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Canine parvovirus (CPV) is a major pathogen in canines, with a high mortality rate in unvaccinated puppies. CPV is traditionally classified into three antigenic variants (CPV-2a, CPV-2b and CPV-2c) based on the amino acid sequence of the VP2 protein. Currently, various mutations are described in the receptor-binding area or in the regions of greatest antigenicity of the VP2 protein, giving rise to new viral variants that are capable of immunological escape, affecting the protective immunity of traditional vaccines. In the present study, a molecular characterization of the VP2 gene was performed, which included phylogenetic analysis, amino acid characterization and determination of selection pressures. Blood samples were initially collected from canine patients with clinical signs of gastrointestinal infection, of which 69 were positive for CPV as measured by means of PCR and 18 samples were selected for the amplification of the complete VP2 gene. The analysis revealed a higher rate of CPV-2c-positive patients compared to CPV-2b. Furthermore, the amino acid characterization of VP2 indicated mutations in the regions of highest antigenicity previously described in the literature (CPV-2b: 297 and 324; CPV-2c: 440), as well as others not previously documented (CPV-2b: 514; CPV-2c: 188, 322, 379, 427 and 463). Our analysis of selection pressure showed that the VP2 gene is under negative selection. However, positive selection point sites were identified, both in CPV-2c (324, 426 and 440) and CPV-2b (297 and 324), at sites that have been associated with evasion of the immune response via antigenic drift, which possibly has implications for the protective immunity generated by traditional vaccines.

Abstract: In order to determine the presence the isolates of Salmonella spp. and Shigella spp. and associated with the clinical manifestations the acute diarrheic syndrome from children under six year of age, 96 stool samples were analyzed by carrying out coprocultures collected from patients under six years of age at the Servicio Autónomo Hospital Universitario “Antonio Patricio de Alcalá” in Cumaná, state of Sucre from July to October 2002. The analyses resulted in 50 positive cases (52.08%), 5 of which were 16% corresponded to Shigella spp. and 10% of Salmonella spp. The distribution of isolates was 50% for Shigella sonnei and 40% each for Salmonella agona and Salmonella enteritidis. For Shigella spp., the statistical analysis revealed a highly significant association (p

Abstract: Diarrhea represents a serious public health problem, and bacteria is one of the most frequent causes of the same, which requires the need to select an effective bacteriological diagnosis. In order to determine the frequency of Aeromonas spp. as a causal agent of gastrointestinal illnesses, a study was carried out in patients under 6 years of age with acute diarrheic syndrome, who were attended in the pediatric emergency service at the □Antonio Patricio de Alcalá□ University Hospital (SAHUAPA), in Cumaná, Sucre state. For this study130 stool samples were collected during the period of May to September 2002, and a microbiological study of the samples was carried out through copro-culture and the antimicrobial susceptibility test using the disk diffusion method. Of the total number of samples analyzed, a positive response was obtained in 24,60%; of which 12,5% corresponded to Aeromonas spp. The species of the Aeromonas gender that were identified were A. caviae, A. hydrophila and A. sobria. Aeromonas caviae was the most frequent, representing 50% of the isolated species. The distribution for age placed the species of Aeromonas spp. in the 1 to 4-year age group, and more specifically in the age group of 1 to 2 years where three of the four isolates were located. In relation to antimicrobial susceptibility, all the isolates of Aeromonas spp. were sensitive to chloramphenicol at 100,00% and to trimetoprim-sulfamethoxazole at 75,00%. They showed resistant to cefalotin at 75,00%. The results obtained in this research indicate that Aeromonas spp. presented a low frequency and ease of treatment with antimicrobials; however, due to their clinical and microbial repercussion, their identification in intestinal samples is justified. Resumen: La enfermedad diarreica representa un grave problema de salud pública, siendo las bacterias una de las causas más frecuentes, lo que obliga a realizar su búsqueda con un diagnóstico bacteriológico certero. Con la finalidad de determinar la frecuencia de Aeromonas spp. como agente causal de enfermedades gastrointestinales, se realizó un estudio en pacientes menores de seis años de edad con síndrome diarreico agudo, asistidos en la emergencia pediátrica del Servicio Autónomo Hospital Universitario Antonio Patricio de Alcalá (SAHUAPA), en Cumaná, estado Sucre; para ello se recolectaron 130 muestras de heces durante el período de mayo a septiembre de 2002, a las cuales se les realizaron estudios microbiológicos a través de coprocultivo y susceptibilidad antimicrobiana mediante la técnica de difusión en disco. Del total de muestras analizadas, se obtuvo un porcentaje de positividad de 24,60%; de los cuales 12,50% correspondieron a Aeromonas spp. Las especies identificadas del género Aeromonas, fueron A. caviae, A. hydrophila y A. sobria; Aeromonas caviae fue la más frecuente, representando el 50,00% de las especies aisladas. La distribución por edad, ubicó las especies de Aeromonas spp. en edades comprendidas de 1 a 4 años, específicamente en el grupo de edad de 1 a 2 años se ubicaron tres de los cuatro aislamientos obtenidos. En relación a la susceptibilidad antimicrobiana, las cepas aisladas de Aeromonas spp. fueron sensibles al cloranfenicol en 100,00% y al trimetoprim-sulfametoxazol en un 75,00%; así mismo, se mostraron resistentes a cefalotina en 75,00%. Los resultados obtenidos en este trabajo de investigación, muestran que Aeromonas spp. es una bacteria de baja frecuencia y de fácil tratamiento con antimicrobianos, en el caso de pacientes que así lo requieran; sin embargo, por su repercusión clínica y microbiológica se justifica su búsqueda en muestras intestinales.

