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1.
Anal Chem ; 96(21): 8807-8813, 2024 05 28.
Artigo em Inglês | MEDLINE | ID: mdl-38714342

RESUMO

Although engineering bacterial sensors have outstanding advantages in reflecting the actual bioavailability and continuous monitoring of pollutants, the potential escape risk of engineering microorganisms and lower detection sensitivity have always been one of the biggest challenges limiting their wider application. In this study, a core-shell hydrogel bead with functionalized silica as the core and alginate-polyacrylamide as the shell have been developed not only to realize zero escape of engineered bacteria but also to maintain cell activity in harsh environments, such as extremely acidic/alkaline pH, high salt concentration, and strong pressure. Particularly, after combining the selective preconcentration toward pollutants by functionalized core and the positive feedback signal amplification of engineering bacteria, biosensors have realized two-stage signal amplification, significantly improving the detection sensitivity and reducing the detection limit. In addition, this strategy was actually applied to the detection of As(III) and As(V) coexisting in environmental samples, and the detection sensitivity was increased by 3.23 and 4.39 times compared to sensors without signal amplification strategy, respectively, and the detection limits were as low as 0.39 and 0.86 ppb, respectively.


Assuntos
Técnicas Biossensoriais , Técnicas Biossensoriais/métodos , Alginatos/química , Dióxido de Silício/química , Resinas Acrílicas/química , Limite de Detecção , Hidrogéis/química
2.
Environ Res ; 263(Pt 1): 119957, 2024 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-39307229

RESUMO

Surface sulfidation has been widely investigated to effectively enhance the utilization and selectivity of iron electrons for enhanced pollutant reduction. However, there is relatively less knowledge on whether sulfidation facilitates the catalytic oxidation process and the mechanism of enhancement. Therefore, in this study, the role of surface sulfidation in modulating the oxidant decomposition pathway and reactive oxygen species generation was investigated with the sulfidated zerovalent iron (S-ZVI) activated persulfate (PS) system. The results revealed that sulfur on the surface of S-ZVI not only facilitates PS activation to generate more SO4•-, but also acts as an essential in the dynamic equilibrium between SO4•- and •OH. Specifically, the S-ZVI surface sulfide first forms sulfur monomers during catalysis, which promotes electron transfer to accelerate Fe3+ to Fe2+ cycling, prompting the generation of more SO4•- also generates SO32-. Then, SO32- is further reacted with •OH to generate the [O--O-SO3-] intermediate of SO4•-, which leads to a dynamic equilibrium of SO4•- and •OH, mitigating the further conversion of SO4•- to •OH. These findings unveiled the dynamic variation of sulfur on the surface of S-ZVI during PS activation, elevating new insights for the sulfate radical-based efficient degradation.

3.
Anal Chem ; 95(33): 12550-12556, 2023 08 22.
Artigo em Inglês | MEDLINE | ID: mdl-37550863

RESUMO

The classes and forms of antibiotics directly determine their ecotoxicity and environmental chemical behavior, and developing a sensor array for simultaneous and in situ detection of antibiotics is highly anticipated. In this study, different morphologies of g-C3N4 with different fluorescence properties and peroxidase activity were prepared by regulating the degree of interlayer stacking and planar connectivity. Subsequently, in order to enhance its enzyme activity and amplify the differences in response signals to different antibiotics, three morphologies of g-C3N4/MIL-101(Fe) were prepared by in situ growth of equivalent amounts of MIL-101(Fe) on g-C3N4, respectively. The sensor array constructed based on the cross-response signals between g-C3N4/MIL-101(Fe) and antibiotics not only realized the simultaneous detection of quinolones, furans, tetracyclines, and lincomamides but also could efficiently identify their seven different forms. In the range of 0.2-0.8 ppm, the minimum detection limit for antibiotics was 12 ppb. In addition, the recovery experiments of multicomponent-mixed antibiotics in environmental samples show that the recovery rate remained at 91.42-107.59%, confirming the reliability and practicality of the sensor array. This study not only revealed the influence of crystal morphology regulation on the optical properties and enzyme activities of nanozymes, but also provided support for tracing, ecological remediation, and in situ environmental chemical behavior research of antibiotics.


