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The secondary organic aerosol (SOA) yield of toluene photooxidation was reported to substantially higher than that of trimethylbenzene due to the effect of the number of methyl substituents. However, the intrinsic mechanism for this disparity is not clear enough. In this study, a highly-sensitive thermal-desorption photoinduced associative ionization mass spectrometer (TD-PAI-MS) was used to real-time characterize the molecular composition and its evolution of the SOA generated from the photooxidation of toluene and 1,2,3-trimethylbenzene (1,2,3-TMB) in a smog chamber. In the new particle formation (NPF) stage, toluene generated more variety of nucleation precursors, such as benzaldehyde (MW 106) and benzoic acid (MW 122), resulting in a much higher nucleation rate and SOA number concentration. In the SOA growth/aging stage, the key SOA components of toluene were mainly dialdehydes, e.g., 2-oxopropanedial (MW 86) and 4-oxopent-2-enedial (MW 112), which played an important role in the formation of highly oxidized species (HOS) through oligomerization or cyclization reactions. In contrast, due to the presence of more methyl groups, 1,2,3-TMB was inclined to produce ketones, e.g., 2,3-butanedione (MW 86) and 3-methyl-4-oxopent-2-enal (MW 112), which would be cleaved into high-volatility low molecular compounds, e.g., acetic acid, through fragmentation. Taken together, relative to 1,2,3-TMB, the higher nucleation rate during NPF and the significant oligomerization/functionalization process during SOA growth are thought to be the major reasons resulting in the higher SOA yield of toluene. This work provides a reference for the insight into the different SOA yields of monocyclic aromatic hydrocarbons (MAHs) through further revealing the SOA formation mechanism during toluene and 1,2,3-TMB photooxidation.

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1,2,3-Trimethylbenzene (1,2,3-TMB) is an important volatile organic compound (VOC) present in petroleum wastewater and the atmosphere. This compound can be degraded by OH radicals via abstraction, addition and substitution mechanisms. Results show that the addition mechanism is dominant and H-abstraction is subdominant, while methyl abstraction and substitution mechanisms are negligible in the gas and aqueous phases. Moreover, H-abstraction products undergo further reactions with O2, NO, NO2, H2O, and OH radicals in the atmosphere. Time-dependent density functional theory (TDDFT) calculations show that the degraded products, including 2,3,4-trimethylphenyl-nitroperoxoite, 1,2,3-trimethyl-4-nitrobenzene, 1,2,3-trimethyl-5-nitrobenzene, 2,6-dimethylbenzyl nitroperoxoite, 2,3-dimethylphenyl nitroperoxoite, 2,6-dimethylbenzaldehyde, and 2,3-dimethylbenzaldehyde, can photolyze under the sunlight. Kinetically, the calculated total rate constant is 5.57 × 10-11 cm3 molecule-1·s-1 at 1 atm and 298 K, which is consistent with available experimental values measured in the atmosphere. In addition, the calculated total reaction rate constant in water is close to that in the gas phase. In terms of ecotoxicity, all degradation products are less toxic than the initial reactant to fish, green algae and daphnia. For mammals represented by rats, 1,2,3-TMB and its products are moderately toxic, except for 2,3-dimethylphenol and 2,6-dimethylphenol, which are slightly toxic.

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Little is known about environmental factors that may increase the risk of prostate cancer. We estimated associations between incident prostate cancer and environmental concentrations of five ambient volatile organic compounds (VOCs): benzene; n-decane; ethylbenzene; hexane; and 1,2,4-trimethylbenzene. Methods: This study is based on a population-based case-control study of incident prostate cancer (PROtEuS) in men ≤ 75 years of age living in Montreal, Canada, in 2005 to 2012. We included 1172 cases and 1177 population controls. We had personal information, lifetime residential addresses, occupational exposures, and a variety of area-wide covariables. We inferred concentrations of the five VOCs using Bayesian geostatistical models using data from a dense environmental survey conducted in Montreal in 2005 to 2006. We used different sets of adjustments to estimate odds ratios (OR) and confidence intervals. Results: We found nonlinear associations such that the ORs increased monotonically and then either flattened or fell off with increased exposures. The model that contained other environmental variables and contextual variables led to lower ORs and results were similar when we restricted analyses to controls recently screened or tested for prostate cancer or cases with low- or high-grade tumors. A change from the 5th to 25th percentile in mean environmental benzene levels led to an adjusted OR of 2.00 (95% confidence interval = 1.47, 2.71). Conclusion: We found positive associations between prostate cancer and concentrations of benzene and ethylbenzene, independently of previous testing for prostate cancer or tumor grade, suggesting that exposure to certain ambient VOCs may increase incidence.

