Catalytic degradation of chlorinated volatile organic compounds (CVOCs) over Ce-Mn-Ti composite oxide catalysts.

Developing industrially moldable catalysts with harmonized redox performance and acidity is of great significance for the efficient disposal of chlorinated volatile organic compounds (CVOCs) in actual exhaust gasses. Here, commercial TiO2, typically used for molding catalysts, was chosen as the carrier to fabricate a series of Ce0.02Mn0-0.24TiOx materials with different Mn doping ratios and employed for chlorobenzene (CB) destruction. The introduction of Mn remarkedly facilitated the synergistic effect of each element via the electron transfer processes: Ce3++Mn4+/3+↔Ce4++Mn3+/2+ and Mn4+/3++Ti4+↔Mn3+/2++Ti3+. These synergistic interactions in Ce0.02Mn0.04-0.24TiOx, especially Ce0.02Mn0.16TiOx, significantly elevated the active oxygen species, oxygen vacancies and redox properties, endowing the superior catalytic oxidation of CB. When the Mn doping amount increased to 0.24, a separate Mn3O4 phase appeared, which in turn might weaken the synergistic effect. Furthermore, the acidity of Ce0.02Mn0.04-0.24TiOx was decreased with the Mn doping, regulating the balance of redox property and acidity. Notably, Ce0.02Mn0.16TiOx featured relatively abundant B-acid sites. Its coordinating redox ability and moderate acidity promoted the deep oxidation of CB and RCOOH- intermediates, as well as the rapid desorption of Cl species, thus obtaining sustainable reactivity. In comparison, CeTiOx owned the strongest acidity, however, its poor redox property was not sufficient for the timely oxidative decomposition of the easier adsorbed CB, resulting in its rapid deactivation. This finding provides a promising strategy for the construction of efficient commercial molding catalysts to decompose the industrial-scale CVOCs.

Insights into Chlorobenzene Catalytic Oxidation over Noble Metal Loading {001}-TiO2: The Role of NaBH4 and Subnanometer Ru Undergoing Stable Ru0↔Ru4+ Circulation.

Catalytic combustion of ubiquitous chlorinated volatile organic compounds (CVOCs) encounters bottlenecks regarding catalyst deactivation by chlorine poisoning and generation of toxic polychlorinated byproducts. Herein, Ru, Pd, and Rh were loaded on {001}-TiO2 for thermal catalytic oxidation of chlorobenzene (CB), with Ru/{001}-TiO2 representing superior reactivity, CO2 selectivity, and stability in the 1000 min on-stream test. Interestingly, both acid sites and reactive active oxygen species (ROS) were remarkably promoted via adding NaBH4. But merely enhancing these active sites of the catalyst in CVOC treatment is insufficient. Continuous deep oxidation of CB with effective Cl desorption is also a core issue successfully tackled through the steady Ru0↔Ru4+ circulation. This circulation was facilitated by the observed higher subnanometer Ru dispersion on {001}-TiO2 than the other two noble metals that was supported by single atom stability DFT calculation. Nearly 88 degradation products in off-gas were detected, with Ru/{001}-TiO2 producing the lowest polychlorinated benzene byproducts. An effective and sustainable CB degradation mechanism boosted by the cooperation of NaBH4 enhanced active sites and Ru circulation was proposed accordingly. Insights gained from this study open a new avenue to the rational design of promising catalysts for the treatment of CVOCs.

Source apportionment and risk assessment for polycyclic aromatic hydrocarbons in soils at a typical coking plant.

