The 50 most-cited articles in Environmental Science & Technology, 2022

We submit that the safe operating space of the planetary boundary of novel entities is exceeded since annual production and releases are increasing at a pace that outstrips the global capacity for assessment and monitoring. The novel entities boundary in the planetary boundaries framework refers to entities that are novel in a geological sense and that could have large-scale impacts that threaten the integrity of Earth system processes. We review the scientific literature relevant to quantifying the boundary for novel entities and highlight plastic pollution as a particular aspect of high concern. An impact pathway from production of novel entities to impacts on Earth system processes is presented. We define and apply three criteria for assessment of the suitability of control variables for the boundary: feasibility, relevance, and comprehensiveness. We propose several complementary control variables to capture the complexity of this boundary, while acknowledging major data limitations. We conclude that humanity is currently operating outside the planetary boundary based on the…

It is hypothesized that environmental contamination by per- and polyfluoroalkyl substances (PFAS) defines a separate planetary boundary and that this boundary has been exceeded. This hypothesis is tested by comparing the levels of four selected perfluoroalkyl acids (PFAAs) (i.e., perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorohexanesulfonic acid (PFHxS), and perfluorononanoic acid (PFNA)) in various global environmental media (i.e., rainwater, soils, and surface waters) with recently proposed guideline levels. On the basis of the four PFAAs considered, it is concluded that (1) levels of PFOA and PFOS in rainwater often greatly exceed US Environmental Protection Agency (EPA) Lifetime Drinking Water Health Advisory levels and the sum of the aforementioned four PFAAs (Σ4 PFAS) in rainwater is often above Danish drinking water limit values also based on Σ4 PFAS; (2) levels of PFOS in rainwater are often above Environmental Quality Standard for Inland European Union Surface Water; and (3) atmospheric deposition also leads to global soils being ubiquitously…

Abstract Microplastic pollution is an emerging environmental problem, and little research has focused on its impact on the human body. Based on retrospective case series, the study required participants to fill out a questionnaire and provide sputum samples in order to investigate the presence of microplastics in human sputum and determine whether humans involuntarily inhale them. A total of 22 patients suffering from different respiratory diseases were recruited. We used an Agilent 8700 laser infrared imaging spectrometer and Fourier-transform infrared microscope to analyze sputum samples and evaluate microplastics in the respiratory tract. Remarkably, the size range of the method for detecting microplastics in our study is 20–500 μm. The results showed that 21 types of microplastics were identified, and polyurethane was dominant, followed by polyester, chlorinated polyethylene, and alkyd varnish, accounting for 78.36% of the total microplastics. Most of the aspirated microplastics detected are smaller than 500 μm in size (median: 75.43 μm; interquartile range: 44.67–210.64 μm).…

In this study, the previously overlooked effects of contaminants’ molecular structure on their degradation efficiencies and dominant reactive oxygen species (ROS) in advanced oxidation processes (AOPs) are investigated with a peroxymonosulfate (PMS) activation system selected as the typical AOP system. Averagely, degradation efficiencies of 19 contaminants are discrepant in the CoCaAl-LDO/PMS system with production of SO 4 •–, • OH, and 1 O 2 . Density functional theory calculations indicated that compounds with high E HOMO, low-energy gap (Δ E = E LUMO – E HOMO ), and low vertical ionization potential are more vulnerable to be attacked. Further analysis disclosed that the dominant ROS was the same one when treating similar types of contaminants, namely SO 4 •–, 1 O 2, 1 O 2, and • OH for the degradation of CBZ-like compounds, SAs, bisphenol, and triazine compounds, respectively. This phenomenon may be caused by the contaminants’ structures especially the commonly shared or basic parent structures which can affect their effective reaction time and second-order rate constants with…

The complexity and dynamics of the environment make it extremely difficult to directly predict and trace the temporal and spatial changes in pollution. In the past decade, the unprecedented accumulation of data, the development of high-performance computing power, and the rise of diverse machine learning (ML) methods provide new opportunities for environmental pollution research. The ML methodology has been used in satellite data processing to obtain ground-level concentrations of atmospheric pollutants, pollution source apportionment, and spatial distribution modeling of water pollutants. However, unlike the active practices of ML in chemical toxicity prediction, advanced algorithms such as deep neural networks in environmental process studies of pollutants are still deficient. In addition, over 40% of the environmental applications of ML go to air pollution, and its application range and acceptance in other aspects of environmental science remain to be increased. The use of ML methods to revolutionize environmental science and its problem-solving scenarios has its own challenges.…

High Resolution Image Download MS PowerPoint Slide p -Phenylenediamines (PPDs) have been extensively used in the rubber industry and found to be pervasive in various environmental compartments for decades, while their transformation products and associated ecological and human health risks remain largely unknown. Herein, we developed and implemented a mass spectrometry-based platform combined with self-synthesized standards for the investigation of rubber-derived quinones formed from PPD antioxidants. Our results demonstrated that five quinones are ubiquitously present in urban runoff, roadside soils, and air particles. All of the identified sources are closely related to mankind’s activities. Among the identified quinones, N -(1,3-dimethylbutyl)- N ′-phenyl- p -phenylenediamine quinone has been recently found to be highly toxic, causing acute mortality of coho salmon in the Pacific Northwest. Ultrahigh-performance liquid chromatography coupled with triple quadrupole mass spectrometry was then applied for quantification of the five quinones and their corresponding PPD antioxidants.…