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Physiologically based pharmacokinetic (PBPK) models are a means of making important linkages between exposure assessment and in vitro toxicity. A key constraint on rapid application of PBPK models in risk assessment is traditional reliance on substance-specific in vivo toxicokinetic data to evaluate model quality. Bounding conditions, in silico, in vitro, and chemical read-across approaches have been proposed as alternative sources for metabolic clearance estimates. A case study to test consistency of predictive ability across these approaches was conducted using trimethylbenzenes (TMB) as prototype chemicals. Substantial concordance was found among TMB isomers with respect to accuracy (or inaccuracy) of approaches to estimating metabolism; for example, the bounding conditions never reproduced the human in vivo toxicokinetic data within two-fold. Using only approaches that gave acceptable prediction of in vivo toxicokinetics for the source compound (1,2,4-TMB) substantially narrowed the range of plausible internal doses for a given external dose for occupational, emergency response, and environmental/community health risk assessment scenarios for TMB isomers. Thus, risk assessments developed using the target compound models with a constrained subset of metabolism estimates (determined for source chemical models) can be used with greater confidence that internal dosimetry will be estimated with accuracy sufficient for the purpose at hand.

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Automotive painting plants are important emission sources of volatile organic compounds (VOCs) that contribute significantly to ground-level ozone (O3) pollution in atmosphere. Here, we investigated process-specified emission characteristics of VOCs, without or with advanced adsorption/incineration after-treatments, from an ultra-low-emission (ULE) waterborne painting process in a modernized automotive plant. Overall, more than 80 VOCs species were identified and sorted into seven main categories. In the stack emissions without after-treatments, oxygenated VOCs (alcohols, esters, ketones, ethers, etc.) were found to be the most abundant components (48.8%), followed by aromatic (30.9%), alkanes (16.9%) and alkenes (1.2%). Among the different VOCs species discharged to atmosphere (i.e. after adsorption/incineration after-treatments), aromatics demonstrated a predominant contribution (by 60.6%) to the total O3 formation potentials (OFPs) despite their relatively lower abundance. Trimethylbenzene was identified to have the highest OFPs, and thus should be controlled with peculiar priority. As compared to traditional organic solvent-based painting process, the ULE waterborne process implemented in the target plant allows to reduce the OFPs from 10.7 mg m-3 to 3 mg m-3 (or by 72%). Additional monitoring by unmanned aerial vehicle (over more than 3000 sampling points in the plant) confirmed that the instantaneous concentrations of fugitive VOCs were well below the regulated limit value during typical working and non-working days. These findings may provide important reference for reduction of VOCs emissions and O3 pollution from automotive painting processes.

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This paper presents the data of chemical composition of the particles from OH oxidation reaction of 1,3,5-trimethylbenzene (1,3,5-TMB). The particle-phase compositions are measured on-line by using a vacuum ultraviolet (VUV) photoionization aerosol mass spectrometer. The assignments of the major peaks of photoionization mass spectrum, as well as their molecular structures, are presented. The optimized structures of the reactants, intermediates and transition states involved in the reaction of the bicyclic peroxy radical with HO2 are shown. The reaction routes of the OH-initiated oxidation of the deuterated 1,3,5-TMB sample are also calculated and displayed for comparison. The data presented here is related to the paper "Direct observation of the particle-phase bicyclic products from OH-initiated oxidation of 1,3,5-trimethylbenzene under NOx-free conditions" by Lin et al. (2022).

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1,3,5-Trimethylbeneze (TMB) is an important constituent of anthropogenic volatile organic compounds that contributes to the formation of secondary organic aerosol (SOA). A series of chamber experiments were performed to probe the effects of NOx and SO2 on SOA formation from TMB photooxidation. The molecular composition of TMB SOA was investigated by ultra-high performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS). We found that the SOA yield increases notably with elevated NOx concentrations under low-NOx condition ([TMB]0/[NOx]0 > 10 ppbC ppb-1), while an opposite trend is observed in high-NOx experiments ([TMB]0/[NOx]0 < 10 ppbC ppb-1). The increase in SOA yield in low-NOx regime is attributed to the increase of NOx-induced OH concentrations. The formation of low-volatility species might be suppressed, thereby leading to a lower SOA yield in high-NOx conditions. Moreover, SOA formation was promoted in experiment with SO2 addition. Multifunctional products containing carbonyl, acid, alcohol, and nitrate functional groups were characterized in TMB/NOx photooxidation, whereas several organosulfates (OSs) and nitrooxy organosulfates were identified in TMB/NOx/SO2 photooxidation based on HR-Q-TOFMS analysis. The formation mechanism relevant to the detected compounds in SOA were proposed. Based on our measurements, the photooxidation of TMB in the presence of SO2 may be a new source of OSs in the atmosphere. The results presented here also deepen the understanding of SOA formation under relatively complex polluted environments.