Abstract: Cysticercosis represents a problem of public health in geographic areas where insalubrity is present. With the objective of determining the prevalence of teniasis and cysticercosis in the town EL Peñón and its possible association with risk factors, 100 children of both sexes were studied, chosen at random, during the period September 2000 to September 2001. A survey was used to collect personal data and epidemiological data. To determined the presence of Taenia sp.eggs, fresh stool samples were collected, and were examined wet with saline physiologic solution at 0.85% using the Ritchie concentration method. Additionally 5 ml of blood were extracted from the vein to quantify specific antibodies of AbG anticysticerci by the ELISA technique, using antigens of T. crassiseps. They were no eggs of taenia sp. in the samples of stool, however, 3.00% presented levels of AbG anticysticerci equal to or higher than 1:512. The largest seroprevalence was in males (3.445), in the status V (7.14%), in the children that did not wash their hands before eating (5.17%), or after going to the bathroom (4.00%), or who drink non-treated water (5.66%), that sleep in crowded conditions (6.66%) and in children who live in houses where pigs are raised (7.14%). No statistically significant association was found between the risk factors and the presence of AbG anticisticerci. The results obtained suggest the need for epidemic surveillance in the infantile population of the community. Resumen: La cisticercosis representa un problema de salud pública en áreas geográficas donde la insa- lubridad esta presente. Con el objetivo de determinar la prevalencia de teniasis y cisticercosis en la localidad El Peñón y su posible asociación con los factores de riesgo, se estudiaron 100 escolares, de uno u otro sexo, escogidos al azar, durante el periodo Septiembre de 2000 a Septiembre 2001. A cada niño se le realizó una encuesta donde se recopilaron datos personales y datos epidemiológi- cos. Se recolectaron muestras seriadas de heces las cuales fueron examinadas al fresco con solu- ción salina fisiológica al 0,85% y el método de concentración de Ritchie. Así mismo se les extrajo 5 mL de sangre venosa para cuantificar los anticuerpos séricos específicos IgG anticisticerco me- diante la técnica de ELISA, usando antígenos de T. crassiseps. No se encontró huevos de Taenia sp. en las muestras de heces; sin embargo, el 3,00% de los individuos presentó títulos de IgG anti- cisticerco iguales o superiores a 1:512. La mayor seroprevalencia se encontró en el sexo masculino (3,44%), en el estrato socioeconómico V (7,14%), en los niños que no se lavan las manos antes de comer (5,17%), después de ir al baño (4,00%), que no tratan el agua antes de su consumo (5,66%), que duermen en ambientes hacinados (6,66%), y en niños en cuyas casas crían cerdos (7,14%). No se encontró asociación estadística significativa entre los factores epidemiológicos evaluados y la presencia de IgG anticisticerco (p>0,05). Los resultados obtenidos sugieren una vigilancia epide- miológica en la población infantil de la comunidad.

Semiconductor photocatalysis with commercial TiO 2 (Degussa P25) has shown significant potential in water treatment of organic pollutants. However, the photoinduced reactions of adsorbed catechol, a phenolic air pollutant from biomass burning and combustion emissions, at the air-solid interface of TiO 2 remain unexplored. Herein we examine the photocatalytic decay of catechol in the presence of water vapor, which acts as an electron acceptor. Experiments under variable cut-off wavelengths of irradiation (λ cut-off ≥ 320, 400, and 515 nm) distinguish the mechanistic contribution of a ligand-to-metal charge-transfer (LMCT) complex of surface chemisorbed catechol on TiO 2 . The LMCT complex injects electrons into the conduction band of TiO 2 from the highest occupied molecular orbital of catechol by visible light (≥2.11 eV) excitation. The deconvolution of diffuse reflectance UV-visible spectral bands from LMCT complexes of TiO 2 with catechol, o -semiquinone radical, and quinone and the quantification of the evolving gaseous products follow a consecutive kinetic model. CO 2 (g) and CO(g) final oxidation products are monitored by gas chromatography and Fourier-transform infrared spectroscopy. The apparent quantum efficiency at variable λ cut-off are determined for reactant loss (Φ - TiO 2 /catechol = 0.79 ± 0.19) and product growth Φ CO 2 = 0.76 ± 0.08). Spectroscopic and electrochemical measurements reveal the energy band diagram for the LMCT of TiO 2 /catechol. Two photocatalytic mechanisms are analyzed based on chemical transformations and environmental relevance., Competing Interests: The authors declare no competing financial interest., (© 2024 American Chemical Society.)

Climate change is a complex, global issue that is impacting human health in various ways, with healthcare being a significant contributor to carbon emissions in the United States. This review discusses the environmental impact of important aspects of gynecologic oncology care, including surgery, anesthesia care, radiology, chemotherapy, and radiation oncology. Operating room energy and material use is highlighted, with a focus on the environmental impact of robotic surgery. The contribution of certain anesthetic gases in increasing greenhouse gas emissions is addressed. Additionally, the environmental impacts of radiologic imaging, chemotherapy, and radiation oncology are also discussed. Despite the complexity of climate change, there are multiple strategies on the individual and institutional level that can help mitigate the environmental impact of gynecologic oncology care. Individual efforts include practicing red bag stewardship, limiting single use-supplies, decreasing the use of potentially deleterious anesthetics, and supporting research into alternative dosing for chemotherapy and radiation which requires less patient travel. Institutional strategies include investing in efficient HVAC systems, utilizing reusable and reprocessed materials and devices, and purchasing renewable energy sources. Both individuals and institutions can advocate with industry and government at all levels for practices and policies that support lower carbon emissions. By recognizing our role in reducing carbon emissions, we can work towards improving the well-being of our patients and the larger community., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Author(s).)

Formate (HCOO - ) is the most dominant intermediate identified during carbon dioxide electrochemical reduction (CO 2 ER). While previous studies showed that copper (Cu)-based materials that include Cu(0), Cu 2 O, and CuO are ideal catalysts for CO 2 ER, 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 (HCO 3 - ) 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 (H 3 C 2 O 3 - ) and glyoxylate (HC 2 O 3 - ) with trace amounts of oxalate (C 2 O 4 2- ), 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.

Deubiquitinating enzymes (DUBs) are an emerging drug target class of ~100 proteases that cleave ubiquitin from protein substrates to regulate many cellular processes. A lack of selective chemical probes impedes pharmacologic interrogation of this important gene family. DUBs engage their cognate ligands through a myriad of interactions. We embrace this structural complexity to tailor a chemical diversification strategy for a DUB-focused covalent library. Pairing our library with activity-based protein profiling as a high-density primary screen, we identify selective hits against 23 endogenous DUBs spanning four subfamilies. Optimization of an azetidine hit yields a probe for the understudied DUB VCPIP1 with nanomolar potency and in-family selectivity. Our success in identifying good chemical starting points as well as structure-activity relationships across the gene family from a modest but purpose-build library challenges current paradigms that emphasize ultrahigh throughput in vitro or virtual screens against an ever-increasing scope of chemical space., (© 2023. The Author(s).)