Polycyclic aromatic hydrocarbons (PAHs) are widely present in the environment. The coking industry is an important industrial source of PAHs. Coke production in China accounts for 67.44% of total global coke production. Tangshan, a coastal city on the Bohai Rim, contains the largest cluster of coking plants in China. Extremely high PAH emissions in Tangshan may cause long-distance cross-border pollution problems. In this study, the concentrations and sources of 16 priority PAHs in soil at a coking plant in Tangshan were determined and the risks posed by the PAHs were assessed. The PAH concentrations were generally higher in surface soil than subsurface soil, particularly near the coke oven, crude benzol, and coal blending areas. The dibenz[a,h]anthracene (DBA) concentrations were higher than the risk screening value (1500 ngg-1) but lower than the control value (15,000 ngg-1) for type II land defined in Chinese standard (GB36600-2018). The main sources of PAHs were coal combustion, the coke oven, and traffic. The PAH concentrations were higher in the ammonium sulfate, boiler room, coal blending, and coke oven areas than in the other areas. Toxic equivalent concentrations were calculated to assess the toxic and carcinogenic risks posed by PAHs. The toxic equivalent concentrations were relatively high in the boiler, crude benzol, and coal blending areas, where the toxic equivalent concentrations for the sums of seven highly carcinogenic PAHs contributed 95% of the toxic equivalent concentrations for the sums of the 16 PAHs that were analyzed. The carcinogenic risks posed to humans were therefore assessed using the concentrations of the seven highly carcinogenic PAHs. Dermal contact was found to be an important exposure pathway leading to carcinogenic risks. The carcinogenic risk posed by DBA was > 1 × 10-6 but < 5 × 10-6, indicating that DBA concentrations at the study site monitored closely.

Environmental impact and health risk assessment of volatile organic compound emissions during different seasons in Beijing.

Volatile organic compounds (VOCs) are major contributors to air pollution. Based on the emission characteristics of 99 VOCs that daily measured at 10 am in winter from 15 December 2015 to 17 January 2016 and in summer from 21 July to 25 August 2016 in Beijing, the environmental impact and health risk of VOC were assessed. In the winter polluted days, the secondary organic aerosol formation potential (SOAP) of VOC (199.70 ± 15.05 µg/m3) was significantly higher than that on other days. And aromatics were the primary contributor (98.03%) to the SOAP during the observation period. Additionally, the result of the ozone formation potential (OFP) showed that ethylene contributed the most to OFP in winter (26.00% and 27.64% on the normal and polluted days). In summer, however, acetaldehyde was the primary contributor to OFP (22.00% and 21.61% on the normal and polluted days). Simultaneously, study showed that hazard ratios and lifetime cancer risk values of acrolein, chloroform, benzene, 1,2-dichloroethane, acetaldehyde and 1,3-butadiene exceeded the thresholds established by USEPA, thereby presenting a health risk to the residents. Besides, the ratio of toluene-to-benzene indicated that vehicle exhausts were the main source of VOC pollution in Beijing. The ratio of m-/p-xylene-to-ethylbenzene demonstrated that there were more prominent atmospheric photochemical reactions in summer than that in winter. Finally, according to the potential source contribution function (PSCF) results, compared with local pollution sources, the spread of pollution from long-distance VOCs had a greater impact on Beijing.

Emission characteristics of 99 NMVOCs in different seasonal days and the relationship with air quality parameters in Beijing, China.

In recent years, the haze incidents have occurred frequently in China. Therefore, more attention should be taken in comprehensively determination and analysis of the extended-ranges of volatile organic compounds (VOCs). Here, up to 99 non-methane VOCs (NMVOCs), including not frequently reported partial halocarbons and oxygenated VOC (OVOC) species, were monitored in atmosphere of Beijing. The mean concentration of total NMVOC (TNMVOC) decreased in the order of winter polluted days (216.05 µg m-3) > summer polluted days (127.01 µg m-3) > summer normal days (95.63 µg m-3) > winter normal days (50.25 µg m-3). The ethane to n-butane, ethylene to 1-butene, BTEX, acetaldehyde, acetone, n-hexanal, dichloromethane, chloroform and 1,2-dichloroethane, were determined to be the main composition in their respective alkane, alkene, aromatic, OVOC and halocarbon classes. The minor propylbenzene, diethylbenzene, ethyltoluene, and trimethylbenzene isomer ratios were within the narrow range of 1.3-3.21. Generally, the most abundant NMVOCs were alkanes in winter but OVOCs in summer. TNMVOC significantly positively correlated with PM10, PM2.5, CO, RH, SO2 (winter), NO2 (winter), but negatively with windspeed, SSD and PRS (winter). The opposite correlation was observed between TNMVOC and O3 in winter and summer. There was no meaningful correlation between TNMVOC and T, PRS (summer), SO2 (summer) and NO2 (summer). 3D surface graphs, built by MATLAB, were drawn to investigate the relationship between PM2.5 and NMVOC taking air quality parameters into account. The PM2.5 concentration increased non-linearly as TNMVOC concentration increased, with various surface graphs. Unlike other air quality parameters, O3 affected the relationship differently between winter and summer. The findings presented herein may provide a new train of thought for occurrence of haze.