Biochar application is a promising strategy for the remediation of contaminated soil, while ensuring sustainable waste management. Biochar remediation of heavy metal (HM)-contaminated soil primarily depends on the properties of the soil, biochar, and HM. The optimum conditions for HM immobilization in biochar-amended soils are site-specific and vary among studies. Therefore, a generalized approach to predict HM immobilization efficiency in biochar-amended soils is required. This study employs machine learning (ML) approaches to predict the HM immobilization efficiency of biochar in biochar-amended soils. The nitrogen content in the biochar (0.3-25.9%) and biochar application rate (0.5-10%) were the two most significant features affecting HM immobilization. Causal analysis showed that the empirical categories for HM immobilization efficiency, in the order of importance, were biochar properties > experimental conditions > soil properties > HM properties. Therefore, this study presents new insights into the effects of biochar properties and soil properties on HM immobilization. This…

Single-atom catalysts (SACs)-based peroxymonosulfate (PMS) systems are highly selective to the type of organic pollutants while the mechanisms remain ambiguous. In this work, we carried out experimental and theoretical investigations to reveal the origins of selectivity of radical and nonradical pathways in a designated Co–N 4 –C/PMS system. Two typical pollutants [bisphenol A (BPA) and metronidazole (MNZ)] with different molecular structures were employed for comparison. We found that radical oxidation (SO 4 •– and HO • ) and nonradical electron-transfer pathway (ETP) co-existed in the Co–N 4 –C/PMS system. Pollutants (e.g., MNZ) with a high redox potential were degraded primarily by free radicals rather than ETP, while the oxidization of low-redox pollutants (e.g., BPA) was dominated by ETP at the surface region of Co–N 4 –C which overwhelmed the contributions of radicals in the homogeneous phase. Intriguingly, the contributions of radical and nonradical pathways could be manipulated by the PMS loading, which simultaneously increased the radical population and elevated the…

Implementation of regulatory standards has reduced exhaust emissions of particulate matter from road traffic substantially in the developed world. However, nonexhaust particle emissions arising from the wear of brakes, tires, and the road surface, together with the resuspension of road dust, are unregulated and exceed exhaust emissions in many jurisdictions. While knowledge of the sources of nonexhaust particles is fairly good, source-specific measurements of airborne concentrations are few, and studies of the toxicology and epidemiology do not give a clear picture of the health risk posed. This paper reviews the current state of knowledge, with a strong focus on health-related research, highlighting areas where further research is an essential prerequisite for developing focused policy responses to nonexhaust particles.

Advanced oxidation processes (AOPs) can degrade a wide range of trace organic contaminants (TrOCs) to improve the quality of potable water or discharged wastewater effluents. Their effectiveness is impacted, however, by the dissolved organic matter (DOM) that is ubiquitous in all water sources. During the application of an AOP, DOM can scavenge radicals and/or block light penetration, therefore impacting their effectiveness toward contaminant transformation. The multiple ways in which different types or sources of DOM can impact oxidative water purification processes are critically reviewed. DOM can inhibit the degradation of TrOCs, but it can also enhance the formation and reactivity of useful radicals for contaminants elimination and alter the transformation pathways of contaminants. An in-depth analysis highlights the inhibitory effect of DOM on the degradation efficiency of TrOCs based on DOM's structure and optical properties and its reactivity toward oxidants as well as the synergistic contribution of DOM to the transformation of TrOCs from the analysis of DOM's redox…

The contamination of soil with organic pollutants has been accelerated by agricultural and industrial development and poses a major threat to global ecosystems and human health. Various chemical and physical techniques have been developed to remediate soils contaminated with organic pollutants, but challenges related to cost, efficacy, and toxic byproducts often limit their sustainability. Fortunately, phytoremediation, achieved through the use of plants and associated microbiomes, has shown great promise for tackling environmental pollution; this technology has been tested both in the laboratory and in the field. Plant-microbe interactions further promote the efficacy of phytoremediation, with plant growth-promoting bacteria (PGPB) often used to assist the remediation of organic pollutants. However, the efficiency of microbe-assisted phytoremediation can be impeded by (i) high concentrations of secondary toxins, (ii) the absence of a suitable sink for these toxins, (iii) nutrient limitations, (iv) the lack of continued release of microbial inocula, and (v) the lack of shelter or…

Plastic debris in the global biosphere is an increasing concern, and nanoplastic (NPs) toxicity in humans is far from being understood. Studies have indicated that NPs can affect mitochondria, but the underlying mechanisms remain unclear. The liver and lungs have important metabolic functions and are vulnerable to NP exposure. In this study, we investigated the effects of 80 nm NPs on mitochondrial functions and metabolic pathways in normal human hepatic (L02) cells and lung (BEAS-2B) cells. NP exposure did not induce mass cell death; however, transmission electron microscopy analysis showed that the NPs could enter the cells and cause mitochondrial damage, as evidenced by overproduction of mitochondrial reactive oxygen species, alterations in the mitochondrial membrane potential, and suppression of mitochondrial respiration. These alterations were observed at NP concentrations as low as 0.0125 mg/mL, which might be comparable to the environmental levels. Nontarget metabolomics confirmed that the most significantly impacted processes were mitochondrial-related. The metabolic…

High-valent iron(IV)–oxo complexes are of great significance as reactive intermediates implicated in diverse chemical and biological systems. The aqueous iron(IV)–oxo complex (Fe aq IV O 2+ ) is the simplest but one of the most powerful ferryl ion species, which possesses a high-spin state, high reduction potential, and long lifetime. It has been well documented that Fe aq IV O 2+ reacts with organic compounds through various pathways (hydrogen-atom, hydride, oxygen-atom, and electron transfer as well as electrophilic addition) at moderate reaction rates and show selective reactivity toward inorganic ions prevailing in natural water, which single out Fe aq IV O 2+ as a superior candidate for oxidative water treatment. This review provides state-of-the-art knowledge on the chemical properties and oxidation mechanism and kinetics of Fe aq IV O 2+, with special attention to the similarities and differences to two representative free radicals (hydroxyl radical and sulfate radical). Moreover, the prospective role of Fe aq IV O 2+ in Fe aq 2+ activation-initiated advanced oxidation…

