected regions, urgently calling for further investigations using field and model studies.

High-time-resolution chemical composition and source apportionment of PM2.5 in northern Chinese cities: implications for policy

Abstract. Fine particulate matter (PM2.5) pollution is still one of China's most important environmental issues, especially in northern cities during wintertime. In this study, intensive real-time measurement campaigns were conducted in Xi'an, Shijiazhuang, and Beijing to investigate the chemical characteristics and source contributions of PM2.5 and explore the formation of heavy pollution for policy implications. The chemical compositions of PM2.5 in the three cities were all dominated by organic aerosol (OA) and nitrate (NO3-). Results of source apportionment analyzed by a hybrid environmental receptor model (HERM) showed that the secondary formation source contributed more to PM2.5 compared to other primary sources. Biomass burning was the dominant primary source in the three pilot cities. The contribution of coal combustion to PM2.5 is non-negligible in Xi'an and Shijiazhuang but is no longer an important contributor in the capital city of Beijing due to the execution of a strict coal-banning policy. The potential formation mechanisms of secondary aerosol in the three cities were further explored by establishing the correlations between the secondary formation sources and aerosol liquid water content (ALWC) and Ox (O3+NO2), respectively. The results showed that photochemical oxidation and aqueous-phase reaction were two important pathways of secondary aerosol formation. According to source variations, air pollution events that occurred in campaigns were classified into three types: biomass-combustion-dominated, secondary-formation-source-dominated, and a combination of primary and secondary sources. Additionally, this study compares the changes in chemical composition and source contributions of PM2.5 in past decades. The results suggest that the clean-energy replacements for rural households should be urgently encouraged to reduce the primary source emissions in northern China, and collaborative control on ozone and particulate matter needs to be continuously promoted to weaken the atmosphere oxidation capacity for the sake of reducing secondary aerosol formation.

Characterization, Sources, and Chemical Processes of Submicron Aerosols at a Mountain Site in Central China

AbstractA field campaign (29 May to 14 June 2018) was conducted at a mountain site in central China. The chemical composition of non‐refractory submicron particulate matter (NR‐PM1) and the particle number size distribution (PNSD) were measured, respectively. The mean NR‐PM1 mass concentration was 20.94 ± 10.14 μg m−3, among which organics (47%) was the most abundant component, followed by sulfate (37%), ammonium (11%), nitrate (4%), and chloride (1%). Notably, sulfate accounted for more than 70% of the secondary inorganic aerosols. Positive matrix factorization (PMF) analysis of the composition data resulted in three organic aerosol (OA) factors: hydrocarbon‐like OA (HOA), oxygenated OA I (OOA‐I), and oxygenated OA II (OOA‐II). The secondary organic aerosol (SOA) composed of the latter two factors (SOA: OOA‐I + OOA‐II) was dominant in OA (80.7%). The PMF analysis of the PNSD data yielded three factors: new particle formation related mode, growth mode, and accumulation mode, among which the last factor dominated both number and volume ratios. The sulfate formation was characterized by the sulfur oxidation ratio (SOR), heterogeneous sulfate production rate (Phet), and gaseous sulfuric acid concentration, representing secondary sulfate transformation, heterogeneous reactions, and gas phase reactions, respectively. The results showed that Phet was well correlated with both sulfate concentrations and SOR, especially during the polluted periods. Our study demonstrates that photochemically‐driven heterogeneous reactions contribute dominantly to the sulfate formation and SOA is formed predominantly by photochemical oxidation of volatile organic compounds under high temperatures and ultraviolet (UV) intensities, and NOX concentrations on Mt. Wudang during the campaign period.