The Regular/Persistent Free Radicals and Associated Reaction Mechanism for the Degradation of 1,2,4-Trichlorobenzene over Different MnO2 Polymorphs.

The role of regular/persistent free radicals on the catalytic activity of K+-tuned MnO2 tunnel structures is poorly understood to date. Herein, three MnO2 polymorphs (α-, ß-, and δ-MnO2) were synthesized and examined toward the degradation of 1,2,4-trichlorobenzene (1,2,4-TrCBz) at 300 °C. δ-MnO2, with a two-dimensional-layered tunnel structure tuned by K+, exhibited the highest activity among the three MnO2 polymorphs. The electron spin resonance spectroscopy results confirmed that δ-MnO2 featured the most abundant reactive oxygen species (ROS: O2-•, •OH, and 1O2), followed by α-MnO2 (O2-• and 1O2), and ß-MnO2 (O2-•), being supported by the calculated energy barrier. It was, intriguingly, noted that persistent organic free radicals, newly recognized as emerging surface-stabilized compound, were remarkably detected in α- and ß-MnO2/1,2,4-TrCBz systems but not in more reactive δ-MnO2/1,2,4-TrCBz system. These might contribute to discrepant oxidative degradation process. During the oxidative process, intermediates, including benzoic acid and glycerol, formed via attack by ROS. Upon further attack, these intermediates fragmented into smaller molecules such as formic, acetic, propionic, and butyric acids. The present findings give deeper insights into the role of free radicals on the catalytic degradation of chlorinated aromatics.

Distribution of polychlorinated naphthalenes (PCNs) in the whole blood of typical meat animals.

The concentrations and distribution of polychlorinated naphthalenes (PCNs) in the whole blood of eight typical terrestrial meat animals (chicken, duck, rabbit, pig, cattle, sheep, horse and donkey) consumed daily in our life were investigated. The total concentrations (on a liquid volume basis) of PCNs were in a range from 305 to 987pg/L. Donkey blood contained the highest PCN concentrations. Mono-CNs were the dominant homolog group, accounting for 38%-71% PCNs. Apart from the mono-CNs and tri-CNs homolog groups, two hepta-CNs (mean: 9.5%) contributed most, followed by tetra-CNs (mean: 6.5%). The congeners CN1, 5/7, 24/14, 27/30, 52/60, 66/67, and 73 were the most abundant congeners or congener groups. The highest toxicity equivalencies (TEQs) were observed in cattle blood (117.4fg TEQ/L) then chicken blood (117.1fg TEQ/L). CN73 contributed 65% to total TEQs, followed by CN70 (20%) and CN66/67 (14%). The dietary intakes of PCNs were also estimated. Chicken meat, which forms the second largest component of meat product consumption in China, contributed most to the total TEQs (61%), followed by beef (27%) and pork (5.9%). The consumption of chicken might pose the highest risk from exposure to PCNs than other types of meat to populations who prefer to eat chicken meat.

Thermal Oxidation Degradation of 2,2',4,4'-Tetrabromodiphenyl Ether over LiαTiOx Micro/Nanostructures with Dozens of Oxidative Product Analyses and Reaction Mechanisms.