Single oxygen-based advanced oxidation processes ( 1 O 2 -AOPs) exhibit great prospects in selective degradation of organic pollutants. However, efficient production of 1 O 2 via tailored design of catalysts to achieve selective oxidation of contaminants remains challenging. Herein, we develop a simple strategy to regulate the components and coordination of Co–N–C catalysts at the atomic level by adjusting the Zn/Co ratio of bimetallic zeolitic imidazolate frameworks (Zn x Co 1 -ZIFs). Zn 4 Co 1 –C demonstrates 98% selective removal of phenol in the mixed phenol/benzoic acid (phenol/BA) solutions. Density functional theory calculations and experiments reveal that more active CoN 4 sites are generated in Zn 4 Co 1 –C, which are beneficial to peroxymonosulfate activation to generate 1 O 2 . Furthermore, the correlation between the origin of selectivity and well-defined catalysts is systematically investigated by the electron paramagnetic resonance test and quenching experiments. This work may provide novel insights into selective removal of target pollutants in a complicated water…

Abstract Tire road wear particles (TRWPs) are one of the largest sources of microplastics to the urban environment with recent concerns as they also provide a pathway for additive chemicals to leach into the environment. Stormwater is a major source of TRWPs and associated additives to urban surface water, with additives including the antioxidant derivative N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine-quinone (6PPD-quinone) demonstrating links to aquatic toxicity at environmentally relevant concentrations. The present study used complementary analysis methods to quantify both TRWPs and a suite of known tire additive chemicals (including 6PPD-quinone) to an urban tributary in Australia during severe storm events. Concentrations of additives increased more than 40 times during storms, with a maximum concentration of 2760 ng/L for ∑15additives, 88 ng/L for 6PPD-quinone, and a similar profile observed in each storm. TRWPs were detected during storm peaks with a maximum concentration between 6.4 and 18 mg/L, and concentrations of TRWPs and all additives were highly correlated.…

High Resolution Image Download MS PowerPoint Slide Nitrogen dioxide (NO 2 ) at the ground level poses a serious threat to environmental quality and public health. This study developed a novel, artificial intelligence approach by integrating spatiotemporally weighted information into the missing extra-trees and deep forest models to first fill the satellite data gaps and increase data availability by 49% and then derive daily 1 km surface NO 2 concentrations over mainland China with full spatial coverage (100%) for the period 2019–2020 by combining surface NO 2 measurements, satellite tropospheric NO 2 columns derived from TROPOMI and OMI, atmospheric reanalysis, and model simulations. Our daily surface NO 2 estimates have an average out-of-sample (out-of-city) cross-validation coefficient of determination of 0.93 (0.71) and root-mean-square error of 4.89 (9.95) μg/m 3 . The daily seamless high-resolution and high-quality dataset “ChinaHighNO 2 ” allows us to examine spatial patterns at fine scales such as the urban–rural contrast. We observed systematic large differences between…

High Resolution Image Download MS PowerPoint Slide PM 2.5 chemical components play significant roles in the climate, air quality, and public health, and the roles vary due to their different physicochemical properties. Obtaining accurate and timely updated information on China’s PM 2.5 chemical composition is the basis for research and environmental management. Here, we developed a full-coverage near-real-time PM 2.5 chemical composition data set at 10 km spatial resolution since 2000, combining the Weather Research and Forecasting–Community Multiscale Air Quality modeling system, ground observations, a machine learning algorithm, and multisource-fusion PM 2.5 data. PM 2.5 chemical components in our data set are in good agreement with the available observations (correlation coefficients range from 0.64 to 0.75 at a monthly scale from 2000 to 2020 and from 0.67 to 0.80 at a daily scale from 2013 to 2020; most normalized mean biases within ±20%). Our data set reveals the long-term trends in PM 2.5 chemical composition in China, especially the rapid decreases after 2013 for sulfate,…

Nanofiltration (NF) membranes have been widely applied in many important environmental applications, including water softening, surface/groundwater purification, wastewater treatment, and water reuse. In recent years, a new class of piperazine (PIP)-based NF membranes featuring a crumpled polyamide layer has received considerable attention because of their great potential for achieving dramatic improvements in membrane separation performance. Since the report of novel crumpled Turing structures that exhibited an order of magnitude enhancement in water permeance ( Science 2018, 360 (6388), 518−521), the number of published research papers on this emerging topic has grown exponentially to approximately 200. In this critical review, we provide a systematic framework to classify the crumpled NF morphologies. The fundamental mechanisms and fabrication methods involved in the formation of these crumpled morphologies are summarized. We then discuss the transport of water and solutes in crumpled NF membranes and how these transport phenomena could simultaneously improve membrane water…

Material-enhanced heterogonous peroxymonosulfate (PMS) activation on emerging organic pollutant degradation has attracted intensive attention, and a challenge is the electron transfer efficiency from material to PMS for radical production. Herein, an interface architecture of Co(OH) 2 nanosheets growing on the KNbO 3 perovskite [Co(OH) 2 /KNbO 3 ] was developed, which showed high catalytic activity in PMS activation. A high reaction rate constant ( k 1 ) of 0.631 min –1 and complete removal of pazufloxacin within 5 min were achieved. X-ray photoelectron spectroscopy, X-ray absorption near edge structure spectra, and density functional theory (DFT) calculations revealed the successful construction of the material interface and modulated electronic structure for Co(OH) 2 /KNbO 3, resulting in the hole accumulation on Co(OH) 2 and electron accumulation on KNbO 3 . Bader topological analysis on charge density distribution further indicates that the occupations of Co-3d and O-2p orbitals in Co(OH) 2 /KNbO 3 are pushed above the Fermi level to form antibonding states (σ*), leading to high…