Biomass burning emissions contain abundant phenolic aldehydes (e.g., syringaldehyde, vanillin, and 4-hydroxybenaldehyde) that are oxidized during atmospheric transport, altering the physicochemical properties of particulates. Herein, the oxidative processing of thin films made of syringaldehyde, vanillin, and 4-hydroxybenaldehyde is studied at the air-solid interface under a variable O 3 (g) molar ratio (410 ppbv-800 ppmv) and relative humidity (0-90%). Experiments monitored the absorption changes of C=C, C=O, and -COOH vibration changes during the oxidation of thin films by transmission Fourier transform infrared spectroscopy (FTIR). Selected spectroscopic features of aromatic ring cleavage by O 3 (g) revealed the production of carboxylic acids. Instead, monitoring O-H stretching provided a comparison of a hydroxylation channel from in situ produced hydroxyl radical. The overall oxidation reactivity trend syringaldehyde > vanillin > 4-hydroxybenzladehyde can be explained based on the additional electron density from methoxide substituents to the ring. The reactive uptake coefficient of O 3 (g) increases for higher relative humidity, e.g., for syringaldehyde by 18 and 215 times at 74% and 90% relative humidity (RH), respectively, as compared to dry conditions. A Langmuir-Hinshelwood mechanism fits well the kinetics of oxidation under a variable O 3 (g) molar ratio at 74% RH, providing useful information that should be included in atmospheric chemistry models., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Abundant substituted catechols are emitted to, and created in, the atmosphere during wildfires and anthropogenic combustion and agro-industrial processes. While ozone (O 3 ) and hydroxyl radicals (HO • ) efficiently react in a 1 μs contact time with catechols at the air-water interface, the nighttime reactivity dominated by nitrate radicals (NO 3 ) remains unexplored. Herein, online electrospray ionization mass spectrometry (OESI-MS) is used to explore the reaction of NO 3 (g) with a series of representative catechols (catechol, pyrogallol, 3-methylcatechol, 4-methylcatechol, and 3-methoxycatechol) on the surface of aqueous microdroplets. The work detects the ultrafast generation of nitrocatechol (aromatic) compounds, which are major constituents of atmospheric brown carbon. Two mechanisms are proposed to produce nitrocatechols, one (equivalent to H atom abstraction) following fast electron transfer from the catechols (QH 2 ) to NO 3 , forming NO 3 - and QH 2 •+ that quickly deprotonates into a semiquinone radical (QH • ). The second mechanism proceeds via cyclohexadienyl radical intermediates from NO 3 attack to the ring. Experiments in the pH range from 4 to 8 showed that the production of nitrocatechols was favored under the most acidic conditions. Mechanistically, the results explain the interfacial production of chromophoric nitrocatechols that modify the absorption properties of tropospheric particles, making them more susceptible to photooxidation, and alter the Earth's radiative forcing.

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-Fe 2 O 3 ) 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 (K 2 O) and a mixed phase, K 2 Fe 22 O 34 . The doping of potassium nitrate on the surface of α-Fe 2 O 3 provides a new material with potential applications in Fisher-Tropsch catalysis, photocatalysis, and photoelectrochemical processes.

The heterogeneous reaction between thin films of catechol exposed to O 3 (g) creates hydroxyl radicals (HO • ) in situ, which in turn generate semiquinone radical intermediates in the path to form heavier polyhydroxylated biphenyl, terphenyl, and triphenylene products. Herein, the alteration of catechol aromatic surfaces and their chemical composition are studied during the heterogeneous oxidation of catechol films by O 3 (g) molar ratios ≥ 230 ppbv at variable relative humidity levels (0% ≤ RH ≤ 90%). Fourier transform infrared micro-spectroscopy, atomic force microscopy, electrospray ionization mass spectrometry, and reverse-phase liquid chromatography with UV-visible and mass spectrometry detection provide new physical insights into understanding the surface reaction. A Langmuir-Hinshelwood mechanism is accounted to report reaction rates, half-lives, and reactive uptake coefficients for the system under variable relative humidity levels. The reactions reported explain how the oligomerization of polyphenols proceeds at interfaces to contribute to the formation of brown organic carbon in atmospheric aerosols., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Substantial amounts of phenolic aldehydes, represented by the structures of syringaldehyde, vanillin, and 4-hydroxybenzaldehyde, are emitted to the atmosphere during biomass burning. The oxidative transformation of phenolic aldehydes during atmospheric transport has the potential to modify the physicochemical properties of particulates, which play a vital role in Earth's climate and human health. Herein, thin solid films made of syringaldehyde, vanillin, and 4-hydroxybenzaldehyde are oxidized in contact with O 3 (g) under a relative humidity of 74% representative of average global conditions. New physical insights into the surface reactions are achieved by analyzing isopropanol-extracted films before and during oxidation by multiple techniques. Changes in electronic transitions at 220, 310, and 350-400 nm registered by UV-vis spectroscopy show that the oxidized films have enhanced mass absorption coefficients at λ > 300 nm. Electrospray ionization (ESI) mass spectrometry (MS) and ion chromatography with conductivity and MS detection of extracted oxidized films confirm aromatic ring cleavage of syringaldehyde and vanillin by O 3 (g) with the production of carboxylic acids. Carboxylic acids were observed as anions ([M - H] - ) at m / z 45 (formic acid), 73 (glyoxylic acid), 75 (glycolic acid), 89 (oxalic acid), 115 (maleic acid), 117 (mesoxalic acid), 119 (tartronic acid), and 129 (maleic acid monomethyl ester), while other polyfunctional products were registered by ultrahigh-pressure liquid chromatography with UV-vis and MS detection. In situ production of hydroxyl radicals is confirmed by demethoxylation products and ipso attack at the C 1 ring position holding the -C(H)═O group. The order of reactivity increased with the number of methoxy substituents that donate electron density to the aromatic ring. Combined oxidation mechanisms for the three compounds are proposed based on all of the experimental observations and explain the contribution of aged biomass burning material to secondary organic aerosol formation.

Nitrogen-containing organic carbon (NOC) in atmospheric particles is an important class of brown carbon (BrC). Redox active NOC like aminophenols received little attention in their ability to form BrC. Here we show that iron can catalyze dark oxidative oligomerization of o- and p-aminophenols under simulated aerosol and cloud conditions (pH 1-7, and ionic strength 0.01-1 M). Homogeneous aqueous phase reactions were conducted using soluble Fe(III), where particle growth/agglomeration were monitored using dynamic light scattering. Mass yield experiments of insoluble soot-like dark brown to black particles were as high as 40%. Hygroscopicity growth factors (κ) of these insoluble products under sub- and super-saturated conditions ranged from 0.4-0.6, higher than that of levoglucosan, a prominent proxy for biomass burning organic aerosol (BBOA). Soluble products analyzed using chromatography and mass spectrometry revealed the formation of ring coupling products of o- and p-aminophenols and their primary oxidation products. Heterogeneous reactions of aminophenol were also conducted using Arizona Test Dust (AZTD) under simulated aging conditions, and showed clear changes to optical properties, morphology, mixing state, and chemical composition. These results highlight the important role of iron redox chemistry in BrC formation under atmospherically relevant conditions., (© 2022. The Author(s).)

Examining the concentration and types of airborne bacteria in waste paper and cardboard sorting plants (WPCSP) is an urgent matter to inform policy makers about the health impacts on exposed workers. Herein, we collected 20 samples at 9 points of a WPCSP every 6 winter days, and found that the most abundant airborne bacteria were positively and negatively correlated to relative humidity and temperature, respectively. The most abundant airborne bacteria (in units of CFU m -3 ) were: Staphylococcus sp. (72.4) > Micrococcus sp. (52.2) > Bacillus sp. (30.3) > Enterococcus sp. (24.0) > Serratia marcescens (20.1) > E. coli (19.1) > Pseudomonas sp. (16.0) > Nocardia sp. (1.9). The lifetime average daily dose (LADD) for the inhalation and dermal routes for the intake of airborne bacteria ranged from 3.7 × 10 -3 ≤ LADD Inhalation ≤ 2.07 × 10 1 CFU (kg d) -1 and 4.75 × 10 -6 ≤ LADD Dermal ≤ 1.64 × 10 -5 CFU (kg d) -1 , respectively. Based on a sensitivity analysis (SA), the concentration of airborne bacteria (C) and the exposure duration (ED) had the most effect on the LADD Inhalation and LADD Dermal for all sampling locations. Although the Hazard Quotient of airborne bacteria was HQ < 1, an acceptable level, the indoor/outdoor ratio (1.5 ≤ I/O ≤ 6.6) of airborne bacteria typically exceeded the threshold value (I/O > 2), indicating worker's exposure to an infected environment. Therefore, in the absence of sufficient natural ventilation the indoor ambient conditions of the WPCSP studied should be controlled by supplying mechanical ventilation., (Copyright © 2022. Published by Elsevier Inc.)

