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Phenolic aldehydes are widespread pollutants in water and soil, originating from lignin-based agro-industries. With increasing wastewater pollution, improved treatment systems are necessary to degrade phenolic aldehydes into less hazardous compounds. Over the past two decades, ozonolysis wastewater treatment has been implemented in the United States, Japan, and South Korea. However, the mechanistic understanding of phenolic aldehyde ozonolysis in water remains incomplete. This study investigates the ozonolysis of three model phenolic aldehydes (syringaldehyde, vanillin, 4-hydroxybenzaldehyde) in representative concentrations for wastewater of 0.5–1.5 mM and pH 4–8. Each compound solution was sparged for 30 min at a fixed O3(g) flow (0.20 to 1.00 L min−1), providing steady-state dissolved concentrations of 5.4 to 16.2 μM. Reactant loss and product generation were monitored using UV–visible (UV–vis) spectroscopy, ultra-high pressure liquid chromatography (UHPLC) with UV–vis and mass spectrometry (MS) detection, and ion chromatography with conductivity and MS detection of anions. Identified products based on their mass-to-charge ratio (m/z−) included oxalic acid (89), glycolic acid (75), formic acid (45), and maleic acid (115). Additional intermediate products were identified under various reaction conditions, revealing competing mechanisms in the degradative oxidation of aqueous phenolic aldehydes exposed to O3(g). A unifying mechanism is proposed to explain the production of smaller, less toxic molecules during phenolic aldehyde ozonolysis, enhancing water quality. This mechanism serves as a basis for evaluating the implementation of ozonolysis in scaled-up water treatment processes. 

Iodinated disinfection by-products (I-DBPs) are of growing concern due to their elevated toxicity compared to their chlorinated counterparts, with links to adverse health effects such as bladder cancer and miscarriages. Medical imaging agents like iohexol, commonly used in healthcare facilities, introduce iodine into wastewater systems. This study investigates the photodegradation of iohexol and the subsequent formation of products, including I-DBPs, during simulated final wastewater treatment under chlorination and sunlight exposure. Experiments were conducted with solutions containing 30 μM iohexol, 3 mg L−1 humic acids, and 5.5 mg L−1 hypochlorite. Samples were irradiated at λ ≥ 295 nm and subject to ion chromatography monitoring of I−, IO3−, Cl−, and ClO3−, providing mechanistic insight into the fate of iodide released from iohexol. UV-visible spectroscopy was employed to monitor the degradation profile of iohexol and the concurrent release of iodide. Electrospray ionization mass spectrometry (ESI-MS) identified a range of anionic products based on their mass-to-charge ratios (m/z), including low molecular weight carboxylic acids, their carcinogenic haloacetic derivatives (chloroacetic acid (m/z 93), iodoacetic acid (IAA, m/z 185), and hydroxyiodoacetic acid (m/z 201)) as well as phenolic halides. Notably, IAA was present at a concentration of 0.16 μM at the conclusion of the reaction. These findings elucidate photodeiodination-coupled radical attack, photooxidative cleavage, and halogenation transformation pathways of iodinated compounds during disinfection and underscore the potential risks associated with their presence in wastewater. The results provide valuable insights for medical facilities and wastewater treatment plants aiming to mitigate the formation of hazardous I-DBPs. 

As the Special Issues “Feature Papers in Photochemistry” and “Feature Papers in Photochemistry II” conclude, it is crucial to acknowledge the remarkable progress and persistent gaps that continue to shape the journey of photochemistry research [...] 

Landfills for disposing of solid waste are designed, located, managed, and monitored facilities expected to comply with government regulations to prevent contamination of the surrounding environment. After the average life expectancy of a typical landfill (30 to 50 years), a large investment in the construction, operation, final closure, and 30-year monitoring of a new site is needed. In this case study, we provide a holistic explanation of the unexpected development of elevated temperature landfills (ETLFs), such as that in the city of Bristol (United States) on the border of the states of Virginia and Tennessee, including the initial role played by coal ash. Despite the increasing frequency of ETLF occurrence, there is limited knowledge available about their associated environmental problems. The study uses mixed (qualitative, quantitative, and mapping) methods to analyze (1) the levels of odoriferous reduced sulfur compounds, ammonia, and volatile organic compounds (VOCs) emitted, (2) the ratio of methane to carbon dioxide concentrations in five locations, which dropped from unity (normal landfill) to 0.565, (3) the location of gas well heads with gradients of elevated temperatures, and (4) the correlation of the filling rate (upward of ~12 m y−1) with depth for registered events depositing coal ash waste. The work identifies spatial patterns that support the conclusion that coal ash served as the initiator for an ETLF creation. The case of the city of Bristol constitutes an example of ETLFs with elevated temperatures above the regulatory United States Environmental Protection Agency (EPA) upper threshold (65 °C), having alongside low methane emissions, large production of leachate, land subsidence, and a large production of organic compounds. Such landfills suffer abnormal chemical reactions within the waste mass that reduce the life expectancy of the site. Residents in such communities suffer intolerable odors from fugitive emissions and poor air quality becomes prominent, affecting the well-being and economy of surrounding populations. Conclusive information available indicates that the Bristol landfill has been producing large amounts of leachate and hazardous gases under the high pressures and temperatures developed within the landfill. A lesson learned, which should be used to prevent this problem in the future, is that the early addition of coal ash into the landfill would have catalyzed the process of ETLF creation. The work considers the public health risks and socioeconomic problems of residents exposed to emissions from an ETLF and discusses the efforts needed to prevent further incidents in other locations. 