Characteristics and atmospheric processes of water-soluble ions in PM2.5 and PM10 over an industrial city in the National Capital Region (NCR) of India

This study investigates water-soluble inorganic ions (WSIIs), their potential formation mechanism, particle bound water content and acidity (pH) in ambient aerosols in Ghaziabad, an industrial city located downwind of Delhi, the Indian National Capital. 24-hour integrated PM2.5 and PM10 samples were collected using collocated samplers at two receptor locations every third day throughout the year. The samples were collected on Nylon filter substrates (preceded by a denuder upstream for capturing acidic gases) and Teflon filter substrates for WSII and mass measurements, respectively. Further, on-site meteorological parameters were recorded at both locations. The annual average PM concentrations observed were: PM2.5: 144 ± 81 μgm−3 (Site A), 163 ± 95 μgm−3 (Site B); and PM10: 245 ± 116 μgm−3 (Site A), 279 ± 152 μgm−3 (Site B). On average, SO42−, NO3−, Cl− and NH4+ contributed to ∼90% to PM2.5WSII mass and ∼82% to PM10WSII mass, which in turn made up ∼35% of PM2.5 mass and ∼23% of the PM10 mass across both sites. SO42− concentration was found to be highest followed by NO3−, NH4+ and Cl− for both PM fractions. Mann-Whitney U test revealed that both sites were similar with respect to WSII mass indicating city's airshed average concentration with respect to the major ions. The highest WSII contribution to the total PM was found in winter season (37–40% for PM2.5 and 27–31% for PM10) followed by monsoon (36–38% for PM2.5 and 18–21% for PM10), post-monsoon (28–34% for PM2.5 and 21–23% for PM10) and pre-monsoon (21–27% for PM2.5 and 15% for PM10). High contribution during winter was because of higher emissions of precursor gases in combination with moderate relative humidity (36–59%) and minimal precipitation (average ∼0.2 mm). Sulphur Oxidation Ratio and Nitrogen Oxidation Ratio indicated high photochemical oxidation with a greater extent of SO42− formation compared to NO3−. Although high concentrations of NH3 gas were observed, there was insufficient NH4+ ions for neutralizing counter ions with Ammonium Neutralization Ratio values of 0.76±0.14 for PM2.5 and 0.62±0.14 for PM10. Finally, aerosol liquid water content (ALWC) and acidity were estimated using a thermodynamic equilibrium model, ISORROPIA-II. It was found that PM2.5 pH varied from 2.9 to 6.2 (avg. 4.4±0.8) and the PM2.5 mass doubled at RH ∼90% because of the high particle bound water. Consequently, a reduction in SO2 would result in instantaneous cuts of SO42−, PM2.5, and ALWC.

Electron‐Deficient Phenanthrenequinone Derivative for Photoactivated Hydrogen Atom Transfer Mediated Oxidation of Secondary Alcohols

AbstractIn 2000, Fukuzumi and co‐workers reported a seminal study on the photochemical oxidation of benzylic alcohols with visible‐light‐excited 9,10‐phenanthrenequinone (PQ) under argon atmosphere (J. Am. Chem. Soc. 2000, 122, 8435). We optimized the reaction conditions they reported and were able to oxidize 1‐(4‐methoxyphenyl)ethanol quantitatively to 4'‐methoxyacetophenone in only 15 min with 10 mol % PQ as a photocatalyst under oxygen. However, we observed a significant decrease in the oxidation rate with more electron‐deficient benzylic alcohols as starting materials. To improve the photooxidation performance, we designed a high‐yielding synthetic route for a novel, more electron‐deficient PQ derivative, 3,6‐bis(trifluoromethyl)‐9,10‐phenanthrenequinone (PQ‐CF3). Its efficiency as a photocatalyst in the fast oxidation of secondary alcohols was demonstrated not only with several electronically diverse benzylic alcohols but also with aliphatic substrates. The comprehensive mechanistic studies based on Hammett plot construction, kinetic isotope experiments, and DFT computations suggest that the mechanistic pathway of the alcohol oxidation is dependent on the electronic properties of both the catalyst and the substrate. As the key mechanistic discovery, we showed that the newly developed PQ‐CF3 operates as a highly efficient hydrogen atom transfer (HAT) catalyst.

