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Autonomous driving technology is considered the trend of future transportation. Millimeter-wave radar, with its ability for long-distance detection and all-weather operation, is a key sensor for autonomous driving. The development of various technologies in autonomous driving relies on extensive simulation testing, wherein simulating the output of real radar through radar models plays a crucial role. Currently, there are numerous distinctive radar modeling methods. To facilitate the better application and development of radar modeling methods, this study first analyzes the mechanism of radar detection and the interference factors it faces, to clarify the content of modeling and the key factors influencing modeling quality. Then, based on the actual application requirements, key indicators for measuring radar model performance are proposed. Furthermore, a comprehensive introduction is provided to various radar modeling techniques, along with the principles and relevant research progress. The advantages and disadvantages of these modeling methods are evaluated to determine their characteristics. Lastly, considering the development trends of autonomous driving technology, the future direction of radar modeling techniques is analyzed. Through the above content, this paper provides useful references and assistance for the development and application of radar modeling methods.
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Polybrominated dibenzofurans (PBDFs) are characteristic dioxin-like products of polybrominated diphenyl ether (PBDE) photolysis. In this study, competition mechanisms of radical-based cyclization and hydrogen abstraction reactions are proposed in PBDF formation. Commonly, the ortho C-Br bond dissociation during photolysis generates aryl radicals, which undergo intramolecular cyclization to form PBDFs or hydrogen abstraction with hydrogen donors (such as organic solvents and water) to form lower brominated PBDEs. By using 2,4,4'-tribromodiphenyl ether (BDE-28) as the model reactant, the experimental PBDF formation ratios in various solutions are explained quantitatively by the calculated rate constants of cyclization and hydrogen abstraction reactions using the density functional theory (DFT) method. The solvent effect of pure and mixed solvents on PBDF formation is illustrated successfully. The structure-related hydrogen donation ability for hydrogen abstraction controls the bias of competition reactions and influences PBDF formation. Water resulted to be the most significant generation of PBDFs. Fulvic and humic acid display higher hydrogen donation ability than small-molecule organics due to the partitioning effect in aqueous solution. Quantitative structure-activity relationship (QSAR) models of the calculated rate constants for 512 cyclization and 319 hydrogen abstraction reactions using 189 PBDEs as the initial reactants in water are established, revealing the high risk of PBDF formation in aqueous solution.
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Éteres Difenil Halogenados , Água , Éteres Difenil Halogenados/química , Fotólise , Ciclização , Solventes , Água/químicaRESUMO
Although the mining area has been restored, the environmental problems caused by years of large-scale oil shale mining are still continuing, coupled with the intensive distribution of the surrounding petrochemical industry, posing a serious threat to the local ecological environment. In this study, we investigated eight heavy metals (Cu, Ni, Pb, Cd, As, Cr, Mn and Zn) contamination and distribution around mining area, evaluated the potential risks of environment, identified the main sources of metal pollution and performed source apportionment. The results showed that the original north and south dumps were seriously polluted, and the CF values were significantly higher than other sampling sites. Ni, Zn and Mn have high coefficients of variation, which may be greatly affected by human factors and especially the waste slag piled up. The concentration of heavy metals in the water was lower than in the soil; soil particles, pH, Eh and acid mine drainage influence the variation of heavy metal concentrations. As and Cd have very high RAC values, and accordingly they were mainly present in the exchangeable and reduced fractions. Mn was exposed to higher ecological risks, followed by Pb, although there were high loads on carbonate bound and oxidizable fractions. APCS-MLL receptor model was used to identify and apportionment three main sources of contamination. The mean contribution rates of industrial activity, atmospheric deposition and mixed sources accounted for 39.77%, 22.24% and 37.99%, respectively. Cluster analysis further classified the metal pollution sources according to the spatial distance of sampling points.