Assuntos
Antibacterianos , Estruturas Metalorgânicas , Reprodutibilidade dos Testes , Estruturas Metalorgânicas/química , Peroxidases
4.
Mikrochim Acta ; 190(8): 311, 2023 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-37468761

RESUMO

To develop simultaneous and in-situ detection techniques towards Cr(VI) and Mn(II), Eu/Tb@CDs with white fluorescence were prepared by a one-step hydrothermal method. With the increase of Cr(VI), all fluorescence channels of Eu/Tb@CDs exhibited obvious quenching, and the detection limit (LOD) was 0.10 µM. In the presence of Mn(II), only the fluorescence from Tb and Eu was quenched, while the fluorescence of CDs was not effected. The LOD for Mn(II) was 0.16 µM. More importantly, in the actual water samples where Cr(VI) and Mn(II) coexist, Eu/Tb@CDs can realize their rapid and simultaneous detection by simple spectral calculation. The selective and competitive experiments have also confirmed that the detection of Cr(VI) and Mn(II) was not interfered by common pollutants in groundwater. It is undeniable that the simultaneous detection of multiple targets by one probe not only greatly improves the detection efficiency, but also has important significance for the field monitoring of water quality parameters.

5.
Mikrochim Acta ; 190(11): 456, 2023 Nov 02.
Artigo em Inglês | MEDLINE | ID: mdl-37917401

RESUMO

To develop a convenient method for simultaneous detection of As(III/V), Cr(III/VI), and Fe(II/III), three morphologies of CeO2 oxidase have been prepared. Based on the difference in oxidase activity and binding ability with substrate TMB of CeO2 of different morphologies, a 3 (Signal unit) × 6 (Target number) × 5 (Repetition) sensor array was constructed to realize simultaneous detection of six variable valence metal ions As(III/V), Cr(III/VI), and Fe(II/III). The lowest detection limit of the array for metal ions was 1.68 µg/L. The analysis of environmental samples with multiple metal ions (binary and ternary mixtures) co-existing has confirmed that the sensor array can achieve simultaneous qualitative and quantitative results for composite samples. This study not only revealed the influencing factors of crystal morphology regulation on oxidase activity, but also provided a scheme for the morphology detection of easily convertible metal ions in the field through the construction of the sensor array.

6.
Environ Sci Technol ; 56(9): 5542-5551, 2022 05 03.
Artigo em Inglês | MEDLINE | ID: mdl-35412804

RESUMO

Sulfidation can greatly improve the efficiency of utilization of reducing equivalents for contaminant removal; however, whether this method benefits Fenton-like reactions or not and the possible mechanism are not well understood. In this study, we revealed that surface sulfidation can greatly promote the heterogeneous Fenton activity of ß-FeOOH (Fe3S4@ß-FeOOH) by 40 times, in which not only the •OH formation was enhanced but also SO4•- as a new oxidation species was generated. Moreover, their contribution to metronidazole (MTZ) degradation was 52.5 and 37.1%, respectively. In comparison, almost no HO2•/O2•- was detected in the Fe3S4@ß-FeOOH/H2O2 system. These results were different from some previously reported Fenton counterparts. Based on the characterization and probe experiments, sulfur species, including S2-, S0, and Sn2-, as an electron donor and electron shuttle were responsible for efficient conversion of Fe(III) into Fe(II) other than via the Haber-Weiss mechanism, leading to excellent •OH generation via a Fenton-like mechanism. Most importantly, HSO5- can be generated from SO32- oxidized by •OH, and its scission into SO4•- was not dependent on the extra electric potential or Fe-O2-S(IV) intermediate. These findings provided new insight for utilizing sulfidation to improve the activity of iron-based Fenton catalysts.


