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Organophosphate esters (OPEs), widely used as flame retardants and plasticizers, have frequently been identified in the atmosphere. However, their atmospheric fate and toxicity associated with atmospheric transformations are unclear. Here, we performed quantum chemical calculations and computational toxicology to investigate the reaction mechanism of peroxy radicals of OPEs (OPEs-RO2), key intermediates in determining the atmospheric chemistry of OPEs, and the toxicity of the reaction products. TMP-RO2 (R1) and TCPP-RO2 (R2) derived from trimethyl phosphate and tris(2-chloroisopropyl) phosphate, respectively, are selected as model systems. The results indicate that R1 and R2 can follow an H-shift-driven autoxidation mechanism under low NO concentration ([NO]) conditions, clarifying that RO2 from esters can follow an autoxidation mechanism. The unexpected autoxidation mechanism can be attributed to the distinct role of the -(O)3P(•O) phosphate-ester group in facilitating the H-shift of OPEs-RO2 from commonly encountered -OC(•O)- and -ONO2 ester groups in the atmosphere. Under high [NO] conditions, NO can mediate the autoxidation mechanism to form organonitrates and alkoxy radical-related products. The products from the autoxidation mechanism have low volatility and aquatic toxicity compared to their corresponding parent compounds. The proposed autoxidation mechanism advances our current understanding of the atmospheric RO2 chemistry and the environmental risk of OPEs.

Surface atomic arrangement and physical properties of aluminum ultrathin layers on c-Si(111)-7 × 7 and hydrogen-terminated c-Si(111)-1 × 1 surfaces deposited using molecular beam epitaxy were investigated. X-ray photoelectron spectroscopy spectra were collected in two configurations (take-off angle of 0° and 45°) to precisely determine the surface species. Moreover, 3D atomic force microscopy (AFM) images of the air-exposed samples were acquired to investigate the clustering formations in film structure. The deposition of the Al layers was monitored in situ using a reflection high-energy electron diffraction (RHEED) experiments to confirm the surface crystalline structure of the c-Si(111). The analysis of the RHEED patterns during the growth process suggests the settlement of aluminum atoms in Al(111)-1 × 1 clustered formations on both types of surfaces. The surface electrical conductivity in both configurations was tested against atmospheric oxidation. The results indicate differences in conductivity based on the formation of various alloys on the surface.

8 pags., 4 figs., 7 tabs., Methyl vinyl ketone is one of the major oxidation products of isoprene, and therefore, an important precursor of secondary organic aerosol. Understanding its interactions with water is relevant to gain insight into aerosol formation and improve the predictive power of atmospheric chemistry models. The molecular complex formed between methyl vinyl ketone and water has been generated in a supersonic jet and characterized using high-resolution microwave spectroscopy in combination with quantum chemistry calculations. In this study, we show that methyl vinyl ketone interacts with water forming four 1:1 isomers connected by O − H···O and C − H···O hydrogen bond interactions. Water has been found to preferentially bind to the antiperiplanar conformation of methyl vinyl ketone. Evidence of a large amplitude motion arising from the methyl internal rotation has been found in the rotational spectra of the dimer. The threefold methyl internal rotation barrier heights have been further determined and discussed for all the species., This research was funded by the Spanish Ministerio de Ciencia e Innovación (PID2020-117925GA-I00 and PGC2018-098561-BC22). M. J. and R. T. S. thank predoctoral contracts from the MICINN and UVa, respectively.

Organic acids are important aerosol compositions with significant implications on particle formation, growth, acidity, phase state, and environmental impacts. Oxalic acid was found to be the most abundant particulate organic diacid in Shanghai during the study period, accounting for ~58% of the total dicarboxylic acids (C2–C10). Biomass burning (BB) explained a small but non-negligible fraction (less than 10%) of oxalate. Significant correlations between oxalate and sulfate indicated a potentially synergistic formation mechanism of oxalate and sulfate. In addition, meteorological factors such as ambient temperature and relative humidity were found to influence the formation of oxalate. Higher oxalate relative to inorganic particulate content was found in summer. Potential source contribution function analysis suggested that most of the oxalate observed in Shanghai was produced locally. The formation of oxalate was largely impacted by atmospheric oxidation capacity as indicated by its significant correlations with both secondary organic carbon (SOC) and sulfur oxidation ratio (SOR). The evolution of oxalate, oxalate/sulfate, oxalate/organic carbon were consistent with the emission trend of volatile organic carbons (VOCs) in recent years, indicating that oxalate may be derived from secondary oxidation of VOCs, which is further confirmed by a positive relationship between Ox and oxalate/VOCs over the study period. With a detailed characterization of oxalate in Shanghai, our study highlights the importance of regulating primary emissions, such as VOCs, as well as mitigation of atmospheric oxidation capacity in controlling air pollution in a coastal megacity.