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Metais Pesados , Poluentes do Solo , China , Monitoramento Ambiental , Humanos , Metais Pesados/análise , Mineração , Medição de Risco , Solo , Poluentes do Solo/análiseRESUMO
Harmful Phaeocystis blooms disrupt seawater recreation and pose serious challenges to aquatic animals. The growth performance, phenotypic traits, and antioxidant responses of Brachionus plicatilis Müller to different proportions of Phaeocystis globosa were evaluated. B. plicatilis rotifers were exposed to cultures with Chlorella sp. and P. globosa alone and in mixtures of these two algae with proportions of 25%, 50%, and 75%. The total proportions of the two algae were maintained at 100%. Results showed that P. globosa inhibited the rotifer net reproduction rate, intrinsic growth rate, and finite rate of increase (P < 0.01). It induced the formation of defense phenotypic traits in terms of the increased posterolateral spine length and the reduced body length, swimming speed, and grazing rate of B. plicatilis (P < 0.001). Superoxide dismutase and catalase activities decreased, but the reactive oxygen species levels increased as the proportions of P. globosa increased (P < 0.01). The mixture of 50% Chlorella and 50% Phaeocystis positively affected the glutathione content, glutathione peroxidase activity, and generation time of rotifers (P < 0.01). Although P. globosa released toxicants with harmful effects on the growth performance of B. plicatilis, rotifers changed their antioxidant defense system and formed defense phenotypic traits in response to eutrophic conditions.
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Antioxidantes/metabolismo , Haptófitas/crescimento & desenvolvimento , Proliferação Nociva de Algas , Rotíferos/crescimento & desenvolvimento , Animais , Chlorella/crescimento & desenvolvimento , Glutationa/metabolismo , Fenótipo , Espécies Reativas de Oxigênio/metabolismo , Rotíferos/metabolismo , Rotíferos/fisiologia , Água do Mar/química , NataçãoRESUMO
Organophosphorus esters (OPEs), as one kind of emerging and toxic contaminant are ubiquitous in various environments. This study investigated the degradation of tris(2-chloroethyl) phosphate (TCEP) as a category OPEs by pyrite (FeS2)-activated persulfate (PS). The result shows that near-100% degradation of TCEP was achieved after 120â¯min in FeS2-PS system. The important role of Fe2+ in the activation mechanism was confirmed by the introduction of Fe2+ into the PS only system. Radical scavengers experiment and electron paramagnetic resonance (EPR) confirmed the presence of SO4·- and ·OHï¼which revealed that ·OH and SO4·- played major roles in TCEP degradation. The effect of various environmental factors, including pyrite and oxidant dosage, inorganic ions and pH were investigated. The result indicated that Fe3+ and Cl- can accelerate the degradation rate of TCEP and the reaction between TCEP and FeS2-PS favors acidic conditions (pH>9). In addition, due to the acidification of pyrite, this system can be applied with a wide pH range. Besides, two oxidation products, C4H9Cl2O4P and C2H6ClO4P were identified, which suggest that hydroxylation was probably the main mechanism. This study greatly improves our understanding on TCEP removal in FeS2-PS system.
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Ferro/química , Fosfinas/química , Sulfatos/química , Sulfetos/química , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/química , Hidroxilação , Oxirredução , Fosfinas/isolamento & purificação , Água/química , Purificação da ÁguaRESUMO
Advanced oxidation processes (AOPs), such as hydroxyl radical (â¢OH) and sulfate radical (â¢SO4-) mediated oxidation, are proved to be effective methods to remove the organophosphorus esters (OPEs) in wastewater effluents. However, few studies have reported about the bimolecular reaction rate constants between free radicals (â¢OH and â¢SO4-) and OPEs. This issue was solved by selecting three OPEs as model compounds, the oxidation of these OPEs in UV/H2O2 and UV/K2S2O8 process were studied. Tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), and tris(2,3-dichloropropyl) phosphate (TDCPP) can hardly be oxidized through direct irradiation methods using UV lamp, with the oxidation rate less than 30% after 7â¯h' irradiation. However, TCEP, TCPP, and TDCPP undergo degradation via UV/H2O2 and UV/K2S2O8 processes easily, the oxidation rates increased with increasing H2O2 and K2S2O8 dosage. The oxidation rates of three OPEs have been studied using competition experiments in the UV/H2O2 and UV/K2S2O8 processes. The bimolecular reaction rate constants of TCEP, TCPP and TDCPP with â¢OH were 2.50â¯×â¯1010, 3.95â¯×â¯1010 and 2.94â¯×â¯1010 respectively; while â¢SO4- were 3.00â¯×â¯107, 1.82â¯×â¯107 and 2.06â¯×â¯107 respectively. Results showed that the simplified kinetic model involves only steady state concentration of free radicals and the molecular reaction rate contents are available for calculating the oxidation rates of OPEs in ultrapure water.