Assuntos
Compostos Férricos , Peróxido de Hidrogênio , Ferro , Oxirredução , Sulfatos
7.
Environ Sci Technol ; 55(4): 2403-2410, 2021 02 16.
Artigo em Inglês | MEDLINE | ID: mdl-33543936

RESUMO

Sulfidated zerovalent iron (S-ZVI) has been extensively used for reducing pollutants. In this study, the oxidation process in the reductive removal of p-nitrophenol (PNP) by S-ZVI was confirmed under anaerobic conditions. We revealed that a PNP oxidation process involving •OH resulted from the H2O2 activation by surface-bound Fe(II) in S-ZVI, in which H2O2 was generated via a surface-mediated reaction between water and FeS2. Only the PNP reduction process occurred for ZVI. Herein, efficient PNP degradation by S-ZVI resulted from two functions: reduction into p-aminophenol due to enhanced electron transfer and PNP oxidation into p-benzoquinone by •OH radicals from the interaction of surface-bound Fe(II) and in situ generated H2O2, the contributions of the oxidation and reduction processes to PNP degradation over S-ZVI were 10 and 90%, respectively. Sulfur in S-ZVI suppressed the pH increase in the reaction media and produced more surface-bound Fe(II) than ZVI for •OH generation via the heterogeneous Fenton reaction process. Since different degradation pathways could lead to different effects on the water environment, such as toxicity, our findings suggest that the oxidizing process induced by S-ZVI during groundwater decontamination should be considered.


Assuntos
Ferro , Poluentes Químicos da Água , Anaerobiose , Peróxido de Hidrogênio , Radical Hidroxila , Nitrofenóis , Oxirredução
8.
Environ Res ; 186: 109626, 2020 07.
Artigo em Inglês | MEDLINE | ID: mdl-32668558

RESUMO

In this study, an efficient and reusable heterogeneous Fenton catalyst Fe3O4@S-doped ZnO magnetic composite was synthesized for the degradation of ofloxacin (OFX) under alkaline conditions without external energy input. The Fe3O4@S-doped ZnO exhibited excellent catalytic activity toward ofloxacin degradation within 120 min. Using 0.25 g/L of catalyst and 5.0 mL/L of H2O2 under optimized conditions, the catalyst was effective in pH values ranging from 5.2 to 9.0. The catalytic performance at optimal conditions was in accordance with a pseudo-first-order kinetics model. The reaction constant of Fe3O4@S-doped ZnO (0.0354 min-1) was three times than that of Fe3O4@ZnO (0.0124 min-1) under alkaline conditions (pH 8.2). The reactive oxygen species were the ·OH and O2·-, with ·OH dominating in the degradation of OFX. It is proposed that the catalyst acts as a Lewis acid, creating an acidic microenvironment on the catalyst's surface and widening the pH range of the Fenton reaction to alkaline conditions. Additionally, the catalyst was stable and reusable after six cycles of use. The Fenton-like Fe3O4@S-doped ZnO catalyst overcomes the problem of the narrow pH of the reaction system, thus providing promising environmental applications.


Assuntos
Ofloxacino , Óxido de Zinco , Catálise , Peróxido de Hidrogênio , Fenômenos Magnéticos , Oxirredução
9.
Environ Sci Technol ; 52(11): 6518-6525, 2018 06 05.
Artigo em Inglês | MEDLINE | ID: mdl-29727187