Hexachlorobenzene is highly persistent, bioaccumulative, toxic and globally distributed, a model persistent organic pollutant. The major atmospheric removal process for hexachlorobenzene is its oxidation by hydroxyl radicals. Unfortunately, there is no information on the reaction mechanism of this important atmospheric process and the respective degradation rates were measured in a narrow temperature range not of environmental relevance. Thus, the geometries and energies of all stationary points significant for the atmospheric oxidation of hexachlorobenzene are optimized using MP2/6-311G(d, p) method. Furthermore, the single point energies were calculated with G3 method on the optimized minima and transition-states. It was demonstrated for the first time that the addition of hydroxyl radicals to hexachlorobenzene proceeds indirectly, via a prereaction complex. In the prereaction complex the hydroxyl radical is almost perpendicular to the aromatic ring while oxygen is pointing to its center. In contrast, in the transition state it is nearly parallel with the aromatic ring. The reliable rate constants are calculated for the first time for the atmospheric oxidation of hexachlorobenzene for all environmentally relevant temperatures. It was also demonstrated for the first time that pentachlorophenol is the major stable product in the addition of hydroxyl radicals to hexachlorobenzene and that atmosphere seems to be a new global secondary source of pentachlorophenol.

The atmospheric reactions leading to the generation of secondary organic aerosol (SOA) from the oxidation of isoprene are generally assumed to produce only racemic mixtures, but aspects of the chemical reactions suggest this may not be the case. In this review, the stereochemical outcomes of published isoprene-degradation mechanisms contributing to high amounts of SOA are evaluated. Despite evidence suggesting isoprene first-generation oxidation products do not contribute to SOA directly, this review suggests the stereochemistry of first-generation products may be important because their stereochemical configurations may be retained through to the second-generation products which form SOA. Specifically, due to the stereochemistry of epoxide ring-opening mechanisms, the outcome of the reactions involving epoxydiols of isoprene (IEPOX), methacrylic acid epoxide (MAE) and hydroxymethylmethyl-α-lactone (HMML) are, in principle, stereospecific which indicates the stereochemistry is predefined from first-generation precursors. The products from these three epoxide intermediates oligomerise to form macromolecules which are proposed to form chiral structures within the aerosol and are considered to be the largest contributors to SOA. If conditions in the atmosphere such as pH, aerosol water content, relative humidity, pre-existing aerosol, aerosol coatings and aerosol cation/anion content (and other) variables acting on the reactions leading to SOA affect the tacticity (arrangement of chiral centres) in the SOA then they may influence its physical properties, for example its hygroscopicity. Chamber studies of SOA formation from isoprene encompass particular sets of controlled conditions of these variables. It may therefore be important to consider stereochemistry when upscaling from chamber study data to predictions of SOA yields across the range of ambient atmospheric conditions. Experiments analysing the stereochemistry of the reactions under varying conditions of the above variables would help elucidate whether there is stereoselectivity in SOA formation from isoprene and if the rates of SOA formation are affected.

Direct aqueous photolysis of cis-pinonic acid (PA; 2-(3-acetyl-2,2-dimethylcyclobutyl)acetic acid; CAS Registry No. 473-72-3) by 280-400 nm radiation was investigated. The photolysis resulted in Norrish type II isomerization of PA leading to 3-isopropenyl-6-oxoheptanoic acid (CAS Registry No. 4436-82-2), also known as limononic acid, as the major product, confirmed by (1)H and (13)C NMR analysis, chemical ionization mass spectrometry, and electrospray ionization mass spectrometry. Several minor products resulting from Norrish type I splitting of PA were also detected. The molar extinction coefficients of aqueous PA were measured and used to calculate the photolysis quantum yield of aqueous PA as 0.5 ± 0.3 (effective average value over the 280-400 nm range). The gas-phase photolysis quantum yield of 0.53 ± 0.06 for PA methyl ester (PAMe; CAS Registry No. 16978-11-3) was also measured for comparison. These results indicate that photolysis of PA is not significantly suppressed by the presence of water. This fact was confirmed by photodissociation dynamics simulations of bare PA and of PAMe hydrated with one or five water molecules using on-the-fly dynamics simulations on a semiempirical potential energy surface. The calculations correctly predicted the occurrence of both Norrish type I and Norrish type II photolysis pathways, both driven by the dynamics on the lowest triplet excited state of PA and PAMe. The rate of removal of PA by direct aqueous photolysis in cloudwater and in aerosol water was calculated for a range of solar zenith angles and compared with rates of other removal processes such as gas-phase oxidation by OH, aqueous-phase oxidation by OH, and gas-phase photolysis. Although the direct photolysis mechanism was not the most significant sink for PA in cloud and fog droplets, direct photolysis can be expected to contribute to removal of PA and more soluble/less volatile biogenic oxidation products in wet particulate matter.