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.

The fast spread of coronavirus disease 2019 (COVID-19) constitutes a worldwide challenge to the public health, educational and trade systems, affecting the overall well-being of human societies. The high transmission and mortality rates of this virus, and the unavailability of a vaccine or treatment, resulted in the decision of multiple governments to enact measures of social distancing. Such measures can reduce the exposure to bioaerosols, which can result in pathogen deposition in the respiratory tract of the host causing disease and an immunological response. Thus, it is important to consider the validity of the proposal for keeping a distance of at least 2 m from other persons to avoid the spread of COVID-19. This work reviews the effect of aerodynamic diameter (size) of particles carrying RNA copies of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). A SARS-CoV-2 carrier person talking, sneezing or coughing at distance of 2 m can still provide a pathogenic bioaerosol load with submicron particles that remain viable in air for up to 3 h for exposure of healthy persons near and far from the source in a stagnant environment. The deposited bioaerosol creates contaminated surfaces, which if touched can act as a path to introduce the pathogen by mouth, nose or eyes and cause disease., (© 2020 The Authors. The International Journal of Health Planning and Management published by John Wiley & Sons Ltd.)

The multiple modes of SARS-CoV-2 transmission including airborne, droplet, contact, and fecal-oral transmissions that cause coronavirus disease 2019 (COVID-19) contribute to a public threat to the lives of people worldwide. Herein, different databases are reviewed to evaluate modes of transmission of SARS-CoV-2 and study the effects of negative pressure ventilation, air conditioning system, and related protection approaches of this virus. Droplet transmission was commonly reported to occur in particles with diameter >5 µm that can quickly settle gravitationally on surfaces (1-2 m). Instead, fine and ultrafine particles (airborne transmission) can stay suspended for an extended period of time (≥2 h) and be transported further, e.g., up to 8 m through simple diffusion and convection mechanisms. Droplet and airborne transmission of SARS-CoV-2 can be limited indoors with adequate ventilation of rooms, by routine disinfection of toilets, using negative pressure rooms, using face masks, and maintaining social distancing. Other preventive measures recommended include increasing the number of screening tests of suspected carriers of SARS-CoV-2, reducing the number of persons in a room to minimize sharing indoor air, and monitoring people's temperature before accessing a building. The work reviews a body of literature supporting the transmission of SARS-CoV-2 through air, causing COVID-19 disease, which requires coordinated worldwide strategies.

Iron-driven secondary brown carbon formation reactions from water-soluble organics in cloud droplets and aerosols create insoluble and soluble products of emerging atmospheric importance. This work shows, for the first time, results on dark iron-catalyzed polymerization of catechol forming insoluble black polycatechol particles and colored water-soluble oligomers under conditions characteristic of viscous multicomponent aerosol systems with relatively high ionic strength ( I = 1-12 m ) and acidic pH (∼2). These systems contain ammonium sulfate (AS)/nitrate (AN) and C3-C5 dicarboxylic acids, namely, malonic, malic, succinic, and glutaric acids. Using dynamic light scattering (DLS) and ultra high pressure liquid chromatography-mass spectrometry (UHPLC-MS), we show results on the rate of particle growth/agglomeration and identity of soluble oligomeric reaction products. We found that increasing I above 1 m and adding diacids with oxygen-to-carbon molar ratio (O:C > 1) significantly reduced the rate of polycatechol formation/aggregation by a factor of 1.3 ± 0.4 in AS solution in the first 60 min of reaction time. Using AN, rates were too slow to be quantified using DLS, but particles formed after 24 h reaction time. These results were explained by the relative concentration and affinity of ligands to Fe(III). We also report detectable amounts of soluble and colored oligomers in reactions with a slow rate of polycatechol formation, including organonitrogen compounds. These results highlight that brown carbon formation from iron chemistry is efficient under a wide range of aerosol physical states and chemical composition.

The quantification of atmospheric gases with small unmanned aerial systems (sUAS) is expanding the ability to safely perform environmental monitoring tasks and quickly evaluate the impact of technologies. In this work, a calibrated sUAS is used to quantify the emissions of ammonia (NH 3 ) gas from the exit stack a 0.1 MWth pilot-scale carbon capture system (CCS) employing a 5 M monoethanolamine (MEA) solvent to scrub CO 2 from coal combustion flue gas. A comparison of the results using the sUAS against the ion chromatography technique with the EPA CTM-027 method for the standard emission sampling of NH 3 shows good agreement. Therefore, the work demonstrates the usefulness of sUAS as an alternative method of emission measurement, supporting its application in lieu of traditional sampling techniques to collect real time emission data.

Biomass burning releases highly reactive methoxyphenols into the atmosphere, which can undergo heterogeneous oxidation and act as precursors for secondary organic aerosol (SOA) formation. Understanding the reactivity of such methoxyphenols at the air-water interface is a matter of major atmospheric interest. Online electrospray ionization mass spectrometry (OESI-MS) is used here to study the oxidation of two methoxyphenols among three phenolic aldehydes, 4-hydroxybenzaldehyde, vanillin, and syringaldehyde, on the surface of water. The OESI-MS results together with cyclic voltammetry measurements at variable pH are integrated into a mechanism describing the heterogeneous oxidative processing of methoxyphenols by gaseous ozone (O 3 ) and hydroxyl radicals (HO • ). For a low molar ratio of O 3 ≤ 66 ppbv, the OESI-MS spectra show that the oxidation is dominated by in situ produced HO • and results in the production of polyhydroxymethoxyphenols. When the level of O 3 increases (i.e., ≥78 times), the ion count of polyhydroxymethoxyphenols increases, while new ring fragmentation products are generated, including conjugated aldehydes and double bonds as well as additional carboxylic acid groups. The interfacial reactivity of methoxyphenols with O 3 and HO • is enhanced as the number of methoxy (-OCH 3 ) groups increases (4-hydroxybenzaldehyde < vanillin < syringaldehyde). The experimental observations are summarized in two reaction pathways, leading to the formation of (1) hydroxylated methoxyphenols and (2) multifunctional carboxylic acids from fragmentation of the aromatic ring. The new highly oxygenated products with low volatility are excellent precursors for aqueous SOA formation.