An insight into environmental footprints of emerging air-conditioning systems towards sustainable cities

In this study, the environmental impacts of six conventional and modern air conditioning systems, including vapor-compression air conditioning (VAC), hybrid membrane-based air conditioning (HMBAC), desiccant enhanced evaporative air conditioning (DEVap), solar HMBAC, solar DEVap, and inverter VAC, are analyzed using a cradle-to-gate life cycle assessment (LCA) approach. The assessment is based on climate change, ozone depletion, terrestrial acidification, freshwater eutrophication, human toxicity, photochemical oxidant formation, ecotoxicity, water depletion, and fossil fuel depletion impacts. The LCA findings reveal that membrane-based systems (HMBAC and DEVap) are highly environmentally-friendly in comparison to the regular VAC systems (household split coolers), showing the capability of membranes in developing efficient air conditioning systems. In addition, solar-assisted systems reduce seven out of eleven environmental impacts, while they cause severe eutrophication, marine and freshwater ecotoxicity, and human toxicity consequences. Furthermore, it is unveiled that the inverter can reduce up to 38% of the environmental impacts of VAC systems which are the most common air conditioning system in buildings. Therefore, the manipulation of the inverter system in VACs can be considered as one of the short-term solutions in reducing the environmental footprints of air conditioning. Finally, the sensitivity analysis is applied to show the reliability of the outcomes.

3H‐Phenothiazin‐3‐one: A Photocatalyst for the Aerobic Photochemical Oxidation of Sulfides to Sulfoxides

AbstractIn this study, 3H‐phenothiazin‐3‐one is identified as a photocatalyst for the photochemical oxidation of sulfides to sulfoxides. This photocatalytic method uses a low catalyst loading (0.05 mol%), molecular oxygen as the sole oxidant, and a blue LED lamp as the irradiation source. It can be applied to the oxidation of both alkyl‐aryl and alkyl‐alkyl sulfides. Moreover, the method is also applicable in the synthesis of the known pharmaceutically active compounds Modafinil and Sulforaphane.

Cobalt doped nitrogen-vacancies-rich C3N5 with optimizing local electron distribution boosts peroxymonsulfate activation for tetracycline degradation: Multiple electron transfer mechanisms

Heterogeneous photocatalysis coupled with peroxymonosulfate (PMS) activation is considered as an advanced water purification technology for emerging contaminates degradation. In this study, Cobalt (Co) doped nitrogen-vacancies-rich C3N5 photocatalysts (Co/Nv-C3N5) were designed to activate PMS for tetracycline removal. The photo-chemical oxidation system displayed superior advantage, in which the observed rate constant of tetracycline degradation (0.1488 min−1) was 10.86 and 1.82 times higher than that of photo-oxidation and chemical-oxidation systems. Density functional theory calculation results verified the reconstruction of local charge distribution during PMS activation, indicating Co doping and nitrogen-vacancy engineering not only promoted photoelectrons capture, but also boosted electron transfer from the C–N framework to PMS and the generation of active species. Furthermore, several unique multiple electron transfer mechanisms were found in nonradicals (h+, 1O2 and Co(IV)) pathways. Additionally, three possible tetracycline degradation pathways were proposed and the toxicity of the intermediates was evaluated. Overall, the findings from this study provided a novel strategy for developing high-efficient photocatalyst for the rapid degradation of organic pollutants.

Removal of Organic Micro-Pollutants from Wastewater in Electrochemical Processes—Review

The aim of the paper is to present information from the literature concerning the course of electrochemical wastewater treatment processes in regard to organic micro-pollutant removal. Most often, in order to remove xenobiotics that are difficult to degrade biochemically, advanced oxidation processes and photochemical processes with or without catalysts are used. The efficiency of these processes can be supported by the flow of electric current through the solution being purified in a special system. This paper presents the theoretical foundations of processes such as electrocoagulation, electroflotation, and advanced chemical and photochemical oxidation supported by electric power. Among the processes where the Fenton’s reagent is the oxidant, the electro-Fenton and photo-electro-Fenton processes are also described. This information is supplemented with examples of the use of these processes for removal/degradation of selected organic compounds such as pesticides, dyes, pharmaceuticals, cosmetic ingredients, and other organic xenobiotics from wastewater.