Flowerlike LiαTiOx micro/nanostructures were successfully synthesized to degrade 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) at 250-350 °C. The pseudo-first-order kinetics rate constant of the reaction at 300 °C was in the range of 0.034-0.055 min-1. The activation energy was as low as 39.9-48.1 kJ/mol. The excellent performance attained over LiαTiOx was attributed to Li dopant having the electron-donating effect, which enhanced the oxygen species mobility. The oxidative reaction was believed to be the dominant degradation pathway following the Mars-van Krevelen mechanism, being accompanied by the weak hydrodebromination occurrence generating the trace mono- to tri-BDEs. More than 70 types of oxidation products containing diphenyl ether backbone, single-benzene rings, and ring-opened products were detected by GC-MS with derivatization, ESI-FT-ICR-MS, and ion chromatography. An increase in the number of ring-cracked oxidative products under prolonged reaction was observed by ESI-FT-ICR-MS analysis according to the van Krevelen diagram. In the oxidative reaction, a series of oxidative products, such as OH-tri-BDEs and OH-tetra-BDEs, first formed via the nucleophilic O2- attack and subsequently transformed into dibromophenol, tribromophenol, and benzenedicarboxylic and benzoic acids, etc. They could be further attacked by electrophilic O2- and O- and completely cracked to small molecules such as formic, acetic, propionic, and butyric acids.

Determination of hexabromocyclododecanes in sediments from the Haihe River in China by an optimized HPLC-MS-MS method.

Hexabromocyclododecanes (HBCDs), a new type of persistent organic pollutants widely used as brominated flame retardants, have attracted wide attention due to their increasing level and toxicity. A method based on high-performance liquid chromatography mass spectrometry (HPLC-MS-MS) in electrospray ionization mode has been developed by optimization of various parameters, which effectively improved the separation degree and responsive intensity of α-, ß- and γ-HBCD isomers. The concentrations and distribution profiles of three HBCD isomers were investigated in sediments from the Haihe River in China. It was observed that the concentrations of HBCDs varied in the range of 0.4-58.82ng/g, showing a decreasing trend along the flow direction, possibly due to attenuation and biodegradation along the flow direction of the Haihe River. The distribution profile of α-, ß-, γ-HBCD was 7.91%-88.6%, 0-91.47%, and 0.62%-42.83%, respectively. Interestingly, α-HBCD dominated in most sample sites. This was different from the distribution profile in commercial industrial products, which might be attributed to the inter-transformation and different degradation rates of the three HBCD isomers. The potential ecological risk of HBCDs in sediment was characterized under the two-tiered procedure of the European Medicines Evaluation Agency for environmental risk assessment. Although the HBCDs in the selected section of the Haihe River presented "no risk" in the sediment compartment, its risk in sediment cannot be neglected since sediment is one of the important sinks and reservoirs of pollutants.

Thermal degradation of octachloronaphthalene over as-prepared Fe(3)O(4) micro/nanomaterial and its hypothesized mechanism.

Decomposition of octachloronaphthalene (CN-75) featuring fully substituted chlorines was investigated over as-prepared Fe3O4 micro/nanomaterial at 300 °C. It conforms to pseudo-first-order kinetics with kobs = 0.10 min(-1) as comparable to that of hexachlorobenzene and decachlorobiphenyl. Analysis of the products indicates that the degradation of CN-75 proceeds via two competitive hydrodechlorination and oxidation pathways. The onset of hydrodechlorination producing lower chlorinated naphthalenes (CNs) is more favored on α-position than ß-position. Higher amounts of CN-73, CN-66/67, CN-52/60, and CN-8/11 isomers were found, while small content difference was detected within the tetrachloronaphthalene and trichloronaphthalene homologues, which might be attributed to lower energy principle and steric effects. The important hydrodechlorination steps, leading to CN-73 ≫ CN-74 in two heptachloronaphthalene isomers contrary to that in technical PCN-mixtures, were specified by calculating the charge of natural bond orbitals in CN-75 and the energy of two heptachloronaphthalene radicals. On the basis of the molecular electrostatic potential of CN-75, the nucleophilic O(2-), and eletrophilic O2(-) and O(-), present on the Fe3O4 surface, might attack the carbon atom and π electron cloud of naphthalene ring, producing naphthol species with Mars-van Krevelen mechanism, and formic and acetic acids.