idation (anammox) was discovered as a new microbial reaction in the late 1990s, which led to the development of an innovative energy- and carbon-efficient technology─partial nitritation and anammox (PN/A)─for nitrogen removal. PN/A was first applied to remove the nitrogen from high-strength wastewaters, e.g., anaerobic digestion liquor (i.e., sidestream), and further expanded to the main line of wastewater treatment plants (i.e., mainstream). While sidestream PN/A has been well-established with extensive full-scale installations worldwide, practical application of PN/A in mainstream treatment has been proven extremely challenging to date. A key challenge is achieving stable suppression of nitrite-oxidizing bacteria (NOB). This study examines the progress of NOB suppression in both sidestream- and mainstream PN/A over the past two decades. The successful NOB suppression in sidestream PN/A was reviewed, and these successes were evaluated in terms of their transferability into mainstream PN/A. Drawing on the learning over the past decades, we anticipate that a hybrid process, comprised…

Hydroxyl radical (•OH) is an active species widely reported in studies across many scientific fields, and hence, its reliable analysis is vitally important. Currently, alcohols are commonly used as scavengers for •OH determination. However, the impacts of alcohols on the reliability of •OH detection remain unknown. In this study, we found that adding different types and different amounts of alcohols in water samples treated with ultraviolet irradiation undesirably produced substantial amounts of hydrogen peroxide (H 2 O 2 ), which is a known •OH precursor. This means that the conventional •OH determination method using alcohols is likely unreliable or even misleading. Through careful investigation, we revealed an overlooked reaction pathway during H 2 O 2 and •OH transformations. Varying oxygen concentrations, pHs, alcohol dosages, and types altered H 2 O 2 formation, which can affect •OH determination accuracy. Among alcohols, n -butanol is the best scavenger because it quenches •OH rapidly but re-forms little H 2 O 2 .

Efficient degradation of organic pollutants by oxidative radicals is challenging in the complex soil environment because of the invalid consumption of radicals by nontarget background substances and the generation of secondary halogenated organic pollutants. Nonradical-based oxidation is a promising pollutant removal method due to its high selectivity and environmental adaptability. Herein, a biochar-supported sheetlike CuO (e-CuO@BC) was developed, which exhibited efficient activation of peroxydisulfate (PDS) via nonradical pathways. The activation mechanisms were identified as (i) formation of surface-bonding active complexes via an outer-sphere interaction between e-CuO@BC and PDS and (ii) the continuous generation of 1 O 2 by the cycling of the Cu(I)/Cu(II) redox couple. In addition, the activation of PDS primarily occurred at the crystal facet (001) of e-CuO occupied by Cu atoms and was well facilitated by the Cu–O–C bond, which induced electron-rich centers around CuO. Two oxidative species from PDS activation, including surface-bonding active complexes and 1 O 2, showed a…

In persulfate activation by copper-based catalysts, high-valent copper (Cu(III)) is an overlooked reactive intermediate that contributes to efficient persulfate utilization and organic pollutant removal. However, the mechanisms underlying heterogeneous activation and enhanced persulfate utilization are not fully understood. Here, copper oxide (CuO) nanosheets (synthesized with a facile precipitation method) exhibited high catalytic activity for peroxymonosulfate (PMS) activation with 100% 4-chlorophenol (4-CP) degradation within 3 min. Evidence for the critical role of surface-associated Cu(III) on PMS activation and 4-CP degradation over a wide pH range (pH 3–10) was obtained using in situ Raman spectroscopy, electron paramagnetic resonance, and quenching tests. Cu(III) directly oxidized 4-CP and other phenolic pollutants, with rate constants inversely proportional to their ionization potentials. Cu(III) preferentially oxidizes 4-CP rather than react with two PMS molecules to generate one molecule of 1 O 2, thus minimizing this less efficient PMS utilization pathway. Accordingly, a…

Microplastics (MPs) interact frequently with dissolved organic matter (DOM) commonly found in the environment, but information on the aging behavior of MPs under the participation of DOM is still lacking. Thus, the polystyrene microplastic (PSMP) aging process with DOM participation was systematically studied by electron paramagnetic resonance spectroscopy, high-performance liquid chromatography, Fourier transform infrared (FTIR) spectroscopy, and two-dimensional correlation spectroscopy analyses under dark and ultraviolet (UV) light conditions. DOM was found to promote electron transfer to generate reactive oxygen species (ROS) under dark conditions and the aging of PSMPs, while the process of DOM generating ROS under UV light was more susceptible to photoelectrons and accelerated the aging process of PSMPs. However, among the four DOM types, fulvic acid (FA) has a more significant promoting effect on the aging process of PSMPs than humic acid, which can be attributed to the stronger conversion ability of FA to semiquinone radicals. Density functional theory calculations are used…

Rapid generation of high-valent cobalt-oxo species (Co(IV)═O) for the removal of organic contaminants has been challenging because of the low conversion efficiency of Co(III)/Co(II) and the high activation energy barrier of the Co(II)-oxidant complex. Herein, we introduced nitrogen (N) vacancies into graphite carbon nitride imbedded with cobalt carbonate (CCH/CN–V n ) in a peroxymonosulfate (PMS)/visible light system to break the limitations of a conventional two-electron transfer path. These N vacancies enhanced the electron distribution of the Co 3d orbital and lowered the energy barrier to cleave the O–O bond of PMS in the Co(II)-PMS complex, achieving the modulation of major active species from 1 O 2 to Co(IV)═O. The developed synergistic system that exhibited adsorption and oxidation showed remarkable selectivity and contaminant removal performance in inorganic (Cl –, NO 3 –, HCO 3 –, and HPO 4 – ) organic (HA) and even practical aqueous matrices (tap water and secondary effluent). This study provides a novel mechanistic perspective to modulate the nonradical path for…