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Peróxido de Hidrogênio/química , Radical Hidroxila/química , Organofosfatos/análise , Sulfatos/química , Raios Ultravioleta , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Ésteres , Cinética , Organofosfatos/efeitos da radiação , Oxirredução , Águas Residuárias/química , Poluentes Químicos da Água/efeitos da radiaçãoRESUMO
In this study, we have investigated the photolysis of 2,4,4'-tribromophenylphenyl ether (BDE-28) in Triton X-100 (TX-100) solutions, and discussed the effect of anthraquinone-2,6-disulfonate (AQDS) on the photolysis of BDE-28. The effect of TX-100 on the photolysis of BDE-28 was mainly related to the concentration of TX-100. The fastest photolysis of BDE-28 was at 500 mg L-1 of the TX-100 solution, and the corresponding photolysis rate constant was 0.12 min-1. The direct photolysis rate of BDE-28 decreased from 0.17 min-1 to 0.08 min-1 and 0.12 min-1 when NaN3 and isopropanol were added, respectively. The effect of AQDS on the photolysis of BDE-28 was also mainly related to the concentration of AQDS. When the concentration of AQDS was 0.6 µM, it has a slight influence in promoting the photodegradation of BDE-28; as the AQDS concentrations increased, the suppressing effect was more obvious. AQDS can inhibit the photolysis of BDE-28. Photolysis kinetics and quenching reactions illustrated that BDE-28 can produce a photosensitization reaction in TX-100 solutions, and the effects of AQDS on the photolysis of BDE-28 were mainly dominated by inhibition. In addition to its light shielding effect, AQDS can also combine with BDE-28 and anti-oxidation to inhibit the photolysis of BDE-28. We found that the degradation pathway of BDE-28 was mainly based on de-bromination, and the ions at para positions were preferentially debrominated.
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Non-targeted screening (NTS) methods are integral in environmental research for detecting emerging contaminants. However, their efficacy can be influenced by variations in hydrophilic-lipophilic balance (HLB) solid phase extraction (SPE) cartridges and high-resolution mass spectrometry (HRMS) instruments across different laboratories. In this study, we scrutinized the influence of five HLB SPE cartridges (Nano, Weiqi, CNW, Waters, and J&K) and four LC-HRMS platforms (Agilent, Waters, Thermo, and AB SCIEX) on the identification of emerging environmental contaminants. Our results demonstrate that 87.6 % of the target compounds and over 59.6 % of the non-target features were consistently detected across all tested HLB cartridges, with an overall 71.2 % universally identified across the four LC-HRMS systems. Discrepancies in detection rates were primarily attributable to variations in retention time stability, mass stability of precursors and fragments, system cleanliness affecting fold change and p-values, and fragment response. These findings confirm the necessity of refining parameter criteria for NTS. Moreover, our study confirms the efficacy of the PyHRMS tool in analyzing and processing data from multiple instrumental platforms, reinforcing its utility for multi-platform NTS. Overall, our findings underscore the reliability and robustness of NTS methods in identifying potential water contaminants, while also highlighting factors that may influence these outcomes.
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Poluentes Químicos da Água , Água , Reprodutibilidade dos Testes , Cromatografia Líquida/métodos , Espectrometria de Massas/métodos , Água/química , Extração em Fase Sólida/métodos , Poluentes Químicos da Água/análiseRESUMO
Micellar-enhanced ultrafiltration (MEUF) technology is an effective method to treat low-concentration heavy metal wastewater. However, the leakage of surfactants in the ultrafiltration (UF) process will inevitably cause secondary pollution. In this study, a biosurfactant of conjugated linoleic acid (CLA) with conjugated double bonds was selected to bind its micelles by simple thermal crosslinking to obtain morphologically stable stearic acid (SA) nanoparticles. The pure SA nanoparticles were obtained by repeated dialysis. The stability of the SA nanoparticles was verified by comparing the particle size distribution and solubility of the materials before and after crosslinking at different pH levels. The effectiveness of SA nanoparticle-enhanced UF in removing heavy metals was verified by exploring the adsorption performance of SA nanoparticles. The dialysis device was used to simplify the UF device, wherein SA nanoparticles were assessed as adsorbents for the elimination of Cu2+, Pb2+, and Cd2+ ions from aqueous solutions under diverse process parameters, including pH, contact time, metal ion concentration, and coexisting ions. The findings indicate that the SA nanoparticles have no evidence of secondary contamination in UF and exhibit compatibility with a broad pH range and coexisting ions. The maximum adsorption capacities for Cu2+, Pb2+, and Cd2+ were determined to be 152.77, 403.56, and 271.46 mg/g, respectively.