RESUMO

The development of efficient heterogeneous Fenton catalysts is mainly by "trial-and-error" concept and the factor determining H2O2 activation remains elusive. In this work, we demonstrate that suitable facet exposure to elongate O-O bond in H2O2 is the key parameter determining the Fenton catalyst's activity. CuFeO2 nanocubes and nanoplates with different surface facets of {110} and {012} are used to compare the effect of exposed facets on Fenton activity. The results indicate that ofloxacin (OFX) degradation rate by CuFeO2 {012} is four times faster than that of CuFeO2 {110} (0.0408 vs 0.0101 min-1). In CuFeO2 {012}-H2O2 system, OFX is completely removed at a pH range 3.2-10.1. The experimental results and theoretical simulations show that •OH is preferentially formed from the reduction of absorbed H2O2 by electron from CuFeO2 {012} due to suitable elongation of O-O (1.472 Å) bond length in H2O2. By contrast, the O-O bond length is elongated from 1.468 to 3.290 Å by CuFeO2 {110} facet, H2O2 tends to be dissociated into -OH group and passivates {110} facet. Besides, the new formed ≡Fe2+* on CuFeO2 {012} facet can accelerate the redox cycle of Cu and Fe species, leading to excellent long-term stability of CuFeO2 nanoplates.


Assuntos
Poluentes Ambientais , Peróxido de Hidrogênio , Catálise , Ofloxacino , Oxirredução
10.
Environ Sci Technol ; 51(21): 12699-12706, 2017 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-28934546

RESUMO

To develop an ultraefficient and reusable heterogeneous Fenton-like catalyst at a wide working pH range is a great challenge for its application in practical water treatment. We report an oxygen vacancy promoted heterogeneous Fenton-like reaction mechanism and an unprecedented ofloxacin (OFX) degradation efficiency of Cu doped Fe3O4@FeOOH magnetic nanocomposite. Without the aid of external energy, OFX was always completely removed within 30 min at pH 3.2-9.0. Compared with Fe3O4@FeOOH, the pseudo-first-order reaction constant was enhanced by 10 times due to Cu substitution (9.04/h vs 0.94/h). Based on the X-ray photoelectron spectroscopy (XPS), Raman analysis, and the investigation of H2O2 decomposition, •OH generation, pH effect on OFX removal and H2O2 utilization efficiency, the new formed oxygen vacancy from in situ Fe substitution by Cu rather than promoted Fe3+/Fe2+ cycle was responsible for the ultraefficiency of Cu doped Fe3O4@FeOOH at neutral and even alkaline pHs. Moreover, the catalyst had an excellent long-term stability and could be easily recovered by magnetic separation, which would not cause secondary pollution to treated water.


Assuntos
Peróxido de Hidrogênio , Nanocompostos , Ofloxacino , Catálise , Ferro , Oxigênio
11.
Water Sci Technol ; 76(5-6): 1308-1317, 2017 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-28953457

RESUMO

A submerged anaerobic membrane reactor (SAnMBR) was employed for comprehensive evaluation of sewage treatment at 25 °C and its performance in removal efficiency, biogas production and membrane fouling. Average 89% methanogenic degradation efficiency as well as 90%, 94% and 96% removal of total chemical oxygen demand (TCOD), biochemical oxygen demand (BOD) and nonionic surfactant were obtained, while nitrogen and phosphorus were only subjected to small removals. Results suggest that SAnMBRs can effectively decouple organic degradation and nutrients disposal, and reserve all the nitrogen and phosphorus in the effluent for further possible recovery. Small biomass yields of 0.11 g mixed liquor volatile suspended solids (MLVSS)/gCOD were achieved, coupled to excellent methane production efficiencies of 0.338 NLCH4/gCOD, making SAnMBR an attractive technology characterized by low excess sludge production and high bioenergy recovery. Batch tests revealed the SAnMBR appeared to have the potential to bear a high food-to-microorganism ratio (F/M) of 1.54 gCOD/gMLVSS without any inhibition effect, and maximum methane production rate occurred at F/M 0.7 gCOD/gMLVSS. Pore blocking dominated the membrane fouling behaviour at a relative long hydraulic retention time (HRT), i.e. >12 hours, while cake layer dominated significantly at shorter HRTs, i.e. <8 hours.