Antimicrobial resistance (AMR) is a grand societal challenge with important dimensions in the water environment that contribute to its evolution and spread. Environmental monitoring could provide vital information for mitigating the spread of AMR; this includes assessing antibiotic resistance genes (ARGs) circulating among human populations, identifying key hotspots for evolution and dissemination of resistance, informing epidemiological and human health risk assessment models, and quantifying removal efficiencies by domestic wastewater infrastructure. However, standardized methods for monitoring AMR in the water environment will be vital to producing the comparable data sets needed to address such questions. Here we sought to establish scientific consensus on a framework for such standardization, evaluating the state of the science and practice of AMR monitoring of wastewater, recycled water, and surface water, through a literature review, survey, and workshop leveraging the expertise of academic, governmental, consulting, and water utility professionals.

ADVERTISEMENT RETURN TO ISSUEPREVViewpointNEXTColor: An Important but Overlooked Factor for Plastic Photoaging and Microplastic FormationXiaoli ZhaoXiaoli ZhaoState Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, ChinaMore by Xiaoli ZhaoView Biographyhttps://orcid.org/0000-0002-5671-389X, Junyu WangJunyu WangState Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, ChinaMore by Junyu Wang, Kenneth Mei Yee LeungKenneth Mei Yee LeungState Key Laboratory of Marine Pollution and Department of Chemistry, City University of Hong Kong, Hong Kong 999077, ChinaMore by Kenneth Mei Yee Leung, and Fengchang Wu*Fengchang WuState Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China*Phone: +86-010-84931804. Email: [email protected]More by Fengchang WuView Biographyhttps://orcid.org/0000-0001-8595-2243Cite this: Environ. Sci. Technol. 2022, 56, 13,…

The environmentally benign Mn oxides play a crucial role in the transformation of organic contaminants, either through catalytically decomposing oxidants, e.g., peroxymonosulfate (PMS), or through directly oxidizing the target pollutants. Because of their dual roles and the complex surface chemical reactions, the mechanism involved in Mn oxide-catalyzed PMS activation processes remains obscure. Here, we clearly elucidate the mechanism involved in the Mn 2 O 3 catalyzed PMS activation process by means of separating the PMS activation and the pollutant oxidation process. Mn 2 O 3 acts as a shuttle that mediates the electron transfer from organic substrates to PMS, accompanied by the redox cycle of surface Mn(IV)/Mn(III). Multiple experimental results indicate that PMS is bound to the surface of Mn 2 O 3 to form an inner-sphere complex, which then decomposes to form long-lived surface reactive Mn(IV) species, without the generation of sulfate radicals (SO 4 •– ) and hydroxyl radicals (HO • ). The surface reactive Mn(IV) species are proposed to be responsible for the degradation of…

Volatile organic compounds (VOCs) are atmospheric pollutants that have been of concern for researchers in recent years because they are toxic, difficult to remove, and widely sourced and easily cause damage to the environment and human body. Most scholars use low-temperature plasma biological treatment, catalytic oxidation, adsorption, condensation, and recovery techniques to treat then effectively. Among them, catalytic oxidation technology has the advantages of a high catalytic efficiency, low energy consumption, high safety factor, high treatment efficiency, and less secondary pollution; it is currently widely used for VOC degradation technology. In this paper, the catalytic oxidation technology for the degradation of multiple types of VOCs as well as the development of a single metal oxide catalyst have been briefly introduced. We also focus on the research progress of composite metal oxide catalysts for the removal of VOCs by comparing and analyzing the metal component ratio, preparation method, and types of precursors and the catalysts' influence on the catalytic performance.…

The conversion of nitrate to ammonia can serve two important functions: mitigating nitrate pollution and offering a low energy intensity pathway for ammonia synthesis. Conventional ammonia synthesis from electrocatalytic nitrate reduction reactions (NO 3 RR) is often impeded by incomplete nitrate conversion, sluggish kinetics, and the competition of hydrogen evolution reactions. Herein, atomic Cu sites anchored on micro-/mesoporous nitrogen-doped carbon (Cu MNC) with fine-tuned hydrophilicity, micro-/mesoporous channels, and abundant Cu(I) sites were synthesized for selective nitrate reduction to ammonia, achieving ambient temperature and pressure hydrogenation of nitrate. Laboratory experiments demonstrated that the catalyst has an ammonia yield rate per active site of 5466 mmol g Cu –1 h –1 and transformed 94.8% nitrate in wastewater containing 100 mg-N L –1 to near drinking water standard (MCL of 5 mg-N L –1 ) at −0.64 V vs RHE. Extended X-ray absorption fine structure (EXAFS) and theoretical calculations showed that the coordination environment of Cu(I) sites (Cu(I)-N 3 C 1 )…

This study conducted the first extensive and comprehensive investigation of the whole-scale sedimentary antibiotic concentration, possible drivers, environmental fate, and potential ecological risks in the Yangtze River. Totally, 20 antibiotics were detected in the sediments. Results revealed that the order of antibiotic abundance in sediment was fluoroquinolones > tetracyclines > macrolides > sulfonamides > amphenicols. The total antibiotic concentrations were 0.10–134.4 ng/g (mean: 11.88 ng/g). Of these, fluoroquinolones and tetracyclines were the two dominant antibiotic categories. The dominant occurrence of fluoroquinolones and tetracyclines in sediments suggested that the distribution coefficient ( K d ) was one of the important factors to determine their fate. Correlation analysis demonstrated that antibiotic contamination was largely influenced by the local scale of animal husbandry, and the positive correlation between antibiotics and heavy metals was likely driven by their common source of contamination and the complexation. Environmental risk assessment showed that…