Super-exchange interaction enables Fe2-xMnxO3 perovskite with excellent catalytic oxidation activity toward hexabromocyclododecane under humidity.

Although enhancing the catalytic oxidation activity is a hotspot in thermal-driven catalytic disposal of persistent organic pollutants, few studies have managed to improve catalysts' water-resistance properties. Herein, we developed Fe2-xMnxO3 perovskite to boost the catalytic oxidation of hexabromocyclododecane under humidity by modulating its super-exchange interaction (SEI, Fe3+ + Mn3+ → Fe2+ + Mn4+). Fe0.4Mn1.6O3, with the strongest SEI, exhibits the biggest oxidation rate-constant, which is 3 times higher than that of commonly used Fe2O3 without SEI. Notably, unlike Fe2O3 which deactivates at a relative humidity of 5 %. Fe0.4Mn1.6O3 maintains its activity and is even boosted by 22 % compared to dry conditions. Mechanistic insights reveal that SEI between Fe and Mn enhances the reactivity of Mn4+- linked Olatt by lowering the reductive temperature from Mn4+ to Mn3+. Meanwhile, SEI promotes the adsorption of the associatively adsorbed H2O (HOH-type water) by reducing adsorption energy, thereby facilitating the formation of hydroxyl species, which are crucial for the oxidation process under humidity.

Environmental occurrence, bioaccumulation and human risks of emerging fluoroalkylether substances: Insight into security of alternatives.

Per- and polyfluoroalkyl substances (PFASs) are widely used due to their unique structure and excellent performance, while also posing threats on ecosystem, especially long-chain perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). As the control of conventional PFASs, fluoroalkylether substances (ether-PFASs) as alternatives are constantly emerging. Subsequently, the three representative ether-PFASs, chlorinated polyfluoroalkyl ether sulfonic acid (F-53B), hexafluoropropylene oxide-dimer acid (HFPO-DA), and 4,8-Dioxa-3H-perfluorononanoicacid (ADONA) are discovered and have received more attention in the environment and ecosystem. But their security is now also being challenged. This review systematically assesses their security from six dimensions including environmental occurrence in water, soil and atmosphere, as well as bioaccumulation and risk in plants, animals and humans. High substitution level is observed for F-53B, whether in environment or living things. Like PFOS or even more extreme, F-53B exhibits high biomagnification ability, transmission efficiency from maternal to infant, and various biological toxicity effects. HFPO-DA still has a relatively low substitution level for PFOA, but its use has emerged in Europe. Although it is less detected in human bodies and has a higher metabolic rate than PFOA, the strong migration ability of HFPO-DA in plants may pose dietary safety concerns for humans. Research on ADONA is limited, and currently, it is detected in Germany frequently while remaining at trace levels globally. Evidently, F-53B has shown increasing risk both in occurrence and toxicity compared to PFOS, and HFPO-DA is relatively safe based on available data. There are still knowledge gaps on security of alternatives that need to be addressed.

Which pollutants and sources should be prioritized for control in multi-pollutants complex contaminated areas?