Assuntos
Biocombustíveis , Reatores Biológicos , Membranas Artificiais , Esgotos , Eliminação de Resíduos Líquidos/métodos , Anaerobiose , Incrustação Biológica , Análise da Demanda Biológica de Oxigênio , Biomassa , Nitrogênio , Fósforo , Purificação da Água/instrumentação , Purificação da Água/métodos
12.
Environ Sci Technol ; 49(3): 1690-7, 2015 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-25564945

RESUMO

Fe2O3 and/or Al2O3 were supported on mesoporous SBA-15 by wet impregnation and calcinations with AlCl3 and FeCl3 as the metal precursor and were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectra (FTIR) of adsorbed pyridine. Fe2O3/Al2O3@SBA-15 was found to be highly effective for the mineralization of ibuprofen aqueous solution with ozone. The characterization studies showed that Al-O-Si was formed by the substitution of Al(3+) for the hydrogen of surface Si-OH groups, not only resulting in high dispersion of Al2O3 and Fe2O3 on SBA-15, but also inducing the greatest amount of surface Lewis acid sites. By studies of in situ attenuated total reflection FTIR (ATR-FTIR), in situ Raman, and electron spin resonance (ESR) spectra, the chemisorbed ozone was decomposed into surface atomic oxygen species at the Lewis acid sites of Al(3+) while it was converted into surface adsorbed (•)OHads and O2(•-) radicals at the Lewis acid sites of Fe(3+). The combination of both Lewis acid sites of iron and aluminum onto Fe2O3/Al2O3@SBA-15 enhanced the formation of (•)OHads and O2(•-) radicals, leading to highest reactivity. Mechanisms of catalytic ozonation were proposed for the tested catalysts on the basis of all the experimental information.


Assuntos
Ibuprofeno/química , Ozônio/química , Adsorção , Óxido de Alumínio/química , Catálise , Espectroscopia de Ressonância de Spin Eletrônica , Compostos Férricos/química , Oxigênio/química , Espectroscopia Fotoeletrônica , Dióxido de Silício/química , Espectroscopia de Infravermelho com Transformada de Fourier , Suspensões , Água/química , Difração de Raios X
13.
Environ Sci Technol ; 49(14): 8639-47, 2015 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-26101896

RESUMO

Mesoporous Cu-doped γ-Al2O3 (γ-Cu-Al2O3) was prepared via an evaporation-induced self-assembly process, in which Cu(+/2+) was co-incorporated into mesoporous γ-Al2O3 by chemical bonding of Al-O-Cu. The catalyst was found to be highly effective and stable for the degradation and mineralization of aromatic pollutants, as demonstrated with bisphenol A, 2,4-dichlorophenoxyacetic acid, ibuprofen, diphenhydramine, and phenytoin in the presence of H2O2 under neutral pH conditions. In addition, the high utilization efficiency of H2O2 was maintained at approximately 90% prior to the disappearance of the initial aromatic pollutants. On the basis of all of the characterization results, the pollutant degradation processes predominantly occurred on the surface of the catalyst due to the formation of σ-Cu-ligand complexes between the phenolic OH group and the surface Cu. In the reaction system, in addition to the unselective oxidation by (•)OH, H2O2 directly attacked the σ-Cu(2+)-complexes aromatic ring with the phenolic OH group, which resulted in the formation of (•)OH and HO-adduct radicals that were oxidized to hydroxylation products by reduction of Cu(2+) in the σ-Cu(2+)-complexes to Cu(+). The process prevented Cu(2+) from oxidizing H2O2 to form HO2(•)/O2(•-) or O2, and enhanced the Cu(+)/Cu(2+) cycle, the formation of (•)OH, and the utilization efficiency of H2O2. Therefore, an extraordinarily high degradation and mineralization of the aromatic pollutants was observed.