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Ácidos Linoleicos Conjugados , Metais Pesados , Poluentes Químicos da Água , Cádmio , Micelas , Água , Chumbo , Metais Pesados/química , Adsorção , Poluentes Químicos da Água/química , Concentração de Íons de Hidrogênio , CinéticaRESUMO
Soil aggregate size plays an important role in controlling the distribution and transport of metals. Metals immobilized in soil particles will pose potential risks through production/sink flow and infiltration. This study explored the distribution behavior of metals based on soil aggregate size in a restored coastal mining area by establishing Structural Equation Model (SEM) and column experiments. The results showed that hydrological factors and a high degree of weathering accelerated the dissolution of metals from the mine, the desorption of Wa-NH4+-N, the release of F-, and the leaching of NO3-. Driven by soil properties, natural factors, and anthropogenic activities, the total metal content (Totalmetal) of Cr, Ni, Zn, Mn, and As showed significant spatial heterogeneity compared to Cd, Co, Cu, and Pb. The geochemical fraction of metals (Geometal) indicated that Cd, Co, Pb, Zn, As, and Cu are mainly present in ironmanganese oxidation bound, organically bound, and residual fractions. The results of SEM showed that the physicochemical properties, Wa-NH4+-N, nitrate nitrogen, and inorganic anions of the soil could explain 69.1 %, 76.4 %, 97.1 %, and 80.0 % of the variation in Kd-Mn, Kd-Pb, Kd-Ni, and Kd-Zn, respectively. While Kd-Cd, Kd-Cu, and Kd-Cr could be predicted by the Totalmetal, but the Geometal seemed to have little influence on metal Kd. The results of column experiments showed that macroaggregates (>0.25 mm) significantly affected the distribution of Co, Cr, Cu, Mn, Ni, Pb, and Zn in the topsoil. The severe disruption of soil aggregate structure resulted in small fluctuations of anthropogenic Cu, Mn, Pb, Zn, and As in different layers of deep soil. In addition, mineral composition in >0.15 mm particle size was more likely to change. Overall, the hydrological cycle of coastal mines increases the uncertainty of their response to risk. Our study provides a basis for future strategies for priority control and risk prevention.
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The environmental problems caused by mining are continuous and multifaceted, in order to help manage and plan restored mining areas, the bioavailability of metals is an effective tool for measuring the potential risks to human health. This study analyzes the geochemical fractions of eight metals (As, Cd, Cr, Cu, Mn, Ni, Pb, and Zn) to compare their bioavailability and establishes a Hierarchical health risk (HHR) model to assess the human health risks of the mine area after restoration. The results indicated that children have the highest non-carcinogenic risks exposed through ingestion (HI-ingestion) due to their special behaviors; HI-dermal may be enriched in the body; and HI-inhalation is lowest, as it is related to soil particle size. Affected by local economic development, environmental climate, soil type, and mining, the carcinogenic risk of exposure through the skin (CR-dermal) for adults significantly exceeds the acceptable safety level (ASL). The spatial distribution shows that the harm of mining to human health is a continuous process. There was still a significant CR for adults after remediation, and the HI of tailings exposure was more serious. The Classification and Regression Tree (CART) model of metal bioavailability was developed by integrating the extrinsic and intrinsic factors of metals to explore the effects of different factors on metal bioavailability and predict. The results showed that the bioavailability of metals was a dynamic process that combined land use, the distance to traffic roads, physicochemical properties of soil, and geochemical fractions of metal, and that it affects human health both directly and indirectly. Due to the fragility and sensitivity of the ecosystem after the mining area is restored, it may face greater environmental health risks.