Smoke from wildfires is a growing health risk across the US. Understanding the spatial and temporal patterns of such exposure and its population health impacts requires separating smoke-driven pollutants from non-smoke pollutants and a long time series to quantify patterns and measure health impacts. We develop a parsimonious and accurate machine learning model of daily wildfire-driven PM 2.5 concentrations using a combination of ground, satellite, and reanalysis data sources that are easy to update. We apply our model across the contiguous US from 2006 to 2020, generating daily estimates of smoke PM 2.5 over a 10 km-by-10 km grid and use these data to characterize levels and trends in smoke PM 2.5 . Smoke contributions to daily PM 2.5 concentrations have increased by up to 5 μg/m 3 in the Western US over the last decade, reversing decades of policy-driven improvements in overall air quality, with concentrations growing fastest for higher income populations and predominantly Hispanic populations. The number of people in locations with at least 1 day of smoke PM 2.5 above 100 μg/m 3…

Per- and polyfluoroalkyl substances (PFASs) are fluorinated organic chemicals that are concerning due to their environmental persistence and adverse human and ecological effects. Remediation of environmental PFAS contamination and their presence in consumer products have led to the production of solid and liquid waste streams containing high concentrations of PFASs, which require efficient and cost-effective treatment solutions. PFASs are challenging to defluorinate by conventional and advanced destructive treatment processes, and physical separation processes produce waste streams (e.g., membrane concentrate, spent activated carbon) requiring further post-treatment. Incineration and other thermal treatment processes are widely available, but their use in managing PFAS-containing wastes remains poorly understood. Under specific operating conditions, thermal treatment is expected to mineralize PFASs, but the degradation mechanisms and pathways are unknown. In this review, we critically evaluate the thermal decomposition mechanisms, pathways, and byproducts of PFASs that are crucial…

Biodegradable polymers are promoted as promising alternatives for conventional non-degradable plastics, but they may also negatively impact soil ecosystems. Here, we estimated the effects of biodegradable (polylactide (PLA) and polybutylene succinate (PBS)) and non-biodegradable (polyethylene (PE) and polystyrene (PS)) microplastics at a concentration of 1% (w/w) on dissolved organic matter (DOM) in two soil types, a black soil (BS) and a yellow soil (YS), by using fluorescence excitation-emission matrix spectroscopy and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). PBS significantly increased the contents of soil dissolved organic carbon (DOC) and the relative intensities of protein-like components. The turnover rates of soil DOM were statistically higher in PBS treatments (0.106 and 0.196, p < 0.001) than those in other microplastic groups. The FT-ICR-MS results indicated that more labile-active DOM molecules were preferentially obtained in biodegradable microplastic treatments, which may be attributed to the polymer degradation. The…

Nanoplastics (NPs) are currently considered an environmental pollutant of concern, but the actual extent of NP pollution in environmental water bodies remains unclear and there is not enough quantitative data to conduct proper risk assessments. In this study, a pretreatment method combining ultrafiltration (UF, 100 kDa) with hydrogen peroxide digestion and subsequent detection with pyrolysis gas chromatography-mass spectrometry (Py-GC/MS) was developed and used to identify and quantify six selected NPs in surface water (SW) and groundwater (GW), including poly(vinylchloride) (PVC), poly(methyl methacrylate) (PMMA), polypropylene (PP), polystyrene (PS), polyethylene (PE), and poly(ethylene terephthalate) (PET). The results show that the proposed method could detect NPs in environmental water samples. Nearly all selected NPs could be detected in the surface water at all locations, while PVC, PMMA, PS, and PET NPs were frequently below the detection limit in the groundwater. PP (32.9-69.9%) and PE (21.3-44.3%) NPs were the dominant components in both surface water and groundwater,…

Understanding the environmental fate of microplastics is essential for their risk assessment. It is essential to differentiate size classes and degradation states. Still, insights into fragmentation and degradation mechanisms of primary and secondary microplastics into micro- and nanoplastic fragments and other degradation products are limited. Here, we present an adapted NanoRelease protocol for a UV-dose-dependent assessment and size-selective quantification of the release of micro- and nanoplastic fragments down to 10 nm and demonstrate its applicability for polyamide and thermoplastic polyurethanes. The tested cryo-milled polymers do not originate from actual consumer products but are handled in industry and are therefore representative of polydisperse microplastics occurring in the environment. The protocol is suitable for various types of microplastic polymers, and the measured rates can serve to parameterize mechanistic fragmentation models. We also found that primary microplastics matched the same ranking of weathering stability as their corresponding macroplastics and that…

Increased use of environmental DNA (eDNA) analysis for indirect species detection has spurred the need to understand eDNA persistence in the environment. Understanding the persistence of eDNA is complex because it exists in a mixture of different states (e.g., dissolved, particle adsorbed, intracellular, and intraorganellar), and each state is expected to have a specific decay rate that depends on environmental parameters. Thus, improving knowledge about eDNA conversion rates between states and the reactions that degrade eDNA in different states is needed. Here, we focus on eukaryotic extraorganismal eDNA, outline how water chemistry and suspended mineral particles likely affect conversion among each eDNA state, and indicate how environmental parameters affect persistence of states in the water column. On the basis of deducing these controlling parameters, we synthesized the eDNA literature to assess whether we could already derive a general understanding of eDNA states persisting in the environment. However, we found that these parameters are often not being measured or reported…

