ACS Environmental Au最新文献

Reliable chemical property data are the key to defensible and unbiased assessments of chemical emissions, fate, hazard, exposure, and risks. However, the retrieval, evaluation, and use of reliable chemical property data can often be a formidable challenge for chemical assessors and model users. This comprehensive review provides practical guidance for use of chemical property data in chemical assessments. We assemble available sources for obtaining experimentally derived and in silico predicted property data; we also elaborate strategies for evaluating and curating the obtained property data. We demonstrate that both experimentally derived and in silico predicted property data can be subject to considerable uncertainty and variability. Chemical assessors are encouraged to use property data derived through the harmonization of multiple carefully selected experimental data if a sufficient number of reliable laboratory measurements is available or through the consensus consolidation of predictions from multiple in silico tools if the data pool from laboratory measurements is not adequate.

Oxygenations of aromatic soil and water contaminants with molecular O₂ catalyzed by Rieske dioxygenases are frequent initial steps of biodegradation in natural and engineered environments. Many of these non-heme ferrous iron enzymes are known to be involved in contaminant metabolism, but the understanding of enzyme–substrate interactions that lead to successful biodegradation is still elusive. Here, we studied the mechanisms of O₂ activation and substrate hydroxylation of two nitroarene dioxygenases to evaluate enzyme- and substrate-specific factors that determine the efficiency of oxygenated product formation. Experiments in enzyme assays of 2-nitrotoluene dioxygenase (2NTDO) and nitrobenzene dioxygenase (NBDO) with methyl-, fluoro-, chloro-, and hydroxy-substituted nitroaromatic substrates reveal that typically 20–100% of the enzyme’s activity involves unproductive paths of O₂ activation with generation of reactive oxygen species through so-called O₂ uncoupling. The ¹⁸O and ¹³C kinetic isotope effects of O₂ activation and nitroaromatic substrate hydroxylation, respectively, suggest that O₂ uncoupling occurs after generation of Fe^III-(hydro)peroxo species in the catalytic cycle. While 2NTDO hydroxylates ortho-substituted nitroaromatic substrates more efficiently, NBDO favors meta-substituted, presumably due to distinct active site residues of the two enzymes. Our data implies, however, that the O₂ uncoupling and hydroxylation activity cannot be assessed from simple structure–reactivity relationships. By quantifying O₂ uncoupling by Rieske dioxygenases, our work provides a mechanistic link between contaminant biodegradation, the generation of reactive oxygen species, and possible adaptation strategies of microorganisms to the exposure of new contaminants.

NO₂ and O₃ simulations have great uncertainties during the COVID-19 epidemic, but their biases and spatial distributions can be improved with NO₂ assimilations. This study adopted two top-down NO_X inversions and estimated their impacts on NO₂ and O₃ simulation for three periods: the normal operation period (P1), the epidemic lockdown period following the Spring Festival (P2), and back to work period (P3) in the North China Plain (NCP). Two TROPOspheric Monitoring Instrument (TROPOMI) NO₂ retrievals came from the Royal Netherlands Meteorological Institute (KNMI) and the University of Science and Technology of China (USTC), respectively. Compared to the prior NO_X emissions, the two TROPOMI posteriors greatly reduced the biases between simulations with in situ measurements (NO₂ MREs: prior 85%, KNMI −27%, USTC −15%; O₃ MREs: Prior −39%, KNMI 18%, USTC 11%). The NO_X budgets from the USTC posterior were 17–31% higher than those from the KNMI one. Consequently, surface NO₂ levels constrained by USTC-TROPOMI were 9–20% higher than those by the KNMI one, and O₃ is 6–12% lower. Moreover, USTC posterior simulations showed more significant changes in adjacent periods (surface NO₂: P2 vs P1, −46%, P3 vs P2, +25%; surface O₃: P2 vs P1, +75%, P3 vs P2, +18%) than the KNMI one. For the transport flux in Beijing (BJ), the O₃ flux differed by 5–6% between the two posteriori simulations, but the difference of NO₂ flux between P2 and P3 was significant, where the USTC posterior NO₂ flux was 1.5–2 times higher than the KNMI one. Overall, our results highlight the discrepancies in NO₂ and O₃ simulations constrained by two TROPOMI products and demonstrate that the USTC posterior has lower bias in the NCP during COVD-19.

Primary succession in mine tailings is a prerequisite for tailing vegetation. Microorganisms, including bacteria, fungi, and protists, play an important role in this process in the driving force for improving the nutritional status. Compared to bacteria and fungi, protist populations have rarely been investigated regarding their role in mine tailings, especially for those inhabiting tailings associated with primary succession. Protists are the primary consumers of fungi and bacteria, and their predatory actions promote the release of nutrients immobilized in the microbial biomass, as well as the uptake and turnover of nutrients, affecting the functions of the wider ecosystems. In this study, three different types of mine tailings associated with three successional stages (original tailings, biological crusts, and Miscanthus sinensis grasslands) were selected to characterize the protistan community diversity, structure, and function during primary succession. Some members classified as consumers dominated the network of microbial communities in the tailings, especially in the original bare land tailings. The keystone phototrophs of Chlorophyceae and Trebouxiophyceae showed the highest relative abundance in the biological crusts and grassland rhizosphere, respectively. In addition, the co-occurrences between protist and bacterial taxa demonstrated that the proportion of protistan phototrophs gradually increased during primary succession. Further, the metagenomic analysis of protistan metabolic potential showed that abundances of many functional genes associated with photosynthesis increased during the primary succession of tailings. Overall, these results suggest that the primary succession of mine tailings drives the changes observed in the protistan community, and in turn, the protistan phototrophs facilitate the primary succession of tailings. This research offers an initial insight into the changes in biodiversity, structure, and function of the protistan community during ecological succession on tailings.