The photochemistry of pyruvic acid (PA) in aqueous atmospheric particles contributes to the production of secondary organic aerosols. This work investigates the fate of ketyl and acetyl radicals produced during the photolysis (λ ≥ 305 nm) of 5-100 mM PA under steady state [O 2 (aq)] = 260 μM (1.0 ≤ pH ≤ 4.5) for photon fluxes between 1 and 10 suns. The radicals diffuse quickly into the water/air interface of microbubbles and react with dissolved O 2 to produce singlet oxygen ( 1 O 2 * ). Furfuryl alcohol is used to trap and bracket the steady-state production of 2 × 10 -12 ≤ [ 1 O 2 * ] ≤ 1 × 10 -11 M. Ion chromatography mass spectrometry shows that 2,3-dimethyltartaric acid (DMTA), 2-(3-oxobutan-2-yloxy)-2-hydroxypropanoic acid (oxo-C 7 product), and 2-(1-carboxy-1-hydroxyethoxy)-2-methyl-3-oxobutanoic acid (oxo-C 8 product) are formed under all conditions investigated. The sigmoidal dependence of initial reaction rates with pH resembles the dissociation curve of PA. For increasing photon fluxes, the branching ratio of products shifts away from the radical recombination that favors DMTA toward multistep radical chemistry forming more complex oxocarboxylic acids (oxo-C 7 + oxo-C 8 ). The large steady-state production of 1 O 2 indicates that PA in aerosols can be a significant source of atmospheric oxidants on par with natural organic matter.

The structure of zymonic acid (systematic name: 4-hy-droxy-2-methyl-5-oxo-2,5-di-hydro-furan-2-carb-oxy-lic acid), C 6 H 6 O 5 , which had previously eluded crystallographic determination, is presented here for the first time. It forms by intra-molecular condensation of parapyruvic acid, which is the product of aldol condensation of pyruvic acid. A redetermination of the crystal structure of pyruvic acid (systematic name: 2-oxo-propanoic acid), C 3 H 4 O 3 , at low temperature (90 K) and with increased precision, is also presented [for the previous structure, see: Harata et al. (1977 ▸). Acta Cryst. B 33 , 210-212]. In zymonic acid, the hy-droxy-lactone ring is close to planar (r.m.s. deviation = 0.0108 Å) and the dihedral angle between the ring and the plane formed by the bonds of the methyl and carb-oxy-lic acid carbon atoms to the ring is 88.68 (7)°. The torsion angle of the carb-oxy-lic acid group relative to the ring is 12.04 (16)°. The pyruvic acid mol-ecule is almost planar, having a dihedral angle between the carb-oxy-lic acid and methyl-ketone groups of 3.95 (6)°. Inter-molecular inter-actions in both crystal structures are dominated by hydrogen bonding. The common R 2 2 (8) hydrogen-bonding motif links carb-oxy-lic acid groups on adjacent mol-ecules in both structures. In zymonic acid, this results in dimers about a crystallographic twofold of space group C 2/ c , which forces the carb-oxy-lic acid group to be disordered exactly 50:50, which scrambles the carbonyl and hydroxyl groups and gives an apparent equalization of the C-O bond lengths [1.2568 (16) and 1.2602 (16) Å]. The other hydrogen bonds in zymonic acid (O-H⋯O and weak C-H⋯O), link mol-ecules across a 2 1 -screw axis, and generate an R 2 2 (9) motif. These hydrogen-bonding inter-actions propagate to form extended pleated sheets in the ab plane. Stacking of these zigzag sheets along c involves only van der Waals contacts. In pyruvic acid, inversion-related mol-ecules are linked into R 2 2 (8) dimers, with van der Waals inter-actions between dimers as the only other inter-molecular contacts.

Small unmanned aircraft systems (sUAS) are rapidly transforming atmospheric research. With the advancement of the development and application of these systems, improving knowledge of best practices for accurate measurement is critical for achieving scientific goals. We present results from an intercomparison of atmospheric measurement data from the Lower Atmospheric Process Studies at Elevation-a Remotely piloted Aircraft Team Experiment (LAPSE-RATE) field campaign. We evaluate a total of 38 individual sUAS with 23 unique sensor and platform configurations using a meteorological tower for reference measurements. We assess precision, bias, and time response of sUAS measurements of temperature, humidity, pressure, wind speed, and wind direction. Most sUAS measurements show broad agreement with the reference, particularly temperature and wind speed, with mean value differences of 1.6 ± 2 . 6 ∘ C and 0.22 ± 0 . 59 m/s for all sUAS, respectively. sUAS platform and sensor configurations were found to contribute significantly to measurement accuracy. Sensor configurations, which included proper aspiration and radiation shielding of sensors, were found to provide the most accurate thermodynamic measurements (temperature and relative humidity), whereas sonic anemometers on multirotor platforms provided the most accurate wind measurements (horizontal speed and direction). We contribute both a characterization and assessment of sUAS for measuring atmospheric parameters, and identify important challenges and opportunities for improving scientific measurements with sUAS.

The use of small unmanned aerial systems (sUAS) for meteorological measurements has expanded significantly in recent years. SUAS are efficient platforms for collecting data with high resolution in both space and time, providing opportunities for enhanced atmospheric sampling. Furthermore, advances in mesoscale weather research and forecasting (WRF) modeling and graphical processing unit (GPU) computing have enabled high resolution weather modeling. In this manuscript, a balloon-launched unmanned glider, complete with a suite of sensors to measure atmospheric temperature, pressure, and relative humidity, is deployed for validation of real-time weather models. This work demonstrates the usefulness of sUAS for validating and improving mesoscale, real-time weather models for advancements toward reliable weather forecasts to enable safe and predictable sUAS missions beyond visual line of sight (BVLOS).

The sunlight photochemistry of the organic chromophore pyruvic acid (PA) in water generates ketyl and acetyl radicals that contribute to the production and processing of atmospheric aerosols. The photochemical mechanism is highly sensitive to dissolved oxygen content, [O₂( aq )], among other environmental conditions. Thus, herein we investigate the photolysis (λ ≥ 305 nm) of 10⁻200 mM PA at pH 1.0 in water covering the relevant range 0 ≤ [O₂( aq )] ≤ 1.3 mM. The rapid consumption of dissolved oxygen by the intermediate photolytic radicals is monitored in real time with a dissolved oxygen electrode. In addition, the rate of O₂( aq ) consumption is studied at air flow rates from 30.0 to 900.0 mL min -1 . For the range of [PA]₀ covered under air saturated conditions and 30 mL min -1 flow of air in this setup, the estimated half-lives of O₂( aq ) consumed by the photolytic radicalsfall within the interval from 22 to 3 min. Therefore, the corresponding depths of penetration of O₂( g ) into water ( x = 4.3 and 1.6 µm) are determined, suggesting that accumulation and small coarse mode aqueous particles should not be O₂-depleted in the presence of sunlight photons impinging this kind of chromophore. These photochemical results are of major tropospheric relevance for understanding the formation and growth of secondary organic aerosol.