Oxygenation of the Earth's atmosphere occurred in two major steps, near the beginning and near the end of the Proterozoic Eon (2500 to 542 Ma ago), but the details of this history are unclear. Chromium isotopes in iron-rich chemical sediments offer a potential to highlight fine-scale fluctuations in the oxygenation of the oceans and atmosphere and to add a further dimension in the use of redox-sensitive tracers to solve the question regarding fluctuations of atmospheric oxygen levels and their consequences for Earth's climate. We observe strong positive fractionations in Cr isotopes (delta Cr-53 up to +5.0 parts per thousand.) in iron-rich cherts and banded iron formation horizons within the Arroyo del Soldado Group (Ediacaran; Uruguay) that can be explained by rapid, effective oxidation of Fe(II)-rich surface waters. These fluctuations are correlated with variations in ratios of highly reactive iron (Fe-HR) to total iron (Fe-tot) which indicate a predominance of anoxic water columns (Fe-HR/Fe-tot>0.38) during the onset of oxidation pulses. We favor the scenario by which isotopically heavy Cr(VI) entered the basin after pulses of oxidative weathering on land and in which Fe(II) accumulated in the water column. Neodymium isotopes reveal that these oxygenation pulses were followed by increased influxes to the basin of continental crust-derived detrital components of Paleoproterozoic (Nd T-DM model ages=2.1-2.2 Ga) provenance typical of the Rio de la Plata Craton. The association of positive delta Cr-53-ferruginous (Fe-HR/Fe-tot>0.38) stratigraphic intervals with low-diversity acritarch assemblages dominated by Bavlinella faveolata strongly support models postulating a stratified, eutrophic Neoproterozoic ocean. Thus, even within a few million years of the Precambrian-Cambrian boundary, paleoceanographic conditions resembled more those of Paleoproterozoic oceans than Phanerozoic and present oceans. This highlights the sheer magnitude of ecological changes at the Precambrian-Cambrian transition, changes which ultimately led to the demise of the Precambrian world and the birth of the metazoan-dominated Phanerozoic. (C) 2012 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved. Oxygenation of the Earth's atmosphere occurred in two major steps, near the beginning and near the end of the Proterozoic Eon (2500 to 542Ma ago), but the details of this history are unclear. Chromium isotopes in iron-rich chemical sediments offer a potential to highlight fine-scale fluctuations in the oxygenation of the oceans and atmosphere and to add a further dimension in the use of redox-sensitive tracers to solve the question regarding fluctuations of atmospheric oxygen levels and their consequences for Earth's climate. We observe strong positive fractionations in Cr isotopes (δ 53Cr up to +5.0%) in iron-rich cherts and banded iron formation horizons within the Arroyo del Soldado Group (Ediacaran; Uruguay) that can be explained by rapid, effective oxidation of Fe(II)-rich surface waters. These fluctuations are correlated with variations in ratios of highly reactive iron (Fe HR) to total iron (Fe tot) which indicate a predominance of anoxic water columns (Fe HR/Fe tot>0.38) during the onset of oxidation pulses. We favor the scenario by which isotopically heavy Cr(VI) entered the basin after pulses of oxidative weathering on land and in which Fe(II) accumulated in the water column. Neodymium isotopes reveal that these oxygenation pulses were followed by increased influxes to the basin of continental crust-derived detrital components of Paleoproterozoic (Nd T DM model ages=2.1-2.2Ga) provenance typical of the Rio de la Plata Craton. The association of positive δ 53Cr-ferruginous (Fe HR/Fe tot>0.38) stratigraphic intervals with low-diversity acritarch assemblages dominated by Bavlinella faveolata strongly support models postulating a stratified, eutrophic Neoproterozoic ocean. Thus, even within a few million years of the Precambrian-Cambrian boundary, paleoceanographic conditions resembled more those of Paleoproterozoic oceans than Phanerozoic and present oceans. This highlights the sheer magnitude of ecological changes at the Precambrian-Cambrian transition, changes which ultimately led to the demise of the Precambrian world and the birth of the metazoan-dominated Phanerozoic.