Electron paramagnetic resonance (EPR) has been extensively used for the identification of free radicals that are generated from advanced oxidation processes (AOPs) so as to establish the reaction mechanism. However, some misinterpretations or controversies on the identity of detected EPR signals remain in the literature. This study, with Cu(II)-based AOPs as examples, comprehensively investigated the origin of 5,5-dimethyl-l-pyrroline N -oxide (DMPO) adducts in Cu(II) alone, Cu(II)/H 2 O 2, Cu(II)/peroxymonosulfate (PMS), and Cu(II)/peroxydisulfate (PDS) systems. In most Cu(II) systems, DMPO-OH signals can be detected even without any peroxygens, indicating the presence of other origins of this adduct in addition to the genuine spin trapping of • OH by DMPO. According to the formed secondary radical adducts (DMPO-OCH 3 from a nonradical process or DMPO-CH 2 OH from a radical oxidation) derived from methanol quenching, we propose that CuO +, instead of free radicals, is involved in the Cu(II)/PMS system, while • OH is indeed generated in the Cu(II)/H 2 O 2 and Cu(II)/PDS systems…

Inorganic scaling caused by precipitation of sparingly soluble salts at supersaturation is a common but critical issue, limiting the efficiency of membrane-based desalination and brine management technologies as well as other engineered systems. A wide range of minerals including calcium carbonate, calcium sulfate, and silica precipitate during membrane-based desalination, limiting water recovery and reducing process efficiency. The economic impact of scaling on desalination processes requires understanding of its sources, causes, effects, and control methods. In this Critical Review, we first describe nucleation mechanisms and crystal growth theories, which are fundamental to understanding inorganic scale formation during membrane desalination. We, then, discuss the key mechanisms and factors that govern membrane scaling, including membrane properties, such as surface roughness, charge, and functionality, as well as feedwater characteristics, such as pH, temperature, and ionic strength. We follow with a critical review of current characterization techniques for both homogeneous and…

Per- and polyfluoroalkyl substances (PFASs) have been a focal point of environmental chemistry and chemical regulation in recent years, culminating in a shift from individual PFAS regulation toward a PFAS group regulatory approach in Europe. PFASs are a highly diverse group of substances, and knowledge about this group is still scarce beyond the well-studied, legacy long-chain, and short-chain perfluorocarboxylates (PFCAs) and perfluorosulfonates (PFSAs). Herein, quantitative and semiquantitative data for 43 legacy short-chain and ultra-short-chain PFASs (≤2 perfluorocarbon atoms for PFCAs, ≤3 for PFSAs and other PFASs) in 46 water samples collected from 13 different sources of German drinking water are presented. The PFASs considered include novel compounds like hexafluoroisopropanol, bis(trifluoromethylsulfonyl)imide, and tris(pentafluoroethyl)trifluorophosphate. The ultra-short-chain PFASs trifluoroacetate, perfluoropropanoate, and trifluoromethanesulfonate were ubiquitous and present at the highest concentrations (98% of sum target PFAS concentrations). "PFAS total" parameters…

This study presents a life-cycle analysis of greenhouse gas (GHG) emissions of biodiesel (fatty acid methyl ester) and renewable diesel (RD, or hydroprocessed easters and fatty acids) production from oilseed crops, distillers corn oil, used cooking oil, and tallow. Updated data for biofuel production and waste fat rendering were collected through industry surveys. Life-cycle GHG emissions reductions for producing biodiesel and RD from soybean, canola, and carinata oils range from 40% to 69% after considering land-use change estimations, compared with petroleum diesel. Converting tallow, used cooking oil, and distillers corn oil to biodiesel and RD could achieve higher GHG reductions of 79% to 86% lower than petroleum diesel. The biodiesel route has lower GHG emissions for oilseed-based pathways than the RD route because transesterification is less energy-intensive than hydro-processing. In contrast, processing feedstocks with high free fatty acid such as tallow via the biodiesel route results in slightly higher GHG emissions than the RD route, mainly due to higher energy use for…

As an efficient active oxidant for the selective degradation of pollutants in wastewater, the high-valent copper species Cu(III) with persulfate activation has attracted substantial attention in some Cu-based catalysts. However, the systematic study of a catalyst structure and mechanism about Cu(III) with peroxydisulfate (PDS) activation is challenging owing to the coexistence of multiple Cu species and the structural symmetry of PDS. Herein, we anchored a Cu atom with two pyridinic N atoms to synthesize a single-atom Cu catalyst (Cu SA -NC). Experimental characterizations and theoretical calculations complemented each other well because of the uniform atomic active sites. The single-atom Cu was identified as the active site, and the unsaturated Cu-N 2 configuration was more conductive to PDS activation than the saturated Cu-N 4 configuration. Benefiting from the generation of Cu(III), Cu SA -NC exhibited an obvious selective and anti-interference performance for pollutant degradation in a complex matrix. The superior catalytic activity of Cu SA -NC compared with that of other…

utilization in treating concentrated PFAS. The optimized UV/S + I system achieved >99.7% removal of most PFSAs and PFCAs and >90% overall defluorination in a synthetic solution of concentrated PFAS mixtures and NaCl. We extended the discussion over molecular transformation mechanisms, development of PFAS degradation technologies, and the fate of iodine species.