Heterogeneous photocatalysis is a prominent area of research with major applications in solar energy conversion, air pollution mitigation, and removal of contaminants from water. A large number of scientific papers related to the photocatalysis field and its environmental applications are published in different journals specializing in materials and nanomaterials. However, many problems exist in the conception of papers by authors unfamiliar with standard characterization methods of photocatalysts as well as with the procedures needed to determine photocatalytic activities based on the determination of "apparent quantum efficiencies" within a wavelength interval or "apparent quantum yields" in the case of using monochromatic light. In this regard, an astonishing number of recent research articles include claims of highly efficient (photo)catalysts or similar terms about materials with superior or enhanced efficiency for a given reaction without proper experimental support. Consequently, the comparison of the efficiencies of photocatalysts may result as being meaningless, especially when reports are only based on expressions determining (1) a reaction rate per weight of catalyst or its surface area, (2) quantum efficiencies or quantum yields, and (3) turnover frequencies or turnover numbers. Herein, we summarize the standards needed for reporting valuable data in photocatalysis and highlight some common discrepancies found in the literature. This work should inform researchers interested in reporting photocatalysis projects about the correct procedures for collecting experimental data and properly characterizing the materials by providing examples and key supporting literature.

Aerosols of variable composition, size, and shape are associated with public health concerns as well as with light-particle interactions that play a role in the energy balance of the atmosphere. Photochemical reactions of 2-oxocarboxylic acids in the aqueous phase are now known to contribute to the total secondary organic aerosol (SOA) budget. This work explores the cross reaction of glyoxylic acid (GA) and pyruvic acid (PA) in water, the two most abundant 2-oxocarboxylic acids in the atmosphere, under solar irradiation and dark thermal aging steps. During irradiation, PA and GA are excited and initiate proton-coupled electron transfer or hydrogen abstraction and α-cleavage reactions, respectively. The time series of photoproducts is studied by ion chromatography (IC) with conductivity and electrospray ionization (ESI) mass spectrometry (MS) detection, direct ESI-MS analysis in the negative ion mode, and nuclear magnetic resonance spectroscopy (NMR). The use of one-dimensional ( 1 H and 13 C NMR) and two-dimensional NMR techniques includes gradient correlation spectroscopy (gCOSY) and heteronuclear single quantum correlation (HSQC). The aging of photoproducts in the dark is monitored by UV-visible spectroscopy. The periodicity in the time domain of the optical properties is explained in terms of chromophores that undergo alternating thermochromism and photobleaching between nighttime and daytime cycles, respectively. A reaction mechanism for the cross reaction of GA and PA explaining the generation of trimers with general formulas C 5 H 8 O 5 (148 Da), C 6 H 10 O 5 (162 Da), and C 5 H 8 O 6 (164 Da) is provided based on all experimental observations.

Understanding the acid-base behavior of carboxylic acids on aqueous interfaces is a fundamental issue in nature. Surface processes involving carboxylic acids such as acetic and pyruvic acids play roles in (1) the transport of nutrients through cell membranes, (2) the cycling of metabolites relevant to the origin of life, and (3) the photooxidative processing of biogenic and anthropogenic emissions in aerosols and atmospheric waters. Here, we report that 50% of gaseous acetic acid and pyruvic acid molecules transfer a proton to the surface of water at pH 2.8 and 1.8 units lower than their respective acidity constants p K a = 4.6 and 2.4 in bulk water. These findings provide key insights into the relative Bronsted acidities of common carboxylic acids versus interfacial water. In addition, the work estimates the reactive uptake coefficient of gaseous pyruvic acid by water to be γ PA = 0.06. This work is useful to interpret the interfacial behavior of pyruvic acid under low water activity conditions, typically found in haze aerosols, clouds, and fog waters.

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Anthropogenic activities contribute benzene, toluene, and anisole to the environment, which in the atmosphere are converted into the respective phenols, cresols, and methoxyphenols by fast gas-phase reaction with hydroxyl radicals (HO • ). Further processing of the latter species by HO • decreases their vapor pressure as a second hydroxyl group is incorporated to accelerate their oxidative aging at interfaces and in aqueous particles. This work shows how catechol, pyrogallol, 3-methylcatechol, 4-methylcatechol, and 3-methoxycatechol (all proxies for oxygenated aromatics derived from benzene, toluene, and anisole) react at the air-water interface with increasing O 3 (g) during τ c ≈ 1 μs contact time and contrasts their potential for electron transfer and in situ production of HO • using structure-activity relationships. A unifying mechanism is provided to explain the oxidation of the five proxies, which includes the generation of semiquinone radicals. Functionalization in the presence of HO • results in the formation of polyphenols and hydroxylated quinones. Instead, fragmentation produces polyfunctional low molecular weight carboxylic acids after oxidative cleavage of the aromatic bond with two vicinal hydroxy groups to yield substituted cis,cis-muconic acids. The generation of maleinaldehydic, maleic, pyruvic, glyoxylic, and oxalic acids confirms the potential of oxy aromatics to produce light-absorbing aqueous secondary organic aerosols in the troposphere.

The variable composition of secondary organic aerosols (SOA) contributes to the large uncertainty for predicting radiative forcing. A better understanding of the reaction mechanisms leading to aerosol formation such as for the photochemical reaction of aqueous pyruvic acid (PA) at λ ≥ 305 nm can contribute to constrain these uncertainties. Herein, the photochemistry of aqueous PA (5-300 mM) continuously sparged with air is re-examined in the laboratory under comparable irradiance at 38° N at noon on a summer day. Several analytical methods are employed to monitor the time series of the reaction, including (1) the derivatization of carbonyl (C═O) functional groups with 2,4-dinitrophenylhydrazine (DNPH), (2) the separation of photoproducts by ultrahigh pressure liquid chromatography (UHPLC) and ion chromatography (IC) coupled to mass spectrometry (MS), (3) high resolution MS, (4) the assignment of 1 H NMR and 13 C gCOSY spectroscopic features, and (5) quantitative 1 H NMR. The primary photoproducts are 2,3-dimethyltartaric acid and unstable 2-(1-carboxy-1-hydroxyethoxy)-2-methyl-3-oxobutanoic acid, a polyfunctional β-ketocarboxylic acid with eight carbons (C 8 ) that quickly decarboxylates into 2-hydroxy-2-((3-oxobutan-2-yl)oxy)propanoic acid. Kinetic isotope effect studies performed for the first time for this system reveal the existence of tunneling during the initial loss of PA. Thus, the KIEs support a mechanism initiated by photoinduced proton coupled electron transfer (PCET). Measured reaction rates at variable initial [PA] 0 were used to calculate the sum of the quantum yields for the products, which displays a hyperbolic dependence: ∑Φ product = 1.99 [PA] 0 /(113.2 + [PA] 0 ). The fast photochemical loss of aqueous PA with an estimated lifetime of 21.7 min is interpreted as a significant atmospheric sink for this species. The complexity of these aqueous phase pathways indicates that the solar photochemistry of an abundant α-ketocarboxylic acid can activate chemical processes for SOA formation.