Assuntos
Óxido de Alumínio/química , Poluentes Ambientais/química , Hidrocarbonetos Aromáticos/química , Ácido 2,4-Diclorofenoxiacético/química , Compostos Benzidrílicos/química , Catálise , Peróxido de Hidrogênio/química , Concentração de Íons de Hidrogênio , Ferro , Ligantes , Oxirredução , Fenóis/química
14.
J Biomater Appl ; 38(8): 932-939, 2024 03.
Artigo em Inglês | MEDLINE | ID: mdl-38317637

RESUMO

Sonodynamic therapy (SDT) is an emerging cancer treatment method in recent years. However, the ultrasound signal utilized for SDT is usually located at a low-frequency spectrum (<2 MHz), and in the field of SDT research, few studies have focused on the exploration and development of ultrasound frequency. Studies have shown that the GHz-level ultrasound can increase cell membrane permeability and have a negligible effect on cell vitality. Herein, we reported the study of a GHz thin film bulk acoustic resonator as an ultrasound source for synergistic treatment with nanoscale calcium peroxide (CaO2). It was discovered that this ultrasound source ultimately achieved an efficient therapeutic outcome on mouse breast cancer cell line 4T1. Such GHz-level ultrasound application in SDT is of high significance to broaden the cognition and application scope of SDT.


Assuntos
Neoplasias , Terapia por Ultrassom , Camundongos , Animais , Terapia por Ultrassom/métodos , Ultrassonografia , Linhagem Celular , Acústica , Linhagem Celular Tumoral
15.
J Hazard Mater ; 478: 135578, 2024 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-39173378

RESUMO

Establishing a method similar to ICP-MS that can quantitatively analyze multiple heavy metals simultaneously, conveniently, and in situ is highly anticipated. In this study, we integrated the sensing elements of multiple targets and different fluorescence reporting elements to construct an engineered Escherichia coli. When these targets are present, the engineered bacteria can emit a fluorescent signal at the corresponding wavelength. To avoid the inability to accurately distinguish and quantify the content of each target due to the overlap of fluorescence signals when multiple targets coexist, a hydrogel-based separation platform similar to a separation column was constructed. The hydrogel platform can change the detection limit (LOD) and sensitivity by adjusting the adsorption strength towards different targets, so as to realize the differentiation and recognition of their respective detection signals. The LODs of this new detection method for Cd(II), Hg(II), As(III), and Pb(II) are 1.249, 0.380, 3.917, and 0.755 µg/L, respectively. In addition, this biosensor system was applied to detect coexisting Cd(II), Hg(II), As(III), and Pb(II) in actual samples with a recovery rate of 85.61-110.30 %, which is consistent with the classical ICP-MS detection results, confirming the accuracy and reliability of the method for detecting multiple heavy metal coexisting samples.


Assuntos
Técnicas Biossensoriais , Escherichia coli , Hidrogéis , Limite de Detecção , Metais Pesados , Hidrogéis/química , Escherichia coli/genética , Escherichia coli/isolamento & purificação , Metais Pesados/análise , Técnicas Biossensoriais/métodos , Arsênio/análise , Poluentes Químicos da Água/análise , Chumbo/análise
16.
J Hazard Mater ; 464: 132962, 2024 02 15.
Artigo em Inglês | MEDLINE | ID: mdl-37976862

RESUMO

Pyrite has been extensively tested for oxidizing contaminants via the activation of water molecule or dissolved oxygen, while the changing of oxidation species induced by contaminant's concentration has been largely underestimated. In this study, we revealed a self-acclimation mechanism of pyrite in terms of •OH conversion to 1O2 during the sulfamethoxazole (SMX) degradation process under oxic conditions. Two reaction stages of SMX degradation by pyrite were observed. The SMX concentration decreased by 70% rapidly in the first 12 h after the reaction was initiated, then, the removal rate began to decrease as the SMX concentration decreased. Importantly, •OH and O2•- were the dominant oxidizing species in stage one, while 1O2 was responsible for the further degradation of SMX in stage two. The self-acclimated mechanism of pyrite was proven to be caused by the conversion of oxidative species at the surface of pyrite. This process can overcome the shortages of •OH such as ultrashort lifetime and limited effective diffusion in the decontamination of micropollutant. Moreover, different reactive oxygen species will lead to different degradation pathways and environmental toxicity while degrading pollutants. This finding of oxidizing species' self-acclimation mechanism should be of concern when using pyrite for water treatment.