Risk assessment and source identification of multi-pollutants are essential for accurate control of soil contamination. However, complexity in pollutant properties and diversity in source types raise challenges to the target. Therefore, this study constructed a hierarchical ecological risk quantification method combined with risk ranking, risk of single pollutant using potential affected fraction (PAF), and joint risk of multi-pollutants employing msPAF. Taking regional contamination in South China as a case, the risk ranking was determined, while single and joint effects showed msPAF reaching 79.4 %, with risk as heavy metals (HMs) > per- and polyfluoroalkyl substances (PFASs) > polycyclic aromatic hydrocarbons (PAHs). Meanwhile, an integrated source apportionment method was established from three layers by principal component analysis to classify source types, multiple linear regression of distance to identify key sources, and positive matrix factorization to track omitted sources. Consequently, key sources were captured, with 80.8 %-93.2 % contribution of farmland and electroplating to three main HMs, 52.2 %-69.4 % contribution of roads to three main PAHs, and 71.1 %-73.2 % contribution of electroplating to two main PFASs. Further, omitted sources were tracked with contribution of 31.2 %-84.1 % to eight pollutants. The established methods can identify control targets, including high-risk pollutants and their key sources.

Occurrence and risks of PPCPs of a typical mountainous region: Implications for sustainable urban water systems.

Urban wastewater treatment plants (WWTPs) and drinking water treatment plants (DWTPs) play vital roles in the urban water cycle, ensuring access to safe drinking water and maintaining aquatic ecosystems. This study comprehensively assessed the occurrence and risks of pharmaceuticals and personal care products (PPCPs) in urban WWTPs and DWTPs. Our findings revealed widespread PPCPs presence, with concentrations ranging from <1 ng/L to several thousand ng/L. Significant regional disparities in occurrence and composition were observed linked to population types and economic structures. Furthermore, strong correlations were observed between DWTPs and WWTPs indicating consistent transport and transformation patterns of PPCPs within the urban water cycle. Approximately two-thirds of PPCPs were degraded post-WWTP treatment, with about one-tenth persisting in drinking water following surface water dilution and purification processes. Thus, we suggested that controlling the total concentration of the five priority PPCPs in the effluent from the WWTP to <1100 ng/L have potential to reduce the environmental and health risk of PPCPs. Additionally, this research identified influential water quality parameters, such as pH, dissolved oxygen, and temperature, through redundancy analysis. This research underscores the importance of establishing emission standards to mitigate PPCP-related risks and supports sustainable urban water system advancement.

Recognition of screening out hierarchical toxic contaminants tuned by quantified pseudo-components from complex engineering co-combustion.

Co-combustion of industrial and municipal solid wastes has emerged as the most promising disposal technology, yet its effect on unknown contaminants generation remains rarely revealed due to waste complexity. Hence, six batches of large-scale engineering experiments were designed in an incinerator of 650 t/d, which overcame the inauthenticity and deviation of laboratory tests. 953-1772 non-targeted compounds were screened in fly ash. Targeting the impact of co-combustion, a pseudo-component matrix model was innovatively integrated to quantitatively extract nine components from complex wastes grouped into biomass and plastic. Thus, the influence was evaluated across eight dimensions, covering molecular characteristics and toxicity. The effect of co-combustion with biomass pseudo-components was insignificant. However, co-combustion with high ratios of plastic pseudo-components induced higher potential risks, significantly promoting the formation of unsaturated hydrocarbons, highly unsaturated compounds (DBE≥15), and cyclic compounds by 19 %- 49 %, 17 %- 31 %, and 7 %- 27 %, respectively. Especially, blending with high ratios of PET plastic pseudo-components produced more species of contaminants. Unique 2 Level I toxicants, bromomethyl benzene and benzofuran-2-carbaldehyde, as well as 4 Level II toxicants, were locked, receiving no concern in previous combustion. The results highlighted risks during high proportion plastics co-combustion, which can help pollution reduction by tuning source wastes to enable healthy co-combustion.

Metagenomic surveillance of antibiotic resistome in influent and effluent of wastewater treatment plants located on the Qinghai-Tibetan Plateau.