How primordial metabolic networks such as the reverse tricarboxylic acid (rTCA) cycle and clay mineral catalysts coevolved remains a mystery in the puzzle to understand the origin of life. While prebiotic reactions from the rTCA cycle were accomplished via photochemistry on semiconductor minerals, the synthesis of clays was demonstrated at low temperature and ambient pressure catalyzed by oxalate. Herein, the crystallization of clay minerals is catalyzed by succinate, an example of a photoproduced intermediate from central metabolism. The experiments connect the synthesis of sauconite, a model for clay minerals, to prebiotic photochemistry. We report the temperature, pH, and concentration dependence on succinate for the synthesis of sauconite identifying new mechanisms of clay formation in surface environments of rocky planets. The work demonstrates that seeding induces nucleation at low temperatures accelerating the crystallization process. Cryogenic and conventional transmission electron microscopies, X-ray diffraction, diffuse reflectance Fourier transformed infrared spectroscopy, and measurements of total surface area are used to build a three-dimensional representation of the clay. These results suggest the coevolution of clay minerals and early metabolites in our planet could have been facilitated by sunlight photochemistry, which played a significant role in the complex interplay between rocks and life over geological time.

Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO 3 ) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO 3 -BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO 3 -BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO 3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO 3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry-climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO 3 -BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO 3 -BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models., Competing Interests: Competing interests. The authors declare that they have no conflict of interest.

Aerosols affect climate change, the energy balance of the atmosphere, and public health due to their variable chemical composition, size, and shape. While the formation of secondary organic aerosols (SOA) from gas phase precursors is relatively well understood, studying aqueous chemical reactions contributing to the total SOA budget is the current focus of major attention. Field measurements have revealed that mono-, di-, and oxo-carboxylic acids are abundant species present in SOA and atmospheric waters. This work explores the fate of one of these 2-oxocarboxylic acids, glyoxylic acid, which can photogenerate reactive species under solar irradiation. Additionally, the dark thermal aging of photoproducts is studied by UV-visible and fluorescence spectroscopies to reveal that the optical properties are altered by the glyoxal produced. The optical properties display periodicity in the time domain of the UV-visible spectrum of chromophores with absorption enhancement (thermochromism) or loss (photobleaching) during nighttime and daytime cycles, respectively. During irradiation, excited state glyoxylic acid can undergo α-cleavage or participate in hydrogen abstractions. The use of (13)C nuclear magnetic resonance spectroscopy (NMR) analysis shows that glyoxal is an important intermediate produced during direct photolysis. Glyoxal quickly reaches a quasi-steady state as confirmed by UHPLC-MS analysis of its corresponding (E) and (Z) 2,4-dinitrophenylhydrazones. The homolytic cleavage of glyoxylic acid is proposed as a fundamental step for the production of glyoxal. Both carbon oxides, CO2(g) and CO(g) evolving to the gas-phase, are quantified by FTIR spectroscopy. Finally, formic acid, oxalic acid, and tartaric acid photoproducts are identified by ion chromatography (IC) with conductivity and electrospray (ESI) mass spectrometry (MS) detection and (1)H NMR spectroscopy. A reaction mechanism is proposed based on all experimental observations.

Natural and anthropogenic emissions of aromatic hydrocarbons from biomass burning, agro-industrial settings, and fossil fuel combustion contribute precursors to secondary aerosol formation (SOA). How these compounds are processed under humid tropospheric conditions is the focus of current attention to understand their environmental fate. This work shows how catechol thin films, a model for oxygenated aromatic hydrocarbons present in biomass burning and combustion aerosols, undergo heterogeneous oxidation at the air-solid interface under variable relative humidity (RH = 0-90%). The maximum reactive uptake coefficient of O3(g) by catechol γO3 = (7.49 ± 0.35) × 10(-6) occurs for 90% RH. Upon exposure of ca. 104-μm thick catechol films to O3(g) mixing ratios between 230 ppbv and 25 ppmv, three main reaction pathways are observed. (1) The cleavage of the 1,2 carbon-carbon bond at the air-solid interface resulting in the formation of cis,cis-muconic acid via primary ozonide and hydroperoxide intermediates. Further direct ozonolysis of cis,cis-muconic yields glyoxylic, oxalic, crotonic, and maleic acids. (2) A second pathway is evidenced by the presence of Baeyer-Villiger oxidation products including glutaconic 4-hydroxy-2-butenoic and 5-oxo-2-pentenoic acids during electrospray ionization mass spectrometry (MS) and ion chromatography MS analyses. (3) Finally, indirect oxidation by in situ produced hydroxyl radical (HO(•)) results in the generation of semiquinone radical intermediates toward the synthesis of polyhydoxylated aromatic rings such as tri-, tetra-, and penta-hydroxybenzene. Remarkably, heavier polyhydroxylated biphenyl and terphenyl products present in the extracted oxidized films result from coupling reactions of semiquinones of catechol and its polyhydroxylated rings. The direct ozonolysis of 1,2,3- and 1,2,4-trihydroxybenezene yields 2- and 3-hydroxy-cis,cis-muconic acid, respectively. The production of 2,4- or 3,4-dihdroxyhex-2-enedioic acid is proposed to result from the sequential processing of cis,cis-muconic acid, 2- and 3-hydroxy-cis,cis-muconic acid. Overall, these reactions contribute precursors to form aqueous SOA from aromatics in atmospheric aerosols and brown clouds.

Anthropogenic emissions of aromatic hydrocarbons promptly react with hydroxyl radicals undergoing oxidation to form phenols and polyphenols (e.g., catechol) typically identified in the complex mixture of humic-like substances (HULIS). Because further processing of polyphenols in secondary organic aerosols (SOA) can continue mediated by a mechanism of ozonolysis at interfaces, a better understanding about how these reactions proceed at the air-water interface is needed. This work shows how catechol, a molecular probe of the oxygenated aromatic hydrocarbons present in SOA, can contribute interfacial reactive species that enhance the production of HULIS under atmospheric conditions. Reactive semiquinone radicals are quickly produced upon the encounter of 40 ppbv-6.0 ppmv O3(g) with microdroplets containing [catechol] = 1-150 μM. While the previous pathway results in the instantaneous formation of mono- and polyhydroxylated aromatic rings (PHA) and chromophoric mono- and polyhydroxylated quinones (PHQ), a different channel produces oxo- and dicarboxylic acids of low molecular weight (LMW). The cleavage of catechol occurs at the 1,2 carbon-carbon bond at the air-water interface through the formation of (1) an ozonide intermediate, (2) a hydroperoxide, and (3) cis,cis-muconic acid. However, variable [catechol] and [O3(g)] can affect the ratio of the primary products (cis,cis-muconic acid and trihydroxybenzenes) and higher order products observed (PHA, PHQ, and LMW oxo- and dicarboxylic acids). Secondary processing is confirmed by mass spectrometry, showing the production of crotonic, maleinaldehydic, maleic, glyoxylic, and oxalic acids. The proposed pathway can contribute precursors to aqueous SOA (AqSOA) formation, converting aromatic hydrocarbons into polyfunctional species widely found in tropospheric aerosols with light-absorbing brown carbon.