Nanoplastics (<1000 nm) have been evidenced to be universal in a variety of environmental media. They pose a potential cytotoxicity and health risk due to their tiny size, which allows them to easily penetrate biological barriers and enter cells. Here, we briefly review the various prevalent analytical techniques or tools for identifying nanoplastics, and further move to focus on their advantages and disadvantages. Surface-enhanced Raman spectroscopy (SERS) has been implemented for the identification of individual nanoparticles because of its high sensitivity to molecules and ease of rapid characterization. Therefore, we introduce the SERS technique in the following aspects, (1) principles of SERS; (2) strategies and advances in SERS detection of nanoplastics; and (3) applying SERS to real environmental samples. We put our effort into the summarization of efficient SERS substrates that essentially enable the better detection of nanoplastics, and extend to discuss how the reported nanoplastics pretreatment methodologies can bring SERS analysis to practical applications. A further…

Abstract Some infectious diseases, including COVID-19, can be transmitted via aerosols that are emitted by an infectious person and inhaled by susceptible individuals. Most airborne transmission occurs at close proximity and is effectively reduced by physical distancing, but as time indoors increases, infections occur in those sharing room air despite maintaining distancing. There have been calls for quantified models to estimate the absolute and relative contribution of these different factors to infection risk. We propose two indicators of infection risk for this situation, i.e., relative risk parameter (H r ) and risk parameter (H). They combine the key factors that control airborne disease transmission indoors: virus-containing aerosol generation rate, breathing flow rate, masking and its quality, ventilation and particulate air cleaning rates, number of occupants, and duration of exposure. COVID-19 outbreaks show a clear trend in relation to these factors that is consistent with airborne infection The observed trends of outbreak size (attack rate) vs. H (H r ) allow us to…

Pregnancy and infancy are vulnerable times for detrimental environmental exposures. However, the exposure situation of microplastics (MPs) for mother-infant pairs and the adverse health effect of MPs are largely unknown. Therefore, we explored MP exposure in placentas and meconium samples, and the potential correlation of MP exposure with microbiota in placentas and meconium. A total of 18 mother-infant pairs were effectively recruited from Shanghai, China. The study required pregnant women to provide placentas and meconium samples. An Agilent 8700 laser infrared imaging spectrometer (LDIR) was applied to identify MPs. Microbiota detection was identified by 16S rRNA sequencing. Sixteen types of MPs were found in all matrices, and polyamide (PA) and polyurethane (PU) were the major types we identified. MPs detected in samples with a size of 20-50 μm were more than 76.46%. At the phylum level, both placenta and meconium microbiota were mainly composed of Proteobacteria, Bacteroidota, and Firmicutes. We also found some significant differences between placenta and meconium microbiota in…

The severe hazard of chlorinated volatile organic compounds (CVOCs) to human health and the natural environment makes their abatement technology a key topic of global environmental research. Due to the existence of Cl, the byproducts of CVOCs in the catalytic combustion process are complex and toxic, and the possible generation of dioxin becomes a potential risk to the environment. Well-qualified CVOC catalysts should process favorable low-temperature catalytic oxidation ability, excellent selectivity, and good resistance to poisoning, which are governed by the reasonable adjustment of acidity and redox properties. This review overviews the application of different types of multicomponent catalysts, that is, supported noble metal catalysts, transition metal oxide/zeolite catalysts, composite transition metal oxide catalysts, and acid-modified catalysts, for CVOC degradation from the perspective of balance between acidity and redox properties. This review also highlights the synergistic degradation of CVOCs and NO x from the perspective of acidity and redox properties. We expect this…

Abstract Selective removal of organic pollutants by advanced oxidation methods has been receiving increasing attention for environmental remediation. In this study, a novel catalyst, which can selectively oxidize phenolic compounds (PCs) based on their hydrophobicity, composed of metal–organic-framework-derived Fe/Fe3O4 and three-dimensional reduced graphene oxide (rGOF) is designed for peroxydisulfate (PDS) activation. This heterogeneous PDS activation system can completely degrade hydrophobic PCs within 30 min. By investigating the hydrophobic properties of eight representative PCs, a positive correlation between the hydrophobicity of PC and the reaction kinetics is reported for the first time. The selective removal stems from the strong interaction between highly hydrophobic PCs and the catalyst. Moreover, the mechanism investigation shows that the degradation reaction is triggered by interface reactive oxygen species (ROS). Our study reveals that the selective degradation of organic pollutants by PDS activation depends on the hydrophilic and hydrophobic properties of the…

Abstract The redox behavior of metal active sites determines the rate of heterogeneous catalysis in peroxymonosulfate activation. Previous reports focused on the construction of catalysts for accelerating interfacial electron transfer. In this work, a new strategy was proposed for facilitating valence cycles of Cu+/Cu2+ by using pollutants. The 2.5Cu/CeO2/PMS system was capable of achieving the efficient removal of pollutants, including tetracycline, oxytetracycline, and rhodamine B, in a wide pH working range. In the presence of tetracycline, a Cu–N bond was formed between the −NH2 group of tetracycline and the Cu site of the catalyst, showing that the coordination of Cu active sites changed to CuO4N1. The charge of CuO4N1 active sites rearranged, making it easier to obtain electrons and promote the PMS oxidation, thereby accelerating the reduction of Cu2+ to Cu+ and PMS activation. The PMS activation system showed excellent sustainability and selectivity for the removal of organic pollutants. This study provides a novel routine to promote peroxymonosulfate activation by utilizing…

Room-temperature molecular oxygen (O 2 ) dissociation is challenging toward chemical reactions due to its triplet ground-state and spin-forbidden characteristic. Herein, we demonstrate that BiOCl of oxygen and chlorine dual vacancies can photocatalytically dissociate O 2 into monatomic reactive oxygen (•O – ) for the ring opening of aromatic refractory pollutants toward deep oxidation. The electron-rich and geometry-flexible dual vacancies of oxygen and chlorine remarkably lengthen the O–O bond of adsorbed O 2 from 1.21 to 2.74 Å, resulting in the rapid O 2 dissociation and the subsequent •O – formation. During the photocatalytic degradation of sulfamethazine, the in situ -formed •O – plays an indispensable role in breaking the critical intermediate of pyrimidine containing a stubborn aromatic heterocyclic ring, thus facilitating the overall mineralization. More importantly, BiOCl of oxygen and chlorine dual vacancies is also superior to its monovacancy counterparts on the degradation of other refractory pollutants containing conjugated six-membered rings, including p -chlorophenol,…