To better understand the impact of plastic burning on atmospheric fine particulate matter (PM_2.5), we evaluated two methods for the quantification of 1,3,5-triphenylbenzene (TPB), a molecular tracer of plastic burning. Compared to traditional solvent-extraction gas chromatography mass spectrometry (GCMS) techniques, thermal-desorption (TD) GCMS provided higher throughput, lower limits of detection, more precise spike recoveries, a wider linear quantification range, and reduced solvent use. This method enabled quantification of TPB in fine particulate matter (PM_2.5) samples collected at rural and urban sites in the USA and Bangladesh. These analyses demonstrated a measurable impact of plastic burning at 5 of the 6 study locations, with the largest absolute and relative TPB concentrations occurring in Dhaka, Bangladesh, where plastic burning is expected to be a significant source of PM_2.5. Background-level contributions of plastic burning in the USA were estimated to be 0.004–0.03 μg m^–3 of PM_2.5 mass. Across the four sites in the USA, the lower estimate of plastic burning contributions to PM_2.5 ranged 0.04–0.8%, while the median estimate ranged 0.3–3% (save for Atlanta, Georgia, in the wintertime at 2–7%). The results demonstrate a consistent presence of plastic burning emissions in ambient PM_2.5 across urban and rural sites in the USA, with a relatively small impact in comparison to other anthropogenic combustion sources in most cases. Much higher TPB concentrations were observed in Dhaka, with estimated plastic burning impacts on PM_2.5 ranging from a lower estimate of 0.3–1.8 μg m^–3 (0.6–2% of PM_2.5) and the median estimate ranging 2–35 μg m^–3 (5–15% of PM_2.5). The methodological advances and new measurements presented herein help to assess the air quality impacts of burning plastic more broadly.

Mineral scaling is a phenomenon that occurs on submerged surfaces in contact with saline solutions. In membrane desalination, heat exchangers, and marine structures, mineral scaling reduces process efficiency and eventually leads to process failure. Therefore, achieving long-term scaling resistance is beneficial to enhancing process performance and reducing operating and maintenance costs. While evidence shows that superhydrophobic surfaces may reduce mineral scaling kinetics, prolonged scaling resistance is limited due to the finite stability of the entrained gas layer present in a Cassie–Baxter wetting state. Additionally, superhydrophobic surfaces are not always feasible for all applications, but strategies for long-term scaling resistance with smooth or even hydrophilic surfaces are often overlooked. In this study, we elucidate the role of interfacial nanobubbles on the scaling kinetics of submerged surfaces of varied wetting properties, including those that do not entrain a gas layer. We show that both solution conditions and surface wetting properties that promote interfacial bubble formation enhances scaling resistance. In the absence of interfacial bubbles, scaling kinetics decrease as surface energy decreases, while the presence of bulk nanobubbles enhances the scaling resistance of the surface with any wetting property. The findings in this study allude to scaling mitigation strategies that are enabled by solution and surface properties that promote the formation and stability of interfacial gas layers and provide insights to surface and process design for greater scaling resistance.

Daily emission estimates are essential for tracking the dynamic changes in emission sources. In this work, we estimate daily emissions of coal-fired power plants in China during 2017–2020 by combining information from the unit-based China coal-fired Power plant Emissions Database (CPED) and real-time measurements from continuous emission monitoring systems (CEMS). We develop a step-by-step method to screen outliers and impute missing values for data from CEMS. Then, plant-level daily profiles of flue gas volume and emissions obtained from CEMS are coupled with annual emissions from CPED to derive daily emissions. Reasonable agreement is found between emission variations and available statistics (i.e., monthly power generation and daily coal consumption). Daily power emissions are in the range of 6267–12,994, 0.4–1.3, 6.5–12.0, and 2.5–6.8 Gg for CO₂, PM_2.5, NO_x, and SO₂, respectively, with high emissions in winter and summer caused by heating and cooling demand. Our estimates can capture sudden decreases (e.g., those associated with COVID-19 lockdowns and short-term emission controls) or increases (e.g., those related to a drought) in daily power emissions during typical socioeconomic events. We also find that weekly patterns from CEMS exhibit no obvious weekend effect compared to those in previous studies. The daily power emissions will help to improve chemical transport modeling and facilitate policy formulation.

The phase separation between a liquid amine and the solid carbamic acid exhibited >99% CO₂ removal efficiency under a 400 ppm CO₂ flow system using diamines bearing an aminocyclohexyl group. Among them, isophorone diamine [IPDA; 3-(aminomethyl)-3,5,5-trimethylcyclohexylamine] exhibited the highest CO₂ removal efficiency. IPDA reacted with CO₂ in a CO₂/IPDA molar ratio of ≥1 even in H₂O as a solvent. The captured CO₂ was completely desorbed at 333 K because the dissolved carbamate ion releases CO₂ at low temperatures. The reusability of IPDA under CO₂ adsorption-and-desorption cycles without degradation, the >99% efficiency kept for 100 h under direct air capture conditions, and the high CO₂ capture rate (201 mmol/h for 1 mol of amine) suggest that the phase separation system using IPDA is robust and durable for practical use.