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Metais Pesados , Poluentes do Solo , Adulto , Disponibilidade Biológica , Criança , China , Ecossistema , Monitoramento Ambiental , Humanos , Metais Pesados/análise , Medição de Risco , Solo , Poluentes do Solo/análiseRESUMO
The effects of ferric iron on the photo-treatment of simulated BDE-47 (2,2',4,4'- terabromodiphenyl ether)-Brij35 (Polyoxyethylene lauryl ether) washing waste were studied to evaluate the influences of ferric iron on BDE-47 removal and Brij35 recovery. The results show that Fe3+ accelerated BDE-47 degradation at lower concentrations (<0.5 mM) but attenuated it at higher concentrations (0.5-5 mM) and that Brij35 loss was increased with increasing Fe3+. These results likely are caused by changes in the rate of â¢OH production due to the ferric ion, association of Fe3+ and electron transfer from Brij35, and light attenuation at high concentration. The BDE-47 and Brij35 had different degradation rates at different pH values and at different dissolved oxygen concentrations. The BDE-47 products were identified by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). The results indicated that BDE-47 transformed into mainly lower-brominated products, a few bromodibenzofurans, some rearrangement products, and some hydroxylated polybrominated diphenyl ethers. A series of Brij35 oxidization products were detected by ultra-performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS), including hydroxylation products, carboxylation products, and some hydrophilic chain-breaking products. Brij35 was mainly oxidized by Fe3+ and/or reactive oxygen species (ROS) with the final products of CO2 and H2O. The iron ions apparently cycled from ferric to ferrous ions in the micelles such that the Fe3+-Brij35 complex dominated the main redox reaction, leading to both BDE-47 and Brij35 degradation. It appears that in any applied soil washing system, the ferric ions in the washing waste need to be removed because of the adverse effects on BDE-47 removal and eluate reuse.
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We synthesized a novel material, namely palladized zero-valent zinc (Pd/ZVZ), and investigated its efficiency for the degradation of polybrominated diphenyl ethers (PBDEs). The plated Pd significantly enhances the degradation rate of PBDEs by ZVZ at the optimum loading of 1% by weight. In the Pd/ZVZ system, very few lower BDEs were accumulated during the degradation of 2,2',4,4'- tetrabromodiphenyl ether (BDE-47) and the final product is diphenyl ether, whereas the ZVZ system only debrominates BDE-47 to di-BDE and further debromination becomes very difficult. The degradation rates of BDEs by ZVZ greatly decreased with decreased bromination level, while in Pd/ZVZ system, the degradation rates of PBDEs did not show a significant difference. These indicate different mechanisms. This was confirmed by investigating the debromination pathways of the PBDEs in both systems. We determined that a H-transfer was the dominant mechanism in the Pd/ZVZ system. In addition, the reactivity of Pd/ZVZ to BDE-47 is pH-independent, which has a great advantage for various applications over ZVZ alone. Our study provides a new approach for the remediation of the PBDEs pollution.
Assuntos
Poluentes Ambientais/análise , Retardadores de Chama/análise , Éteres Difenil Halogenados/análise , Ferro/química , Paládio/química , Bifenil Polibromatos/análise , Zinco/química , Halogenação , Cinética , Tamanho da Partícula , Éteres Fenílicos/análise , PósRESUMO
This study aims to use ultraviolet (UV) irradiation to decompose polybrominated diphenyl ethers (PBDEs) in the elutes and then reuse the surfactants. The results indicate that UV can remove 2,2',4,4'-tetrabrominated diphenyl ether (BDE-47) from surfactant eluents and Triton X series surfactants also can remove BDE-47 from the soil. Triton X-100 (TX-100) is the most promising surfactant during the washing and photodegradation processes. Quench experiments suggest that both 1O2 and OH⢠were involved in the TX-100 decomposition but only 1O2 is responsible for the degradation of BDE-47. In analysis of the photoproducts of BDE-47 by Gas Chromatography Mass Spectrum (GC-MS) and Liquid Chromatography High Resolution Mass Spectrometry (LC-HRMS), BDE-47 was mainly debrominated to the lower-brominated BDEs and then oxidized to ring-opening products. The little loss of TX-100 can mainly be attributed to the breakage of polyethylene oxide (PEO) chain. Nevertheless, the washing wastes treated by UV light can exhibit higher solubility for BDE-47 than before, indicating they can be reused for BDE-47 removal from soil. The toxicity assessment experiments were performed using Escherichia coli (E.coli) as an indicator. The results indicate that the removal of BDE-47 by UV irradiation can reduce the toxicity of eluent.