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Trimethylbenzene (TMB) isomers (1,2,3-TMB, 1,2,4-TMB, and 1,3,5-TMB) are often used as conservative tracers in anaerobic, contaminated aquifers for assessing BTEX (benzene, toluene, ethylbenzene, xylenes) biodegradation at field sites. However, uncertainties exist about the behavior of these compounds under anaerobic conditions. For this reason, the influence of various parameters (temperature, residence time) on the biodegradability of TMB isomers was investigated under denitrifying and sulfate-reducing conditions in microcosms and 1D-column experiments. Soil and groundwater contaminated with a cocktail of aromatic hydrocarbons including the TMB isomers, both collected from an industrial site in Berlin, Germany, were used for the laboratory investigations. A continuous and complete biodegradation of 1,3,5-TMB and 1,2,4-TMB under denitrifying conditions was observed independent of realized temperature (10⁻20 °C) and residence time. Biodegradation of 1,2,3-TMB started after longer lag-phases and was not continuous over the whole experimental period; a strong dependence on temperature and residence time was identified. The biodegradability of all TMB isomers under sulfate-reducing conditions was continuous and complete at higher temperatures (20 °C), whereas no degradation was observed for lower temperatures (10 °C). First-order biodegradation rate constants ranged from 0.05 to 0.21 d-1 for 1,3,5-TMB and 1,2,4-TMB and from 0.01 to 0.11 d-1 for 1,2,3-TMB.

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The aim of this study was to investigate the aroma and sensory profiles of various types of peaches (Prunus persica L. Batsch.). Forty-three commercial cultivars comprising peaches, flat peaches, nectarines, and canning peaches (pavías) were grown over two consecutive harvest years. Fruits were assessed for chemical aroma and sensory profiles. Chemical aroma profile was obtained by proton transfer reaction-mass spectrometry (PTR-MS) and spectral masses were tentatively identified with PTR-Time of Flight-MS (PTR-Tof-MS). Sensory analysis was performed at commercial maturity considering seven aroma/flavor attributes. The four types of peaches showed both distinct chemical aroma and sensory profiles. Flat peaches and canning peaches showed most distinct patterns according to discriminant analysis. The sensory data were related to the volatile compounds by partial least square regression. γ-Hexalactone, γ-octalactone, hotrienol, acetic acid and ethyl acetate correlated positively, and benzeneacetaldehyde, trimethylbenzene and acetaldehyde negatively to the intensities of aroma and ripe fruit sensory scores.

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Entomopathogenic nematodes (EPNs) play a role in indirect defense of plants under attack by root herbivores. Several investigations have shown that EPNs are attracted or repelled by various volatile compounds (VOCs) released from insect damaged plant roots. We hypothesized that the directional responses of EPNs to the VOCs would be affected by foraging strategy and would vary among species, VOC type, and VOC concentrations. We tested the chemotactic responses of four commercial EPN species (Steinernema feltiae, S. carpocapsae, S. kraussei, and Heterorhabditis bacteriophora) to seven compounds released from insect (Melolontha hippocastani)-damaged (decanal, nonanal, octanal, undecane, 6-methyl-5-hepten-2-one, and 1,2,4-trimethylbenzene) and undamaged (2-ethyl-1-hexanol) potato tubers. Our results suggest that EPNs are able to distinguish herbivore-induced VOCs from those that are typical for healthy potato tubers. In our investigation, nonanal, octanal, and decanal had a greater influence on the movement of EPNs than other tested synthetic volatiles. Decanal was an attractant for H. bacteriophora and S. kraussei at both tested concentrations (as a pure compound and at a concentration of 0.03 ppm). The results suggest that the susceptibility to perception of chemical stimuli from the environment is a species-specific characteristic that prevails over the influence of the foraging strategy.

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The systemic toxicity of a trimethylbenzene isomer and constituent of C9 aromatic solvents (1,3,5-trimethylbenzene, 135-TMB) was studied in Sprague-Dawley rats following a 90-day oral gavage exposure to 0, 50, 200 and 600 mg/kg/day. No statistically significant effects on body weight, body weight gain or food consumption were observed at study termination. Treatment-related changes in clinical chemistry parameters at the end of the 90-day dosing period were limited to small, but statistically significant, increases in phosphorus levels in high dose males and females. Liver enlargement in high dose male/female rats was considered an adaptive response as this was reversible and was not associated with histopathological lesions or increased liver enzyme markers indicative of liver damage. Kidney weight changes were limited to a small, but statistically significant, increase in relative weights in high dose males. This was not associated with histopathological lesions and thus not considered toxicologically relevant. Overall, the No-Observed-Adverse-Effect-Level (NOAEL) was the highest concentration tested (600 mg/kg/day). The results of the present study are relevant for assessing the risk of trimethylbenzenes through the oral route of exposure and provide a basis for the development of provisional screening values for trimethylbenzene isomers while avoiding the uncertainty associated with route-to-route extrapolation.

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1,3,5-triethylbenzenes have been widely used as supramolecular templates to organize molecular-recognition elements. It is believed that the steric-gearing effect of the 1,3,5-triethylbenzene template directs the binding elements toward the same face of the central ring, hence increasing the binding affinity. At the same time the 1,3,5-trimethylbenzene scaffold, without steric-gearing effects, has also been found to improve the binding affinities of hosts compared to the unsubstituted analogues. By studying experimental data from the literature and the Cambridge Structural Database, as well as by conducting computational studies of representative structures, we concluded that the steric gearing offered by the ethyl groups confers some energetic advantage over the methyl groups, but the size of this advantage can be small and is dependent on the groups involved.