Mass-Integration and Environmental Evaluation of Chitosan Microbeads Production Modified with of Thiourea and Magnetite Nanoparticles

Bioadsorbents based on biopolymers modified with magnetic nanoparticles stand out for being non-toxic, effective, and easy to recover. Thus, the objective of the present work was to carry out a computer-aided environmental evaluation of the industrial-scale production of bioadsorbents from chitosan modified with iron nanoparticles and functionalized with thiourea as a chelating agent plus mass integration. The plant simulation was carried out in Aspen Plus, and for the mass integration of the process, a pinch analysis was used to determine the minimum target fresh and residual water amount, assuming two process stages: (1) the synthesis of magnetite nanoparticles, and (2) the production of chitosan-based bioadsorbents. The environmental assessment was performed using the waste reduction algorithm (WAR). The potential environmental impact (PEI) was quantified, taking into account the impact of the products and energy, obtaining a value below zero of −0.78 PEI/kg of the product. The photochemical oxidation potential (PCOP) stood out as the category with the greatest impact, mainly related to the use of ethanol during washing. The categories related to toxicological impacts (HTPI, HTPE, TTP, and ATP) had lower values than those related to atmospheric impacts (GWP, ODP, PCOP, and AP). The mass integration of the process resulted in fewer impacts in the HTPE category, as a consequence of the decrease in NaOH in the residual streams and the release of 0.297 PEI/kg of product in the ATP category caused by the presence of Al(OH)₃. It can be concluded that the mass integration managed to reduce up to 51% of the freshwater used in the processes, and it is a useful tool, as it slightly decreased the total potential impacts.

Photochemical Oxidation of Dimethyl Sulfide with Triplet Nitro Compounds

Photochemical Oxidation of Dimethyl Sulfide with Triplet Nitro Compounds

Daytime Atmospheric Halogen Cycling through Aqueous-Phase Oxygen Atom Chemistry.

Halogen atoms are important atmospheric oxidants that have unidentified daytime sources from photochemical halide oxidation in sea salt aerosols. Here, we show that the photolysis of nitrate in aqueous chloride solutions generates nitryl chloride (ClNO2) in addition to Cl2 and HOCl. Experimental and modeling evidence suggests that O(3P) formed in the minor photolysis channel from nitrate oxidizes chloride to Cl2 and HOCl, which reacts with nitrite to form ClNO2. This chemistry is different than currently accepted mechanisms involving chloride oxidation by OH and could shift our understanding of daytime halogen cycling in the lower atmosphere.

Photo-on-Demand In Situ Phosgenation Reactions That Cross Three Phases of a Heterogeneous Solution of Chloroform and Aqueous NaOH.

Here, we report a novel photo-on-demand in situ phosgenation reaction that crosses three phases of a heterogeneous solution of chloroform (CHCl3) and aqueous NaOH containing an aryl alcohol or amine. This reaction system enables the safe, convenient, and inexpensive synthesis of carbonate esters, polycarbonates, and N-substituted ureas from aryl alcohols, aryl diols, and primary/secondary amines, respectively, on a practical scale and with good yield. The photochemical oxidation of CHCl3 to phosgene (COCl2) occurs upon irradiation with UV light from a low-pressure mercury lamp of both the gas and liquid phases of the reaction system under O2 bubbling of the vigorously stirred sample solution. The following reaction mechanisms are suggested: The aryl alcohol reacts in situ with the generated COCl2 at the interfaces of the organic/aqueous phases and aqueous/gas phases, in competition with the decomposition of COCl2 due to hydrolysis. Nucleophilicity and hydrophilicity are enhanced by the formation of aryl alkoxide ion through the reaction with NaOH, whereas the reaction of amine proceeds through neutralization of the generated HCl by the aqueous NaOH.