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Bifenil Polibromatos , Tensoativos , Cromatografia Gasosa-Espectrometria de Massas , Éteres Difenil Halogenados/análise , Octoxinol , Fotólise , SoloRESUMO
This study presents comprehensive formation pathways of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) from the pyrolysis of polybrominated diphenyl ethers (PBDEs). A total of 23 PBDE congeners, from mono- to hepta- brominated, were selected to conduct the pyrolysis experiments. The results suggest that n-PBDEs (where n means the number of bromine substituents) can transform into n/(n-1) PBDFs and (n-1)/(n-2) PBDDs as long as they meet certain structural requirement. One single PBDE congener can only transform (if possible) specific PBDF or PBDD based on their specific brominated arrangement by direct/oxygen bridge connecting the two ortho-carbon atoms. Among all selected BDEs, we found that only 2,2',4,4',5,5'-hexaBDE (BDE-153) can transform into 2,3,7,8-tetraBDD, which is most toxic congener among these group of compounds. When the degree of bromination increased, the yield of polybromobenzene increased, while that of the PBDD/Fs decreased, suggesting that the higher PBDEs favors to break the ether bond to form polybromobenzene, while the lower PBDEs favor transformation into PBDD/Fs. We proposed that the results in this study greatly improved our understanding on the transformation of PBDD/Fs from PBDEs in the pyrolysis process.
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This study aimed to investigate the effects of nitrate on the ultraviolet (UV) treatment of simulated washing wastes containing Trion X-100 (TX-100) surfactant and 4,4'-dibromodiphenyl ether (BDE-15) pollutant. The presence of nitrate accelerated the photodegradation of BDE-15 and TX-100, because they reacted with reactive oxygen species (ROS) produced from conversion between nitrate and nitrite. Due to nitrite having a stronger radical quenching property than nitrate, nitrite hindered TX-100 decay while the photodegradation rate of BDE-15 was similar to that in the presence of nitrate. This indicated that nitrate/nitrite affected BDE-15 photodegradation by photosensitization and TX-100 loss by ROS attack. An increased TX-100 concentration increased the loss of total inorganic nitrogen possibly owing to an increase in organic nitrogen formation through TX-100 nitration reactions. At pH < 7 HOONO rapidly isomerized to NO3-, and at pH = 7-9 it homolyzed to ONOO-, which increased OH production to decay the BDE-15 and TX-100 and also increased NO2- formation. BDE-15 mainly underwent debromination, and some rearrangement, ring formation, nitration and hydroxylation products were detected, indicating that the produced OH and NO2 attacked the BDE-15 and products. Furthermore, broken-chain, carboxylation, hydroxylation and nitro products were detected by Liquid chromatography high resolution mass spectrometry (LC-HRMS). Escherichia coli was used to assess the toxicity of washing waste containing nitrate: the presence of nitrate will increase the wastes' toxicity during UV treatment. Therefore, the presence of nitrate is deleterious to the UV treatment of washing wastes, and it is important to remove nitrates and nitrites from washing waste before UV irradiation.
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Nitratos/análise , Éteres Difenil Halogenados , Cinética , Nitritos , OctoxinolRESUMO
Nanoparticles of four noble metal doped titanium dioxide (i.e., Pd/TiO2, Ag/TiO2, Pt/TiO2 and Cu/TiO2) were synthesized and investigated for their effectiveness to degrade polybrominated diphenyl ethers (PBDEs) under UV light. All the investigated noble metal additives can greatly enhance the performance of TiO2 to degrade 2,2',4',4'-tetrabromodiphenyl ether (BDE-47). However, the debromination pathways of BDE-47 in Ag/TiO2 and Cu/TiO2 systems are just contrary to those in Pd/TiO2 and Pt/TiO2 systems, and there was an induction period in the former systems but not in the latter systems. The hydrogenation experiment suggests a direct H-atom transfer mechanism in Pd/TiO2 and Pt/TiO2 systems, while in Ag/TiO2 and Cu/TiO2 systems, electron transfer is still the dominant mechanism. Electronic method was applied to explain why BDE-47 exhibit different debromination pathways based on different degradation mechanism. In addition, oxygen was proved to be able to capture both electrons and H atoms, and thus can greatly inhibit the degradation of PBDEs in all investigated systems. Finally, the merit and demerit of each metal doped TiO2 were discussed in detail, including the reactivity, stability and the generation of byproducts. We proposed our study greatly enhance our understanding on the mechanisms of PBDE degradation in various metal doped TiO2 systems.