Ground-level ozone pollution in Beijing has been causing concern among the public due to the risks posed to human health. This study analyzed the temporal and spatial distribution of, and investigated population exposure to, ground-level ozone. We analyzed hourly ground-level ozone data from 35 ambient air quality monitoring sites, including urban, suburban, background, and traffic monitoring sites, during the summer in Beijing from 2014 to 2017. The results showed that the four-year mean ozone concentrations for urban, suburban, background, and traffic monitoring sites were 95.1, 99.8, 95.9, and 74.2 μg/m3, respectively. A total of 44, 43, 45, and 43 days exceeded the Chinese National Ambient Air Quality Standards (NAAQS) threshold for ground-level ozone in 2014, 2015, 2016, and 2017, respectively. The mean ozone concentration was higher in suburban sites than in urban sites, and the traffic monitoring sites had the lowest concentration. The diurnal variation in ground-level ozone concentration at the four types of monitoring sites displayed a single-peak curve. The peak and valley values occurred at 3:00–4:00 p.m. and 7:00 a.m., respectively. Spatially, ground-level ozone concentrations decreased in gradient from the north to the south. Population exposure levels were calculated based on ground-level ozone concentrations and population data. Approximately 50.38%, 44.85%, and 48.49% of the total population of Beijing were exposed to ground-level ozone concentrations exceeding the Chinese NAAQS threshold in 2014, 2015, and 2016, respectively.

Despite orders of magnitude difference in atmospheric reactivity and great diversity in biological functioning, little is known about monoterpene speciation in tropical forests. Here we report vertically resolved ambient air mixing ratios for 12 monoterpenes in a central Amazon rainforest including observations of the highly reactive cis-β-ocimene (160 ppt), trans-β-ocimene (79 ppt), and terpinolene (32 ppt) which accounted for an estimated 21% of total monoterpene composition yet 55% of the upper canopy monoterpene ozonolysis rate. All 12 monoterpenes showed a mixing ratio peak in the upper canopy, with three demonstrating subcanopy peaks in 7 of 11 profiles. Leaf level emissions of highly reactive monoterpenes accounted for up to 1.9% of photosynthesis confirming light-dependent emissions across several Amazon tree genera. These results suggest that highly reactive monoterpenes play important antioxidant roles during photosynthesis in plants and serve as near-canopy sources of secondary organic aerosol precursors through atmospheric photooxidation via ozonolysis.

Iron bioavailability of diets containing oxidized turkey and oxidized beef meat was investigated in two experiments. In both vi studies male, weanling rats were made anemic by consumption of a low iron diet and bleeding. The experimental diets were prepared so that meat was the only source of iron. Hemoglobin regeneration served as the basis for measuring iron utilization. In experiment 1, lyophilized, uncooked turkey meat was allowed to oxidize at 20-22��C for 0, 48, 96, 144, 216, or 264 hours and then fed to the rats. The length of oxidation time of the turkey meat did not significantly affect the growth of the rats or the bioavailability of the meat iron. In experiment 2, lyophilized, uncooked beef was allowed to oxidize at 20-22��C for 14 days. Anemic rats were fed diets composed of basal, basal + iron, basal + iron + formaldehyde, 100% fresh beef, 75% fresh 25% oxidized beef, 50% fresh-50% oxidized beef, 25% fresh-75% oxidized, 100% oxidized beef and 100% fresh beef + formaldehyde. Rats fed severely oxidized beef diets had decreased body weight, enlarged livers and depressed hematinic responses. Formaldehyde did not significantly affect iron utilization in rats fed basal diets, but depressed liver iron storage in rats fed fresh beef. A third experiment to further compare the chemical properties of uncooked, lyophilized hand deboned and mechanically deboned beef and turkey meat was performed. Analysis by the Thiobarbituric Acid Method, Formaldehyde Value, and Iodine Number indicated increased sophistication of testing methods for lyophilized meats needs to be developed. Although the Thiobarbituric Acid Method was successfully used in Experiment 1, unreliable results were obtained using this method in Experiment 3. It is assumed that this variability in results is due to using the Thiobarbituric Acid Method with a dry system. The problems encountered with the Formaldehyde Value included contamination of the water supply with aldehydes and unreliable reagent. The Iodine Number was unreliable used on meat samples. Possibly the fat could be extracted from the meat under cool nitrogen to prevent further oxidation of the fat. Then the iodine number could be determined on the extracted fat.