Formate (HCOO–) is the most dominant intermediate identified during carbon dioxide electrochemical reduction (CO2ER). While previous studies showed that copper (Cu)-based materials that include Cu(0), Cu2O, and CuO are ideal catalysts for CO2ER, challenges to scalability stem from low selectivity and undesirable products in the −1.0–1.0 V range. There are few studies on the binding mechanism of intermediates and products for these systems as well as on changes to surface sites upon applying potential. Here, we use an in situ approach to study the redox surface chemistry of formate on Cu thin films deposited on Si wafers using a VeeMAX III spectroelectrochemical (SEC) cell compatible with attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). Spectra for surface species were collected in real time as a function of applied potential during cyclic voltammetry (CV) experiments. Results showed the reproducibility of CV curves on freshly prepared Cu/Si wafers with relatively high signal-to-noise ATR-FTIR absorbance features of surface species during these electrochemical experiments. The oxidation reaction of HCOO– to bicarbonate (HCO3–) was observed using ATR-FTIR at a voltage of 0.27 V. Samples were then subjected to reduction in the CV, and the aqueous phase products below the detection limit of the SEC-ATR-FTIR were identified using ion chromatography (IC). We report the formation of glycolate (H3C2O3–) and glyoxylate (HC2O3–) with trace amounts of oxalate (C2O42–), indicating that C–C coupling reactions proceed in these systems. Changes to the oxidation state of surface Cu were measured using X-ray photoelectron spectroscopy, which showed a reduction in Cu(0) and an increase in Cu(OH)2, indicating surface oxidation. 

Potassium is used extensively as a promoter with iron catalysts in Fisher–Tropsch synthesis, water–gas shift reactions, steam reforming, and alcohol synthesis. In this paper, the identification of potassium chemical states on the surface of iron catalysts is studied to improve our understanding of the catalytic system. Herein, potassium-doped iron oxide (α-Fe2O3) nanomaterials are synthesized under variable calcination temperatures (400–800 °C) using an incipient wetness impregnation method. The synthesis also varies the content of potassium nitrate deposited on superfine iron oxide with a diameter of 3 nm (Nanocat®) to reach atomic ratios of 100 Fe:x K (x = 0–5). The structure, composition, and properties of the synthesized materials are investigated by X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, Fourier-transform infrared, Raman spectroscopy, inductively coupled plasma-atomic emission spectroscopy, and X-ray photoelectron spectroscopy, as well as transmission electron microscopy, with energy-dispersive X-ray spectroscopy and selected area electron diffraction. The hematite phase of iron oxide retains its structure up to 700 °C without forming any new mixed phase. For compositions as high as 100 Fe:5 K, potassium nitrate remains stable up to 400 °C, but at 500 °C, it starts to decompose into nitrites and, at only 800 °C, it completely decomposes to potassium oxide (K2O) and a mixed phase, K2Fe22O34. The doping of potassium nitrate on the surface of α-Fe2O3 provides a new material with potential applications in Fisher–Tropsch catalysis, photocatalysis, and photoelectrochemical processes. 

Atmospheric organic aerosols play a major role in climate, demanding a better understanding of their formation mechanisms by contributing multiphase chemical reactions with the participation of water. The sunlight driven aqueous photochemistry of small 2-oxocarboxylic acids is a potential major source of organic aerosol, which prompted the investigations into the mechanisms of glyoxylic acid and pyruvic acid photochemistry reviewed here. While 2-oxocarboxylic acids can be contained or directly created in the particles, the majorities of these abundant and available molecules are in the gas phase and must first undergo the surface uptake process to react in, and on the surface, of aqueous particles. Thus, the work also reviews the acid-base reaction that occurs when gaseous pyruvic acid meets the interface of aqueous microdroplets, which is contrasted with the same process for acetic acid. This work classifies relevant information needed to understand the photochemistry of aqueous pyruvic acid and glyoxylic acid and motivates future studies based on reports that use novel strategies and methodologies to advance this field.