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Éteres Difenil Halogenados/química , Nanocompostos/química , Processos Fotoquímicos , Titânio/química , Catálise , Raios UltravioletaRESUMO
This study investigated the relative significance of electron transfer (e-transfer) and H-atom transfer (H-transfer) in a nanoscale zerovalent iron (n-ZVI) system and six n-ZVI-based bimetallic systems (Fe/Cu, Fe/Ni, Fe/Pd, Fe/Ag, Fe/Pt, and Fe/Au) through a case study of the debromination of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47). The results revealed that the reactivities of these bimetallic particles to BDE-47 decreased in the following order: Fe/Pd>Fe/Ag>Fe/Cu>Fe/Ni>Fe/Au>Fe/Pt≈n-ZVI. Debromination of BDE-47 in metal-H2 systems suggested that Ni, Pd, Pt, Cu and Au can utilize H2 to debrominate BDE-47. In the H-transfer process, BDE-47 preferentially debrominated the parabromine substituent to generate BDE-17, whereas in the e-transfer process, BDE-47 preferentially debrominate orthobromine substituent to generate BDE-28. The debromination pathways of BDE-47 in bimetallic and NaBH4-metal systems suggested that Fe/Ni, Fe/Pd and Fe/Pt debrominate polybrominated diphenyl ethers (PBDEs) through a H-transfer dominant mechanism, while Fe/Ag debrominate PBDEs through an e-transfer dominant mechanism. In the cases of Fe/Cu and Fe/Au, the e-transfer and H-transfer may be equally involved in the debromination of PBDEs. These results greatly improve our understanding of the relative significance of e-transfer and H-transfer in the dehalogenation of halogenated aromatic compounds (HACs) in various n-ZVI-based bimetallic systems.
RESUMO
Surfactants are known to enhance the degradation of halogenated organics by nanoscale zerovalent iron (n-ZVI) or n-ZVI-based bimetallic particles, but the mechanism of the promotion is not well understood. In this study, we used nanoscale Ag/Fe particles (n-Ag/Fe) to degrade 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) in different surfactant solutions. The results show that the nonionic surfactant TX-100 had the best promoting effect, which might be attributed to the decrease in particle agglomeration and improvement of mass transfer efficiency after the adsorption of TX-100 on n-Ag/Fe. The distribution analysis of BDE-47 in solid and liquid phases indicates that when the concentration of TX-100 in aqueous solution was above critical micelle concentration, BDE-47 started to dissolve in the liquid phase. Thus, TX-100 micelles can enhance the mass transfer efficiency of BDE-47. However, a too high concentration of TX-100 (above 1.0â¯mM) would influence the promotion effect of BDE-47 degration, which might be attributed to the excessive and thicker micelles of TX-100 hindering the contact between BDE-47 and n-Ag/Fe. We also studied the degradation pathway of BDE-47 and its products, and found that surfactants did not change the degradation pathway of BDE-47.
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Éteres Difenil Halogenados/química , Modelos Químicos , Tensoativos/química , Adsorção , Éter , Halogenação , Ferro/química , Cinética , Micelas , Prata/químicaRESUMO
Polybrominated diphenyl ethers (PBDEs) are typical flame retardant that have arose widely environmental concerns. Previous studies have found that PBDEs can generate lower BDEs and polybrominated dibenzofuran (PBDFs) under UV exposure, but these two processes were not well understood. In this study, we have investigated them through the case study of three BDE congeners (i.e. BDE-29, BDE-25 and BDE-21), which all have an ortho-, a meta- and a para-bromine substituents. The results shows that the vulnerability rank order of brominated position for these three BDE congeners are totally different, the bromine substituent at each position (ortho-, meta- or para-) can be preferentially removed, indicating it is not scientific to summarize the debromination pathways of PBDEs by comparing the brominated position. The lowest unoccupied molecular orbital (LUMO) of PBDEs in first excited state are well consistent with their actual debromination pathways, suggesting it is a good descriptor to predict the photodebromination pathways of PBDEs. In addition, the PBDEs with an ortho-bromine substituent can generate lower PBDFs, and the first step is to generate lower BDEs with an ortho-carbon radical, followed by ring closure reaction to generate PBDFs.