As hotspots for the dissemination of antibiotic resistance genes (ARGs), wastewater treatment plants (WWTPs) have attracted global attention. However, there lacks a sufficient metagenomic surveillance of antibiotic resistome in the WWTPs located on the Qinghai-Tibet Plateau. Here, metagenomic approaches were used to comprehensively investigate the occurrence, mobility potential, and bacterial hosts of ARGs in influent and effluent of 18 WWTPs located on the Qinghai-Tibet Plateau. The total ARG relative abundances and diversity were significantly decreased from influent to effluent across the WWTPs. Multidrug, bacitracin, sulfonamide, aminoglycoside, and beta-lactam ARGs generally consisted of the main ARG types in effluent samples, which were distinct from influent samples. A group of 72 core ARGs accounting for 61.8-95.8 % of the total ARG abundances were shared by all samples. Clinically relevant ARGs mainly conferring resistance to beta-lactams were detected in influent (277 ARGs) and effluent (178 ARGs). Metagenomic assembly revealed that the genetic location of an ARG on a plasmid or a chromosome was related to its corresponding ARG type, demonstrating the distinction in the mobility potential of different ARG types. The abundance of plasmid-mediated ARGs accounted for a much higher proportion than that of chromosome-mediated ARGs in both influent and effluent. Moreover, the ARGs co-occurring with diverse mobile genetic elements in the effluent exhibited a comparable mobility potential with the influent. Furthermore, 137 metagenome-assembled genomes (MAGs) assigned to 13 bacterial phyla were identified as the ARG hosts, which could be effectively treated in most WWTPs. Notably, 46 MAGs were found to carry multiple ARG types and the potential pathogens frequently exhibited multi-antibiotic resistance. Some ARG types tended to be carried by certain bacteria, showing a specific host-resistance association pattern. This study highlights the necessity for metagenomic surveillance and will facilitate risk assessment and control of antibiotic resistome in WWTPs located on the vulnerable area.

Application of a hybrid GEM-CMB model for source apportionment of PAHs in soil of complex industrial zone.

Accurate source apportionment is essential for preventing the contamination of pervasive industrial zones. However, a limitation of traditional receptor models is their negligence of transmission loss, which consequently reduces their accuracy. Herein, chemical mass balance (CMB) and generic environmental model (GEM) was fused into a new method, which was employed to determine the traceability of polycyclic aromatic hydrocarbons (PAHs) in a complex zone containing three coking plants, two steel plants, and one energy plant. Five categories of fingerprints comprising various compounds were established for the six plant sources where seven PAHs with low-high rings were screened as the best. Considering volatilization, dry deposition, and advective and dispersive transport, the GEM model generated 232 "compartments" in multimedia to capture subtle variations of PAHs during transmission. More than 90 % of the transmission of the seven PAHs varied between 0.4 % and 6.0 %. Over pure CMB model, acceptable results and best-fit results improved by 1.6-44.4 % and 0.3-80.8 % in the GEM-CMB model. Additionally, the coking, steel, and energy industries accounted for 36.4-56.1 %, 25.6-41.7 %, and 18.3-23.6 % of PAHs sources at four receptor points, respectively. Furthermore, quantifying contaminant loss rendered the traceability results more realistic, judged by distances and discharge capacities. Accordingly, these outcomes can help in precisely determining soil contamination.

Scientific and regulatory challenges of environmentally persistent free radicals: From formation theory to risk prevention strategies.

EPFRs (Environmentally Persistent Free Radicals) are a class of pollutants that have been identified as potential environmental contaminants due to their persistence and ability to generate reactive oxygen species (ROS) that can cause oxidative stress in living organisms. However, no study has comprehensively summarized the production conditions, influencing factors and toxic mechanisms of EPFRs, impeding exposure toxicity assessments and risk prevention strategies. To bridge the gap between theoretical research and practical application, a thorough literature review to summarize the formation, environmental effects, and biotoxicity of EPFRs are conducted. A total of 470 relevant papers were screened in Web of Science Core collection databases. The transfer of electrons between interfaces and the cleavage of covalent bonds of persistent organic pollutants is crucial to the generation of EPFRs, which is induced by external sources of energy, including thermal energy, light energy, transition metal ions, and others. In the thermal system, the stable covalent bond of organic matter can be destroyed by heat energy at low temperature to form EPFRs, while the formed EPFRs can be destroyed at high temperature. Light can also accelerate the production of free radicals and promote the degradation of organic matter. The persistence and stability of EPFRs are synergistically influenced by individual environmental factors such as environmental humidity, oxygen content, organic matter content, and environmental pH. Studying the formation mechanism of EPFRs and their biotoxicity is essential for fully understanding the hazards posed by these emerging environmental contaminants.