Halides are incorporated into aerosol sea spray, where they start the catalytic destruction of ozone (O3) over the oceans and affect the global troposphere. Two intriguing environmental problems undergoing continuous research are (1) to understand how reactive gas phase molecular halogens are directly produced from inorganic halides exposed to O3 and (2) to constrain the environmental factors that control this interfacial process. This paper presents a laboratory study of the reaction of O3 at variable iodide (I(-)) concentration (0.010-100 μM) for solutions aerosolized at 25 °C, which reveal remarkable differences in the reaction intermediates and products expected in sea spray for low tropospheric [O3]. The ultrafast oxidation of I(-) by O3 at the air-water interface of microdroplets is evidenced by the appearance of hypoiodous acid (HIO), iodite (IO2(-)), iodate (IO3(-)), triiodide (I3(-)), and molecular iodine (I2). Mass spectrometry measurements reveal an enhancement (up to 28%) in the dissolution of gaseous O3 at the gas-liquid interface when increasing the concentration of NaI or NaBr from 0.010 to 100 μM. The production of iodine species such as HIO and I2 from NaI aerosolized solutions exposed to 50 ppbv O3 can occur at the air-water interface of sea spray, followed by their transfer to the gas-phase, where they contribute to the loss of tropospheric ozone.

During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air-water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO(2), NaNO(3), NaClO(4), and NaIO(4). The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of anions (f(X(-))) and their correlation with ion properties. Although no correlation exists between f(X(-)) and the limiting equivalent ionic conductivity, the correlation coefficient of the linear fit with the size of the anions R(X(-)), dehydration free-energy ΔG(dehyd), and polarizability α, follows the order: R(X(-))(-2) > R(X(-))(-1) > R(X(-)) > ΔG(dehyd) > α. The same pure physical process is observed in H(2)O and D(2)O. The factor f(X(-)) does not change with pH (6.8-8.6), counterion (Li(+), Na(+), K(+), and Cs(+)) substitution effects, or solvent polarity changes in methanol- and ethanol-water mixtures (0 ≤ x(H(2)O) ≤ 1). Sodium polysorbate 20 surfactant is used to modify the structure of the interface. Despite the observed enrichment of I(-) on the air-water interface of equimolar solutions, our results of seawater mimic samples agree with a model in which the interfacial composition is increasingly enriched in I(-) < Br(-) < Cl(-) over the oceanic boundary layer due to concentration effects in sea spray aerosol formation.

The reaction of glyoxylate with carbon dioxide to produce lactate is promoted when zinc sulfide is irradiated by ultraviolet light. These results, representing a model for the action of colloidal mineral semiconductors on early Earth, complete a consecutive series that culminates in entry-point molecules of the reductive tricarboxylic acid cycle.

A reductive tricarboxylic acid (rTCA) cycle could have fixed carbon dioxide as biochemically useful energy-storage molecules on early Earth. Nonenzymatic chemical pathways for some steps of the rTCA cycle, however, such as the production of the alpha-ketocarboxylic acids pyruvate and alpha-ketoglutarate, remain a challenging problem for the viability of the proposed prebiotic cycle. As a class of compounds, alpha-ketocarboxylic acids have high free energies of formation that disfavor their production. We report herein the production of pyruvate from lactate and of alpha-ketoglutarate from pyruvate in the millimolar concentration range as promoted by ZnS mineral photoelectrochemistry. Pyruvate is produced from the photooxidation of lactate with 70% yield and a quantum efficiency of 0.009 at 15 degrees C across the wavelength range of 200-400 nm. The produced pyruvate undergoes photoreductive back reaction to lactate at a 30% yield and with a quantum efficiency of 0.0024. Pyruvate alternatively continues in photooxidative forward reaction to alpha-ketoglutarate with a 50% yield and a quantum efficiency of 0.0036. The remaining 20% of the carbon follows side reactions that produce isocitrate, glutarate, and succinate. Small amounts of acetate are also produced. The results of this study suggest that alpha-ketocarboxylic acids produced by mineral photoelectrochemistry could have participated in a viable enzyme-free cycle for carbon fixation in an environment where light, sulfide minerals, carbon dioxide, and other organic compounds interacted on prebiotic Earth.

Ice is selectively intolerant to impurities. A preponderance of implanted anions or cations generates electrical imbalances in ice grown from electrolyte solutions. Since the excess charges are ultimately neutralized via interfacial (H(+)/HO(-)) transport, the acidity of the unfrozen portion can change significantly and permanently. This insufficiently recognized phenomenon should critically affect rates and equilibria in frozen media. Here we report the effective (19)F NMR chemical shift of 3-fluorobenzoic acid as in situ probe of the acidity of extensively frozen electrolyte solutions. The sign and magnitude of the acidity changes associated with freezing are largely determined by specific ion combinations, but depend also on solute concentration and/or the extent of supercooling. NaCl solutions become more basic, those of (NH(4))(2)SO(4) or Na(2)SO(4) become more acidic, while solutions of the 2-(N-morpholino)ethanesulfonic acid zwitterion barely change their acidity upon freezing. We discuss how acidity scales based on solid-state NMR measurements could be used to assess the degree of ionization of weak acids and bases in frozen media.

The 320 nm-band photodecarboxylation of aqueous pyruvic acid (PA), a representative of the alpha-oxocarboxylic acids widely found in the atmospheric aerosol, yields 2,3-dimethyltartaric (A) and 2-(3-oxobutan-2-yloxy)-2-hydroxypropanoic (B) acids, rather than 3-hydroxy-2-oxobutanone as previously reported. A and B are identified by liquid chromatography with UV and ESI-MS detection, complemented by collisionally induced dissociation and 2H and 13C isotope labeling experiments. The multifunctional ether B gives rise to characteristic delta approximately 80 ppm 13C NMR resonances. Product quantum yields are proportional to [PA](a + [PA])(-1) in the range [PA] = 5-100 mM. CO2(g) release rates are halved, while A and B are suppressed by the addition of >1.5 mM TEMPO. A and B are only partially quenched in air-saturated solutions. These observations are shown to be consistent with an oligomerization process initiated by a bimolecular reaction between 3PA and PA producing ketyl, CH3C(OH)C(O)OH, and acetyl, CH3C(O)*, radicals, rather than by the unimolecular decomposition of 3PA into 1-hydroxyethylidene, 3HO(CH3)C: (+CO2), or [CH(3)C(O)* + *C(O)OH] pairs. A arises from the dimerization of ketyl radicals, while B ensues the facile decarboxylation of the C8beta-ketoacid formed by association of acetyl radicals with the ketyl radical adduct of PA. Since the radical precursors to A and B are scavenged by O2 with a low probability per encounter (k(sc) approximately 1 x 10(6) M(-1) s(-1)), PA is able to accrete into multifunctional polar species in aerated aqueous media under solar illumination.