Ecological risks induced by consumption and emission of Pharmaceutical and personal care products in Qinghai-Tibet Plateau: Insights from the polar regions.

As the third pole of the world and Asia's water tower, the Tibetan Plateau experiences daily release of pharmaceutical and personal care products (PPCPs) due to increasing human activity. This study aimed to explore the potential relationship between the concentration and composition of PPCPs and human activity, by assessing the occurrence of PPCPs in areas of typical human activity on the Qinghai-Tibet Plateau and evaluating their ecological risk. The results indicate that 28 out of 30 substances were detected in concentrations ranging from less than 1 ng/L to hundreds of ng/L, with the average concentration of most PPCPs in the Tibet Autonomous Region being higher than that in Qinghai Province. Among the detected substances, CAF, NOR, CTC, CIP, TCN, OTC, AZN, and DOX accounted for over 90% of the total concentration. The emission sources of PPCPs were identified by analyzing the correlation coefficients of soil and water samples, with excess PPCPs used by livestock breeding discharged directly into soil and then into surface water through leaching or runoff. By comparing the concentration and composition of PPCPs with those in other regions, this study found that CIP, ENR, LOM, NOR, CTC, DOX, OTC, and TCN were the most commonly used PPCPs in the Qinghai-Tibet Plateau. To assess the ecological risk of PPCPs, organisms at different trophic levels, including algae, crustaceans, fish, and insects, were selected. The prediction of the no effect concentration of each PPCP showed that NOR, CTC, TCN, CAF, and CBZ may have deleterious effects on water biota. This study can assist in identifying the emission characteristics of PPCPs from different types and intensities of human activities, as well as their occurrence and fate during the natural decay of aquatic systems.

New insights into the distribution, potential source and risk of microplastics in Qinghai-Tibet Plateau.

Microplastics (MPs) as emerging contaminants have become a major global concern, however, the distribution and origin of MPs in Qinghai-Tibet Plateau (QTP) and their impacts on ecosystem are poorly known. Hence, we systematically evaluated the profile of MPs on the representative metropolitan locations of Lhasa and Huangshui Rivers and the scenic sites of Namco and Qinghai Lake. The average abundance of MPs in the water samples was 7020 items/m3, which was 34 and 52 times higher than those for the sediment (206.7 items/m3) and soil samples (134.7 items/m3), respectively. Huangshui River had the highest levels, followed by Qinghai Lake, Lhasa River and Namco. Human activities rather than altitude and salinity impacted the distribution of MPs in those areas. Besides the consumption of plastic products by locals and tourists, laundry wastewater and exogenous tributary inputs, the unique prayer flag culture also contributed to the MPs emission in QTP. Notably, the stability and fragment of MPs were crucial for their fate. Multiple assessment models were employed to evaluate the risk of MPs. PERI model took MP concentration, background value and toxicity into account, comprehensively describing the risk differences of each site. The large PVC proportion in Qinghai Lake posed the highest risk. Furthermore, concerns should be raised about PVC, PE and PET in Lhasa and Huangshui Rivers, and PC in Namco Lake. Risk quotient suggested that aged MPs in sediments slowly released biotoxic DEHP and should be cleaned up promptly. The findings offer baseline data of MPs in QTP and ecological risks, providing important support for the prioritization of future control measures.