Assuntos
Sulfametoxazol , Poluentes Químicos da Água , Espécies Reativas de Oxigênio , Sulfametoxazol/toxicidade , Poluentes Químicos da Água/toxicidade , Ferro , Oxigênio , Oxirredução
17.
Food Chem ; 443: 138460, 2024 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-38295566

RESUMO

Currently, planting selenium-rich crops using inorganic selenium such as selenate and selenite is used to address human selenium deficiency problems. In this paper, besides the above two traditional inorganic selenium speciation, we chose a new organic selenium speciation of potassium selenocyanoacetate to investigate the different effects of selenium speciation on selenium absorption, selenium transformation and cadmium antagonism via foliar application. Plantingexperiments showed that the selenium content of garlic bulbs treated with organic selenium was 1.8-3.9 times higher than that of inorganic selenium. Additionally, the absorption and transformation efficiency of organic selenium in garlic was also the highest, reaching over 95 %. Importantly, it was noteworthy that the cadmium content in bulbs treated with organic selenium was significantly lower than the Chinese food safety standard (0.2 mg/kg). Hence, this study provides an efficient organic selenium speciation which is beneficial to meet human selenium requirements and ensure safe utilization of cadmium-contaminated soils.


Assuntos
Alho , Selênio , Humanos , Selênio/farmacologia , Cádmio , Ácido Selenioso , Antioxidantes , Ácido Selênico
18.
J Hazard Mater ; 466: 133640, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38309162

RESUMO

The environmental fate of arsenic (As) relies substantially on its speciation, which occurs frequently coupled to the redox transformation of manganese. While trivalent manganese (Mn(III)), which is known for its high reactivity, is believed to play a role in As mobilization by iron (oxyhydr)oxides in dynamic aquifers, the exact roles and underlying mechanisms are still poorly understood. Using increasingly complex batch experiments that mimick As-affected aquifer conditions in combination with time-resolved characterization, we demonstrate that Mn(III)-NOM complexes play a crucial role in the manganese-mediated immobilization of As(III) by ferrihydrite and goethite. Under anaerobic condition, Mn(III)-fulvic acid (FA) rapidly oxidized 31.8% of aqueous As(III) and bound both As(III) and As(V). Furthermore, Mn(III)-FA exerted significantly different effects on the adsorption of As by ferrihydrite and goethite. Mn(III)-FA increased the adsorption of As by 6-16% due to the higher affinity of oxidation-produced As(V) for ferrihydrite under circumneutral conditions. In contrast, As adsorption by crystalline goethite was eventually inhibited due to the competitive effect of Mn(III)-FA. To summarize, our results reveal that Mn(III)-NOM complexes play dual roles in As retention by iron oxides, depending on the their crystallization. This highlights the importance of Mn(III) for the fate of As particularly in redox fluctuating groundwater environments.

19.
ACS Appl Mater Interfaces ; 15(8): 11324-11332, 2023 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-36790437

RESUMO

In this work, a novel strategy for Fenton activity improvement of Cu2X was reported, in which the local electron density of Cu sites was regulated via manipulation of simple chalcogen elements (O, S, and Se). Among them, Cu2Se catalysts show excellent catalytic activity to activate H2O2 for the complete removal of ofloxacin (10 mg/L) at an initial pH of 6.5 within 120 min. Radical scavenger experiments and electron spin resonance spectroscopy confirm that •OH radicals are the primary oxygen reactive species to drive ofloxacin degradation. In addition, density functional theory calculations further proved that electrons would migrate from X and accumulate on Cu active sites in the order Se > S > O. Compared with Cu2O and Cu2S, the highly concentrated electron density of Cu atoms in Cu2Se not only decreased the activation energy of the Fenton-like reaction but also boosted the Cu2+/Cu+ cycle with the generation of more •OH radicals (18-66 µm) and the maintenance of high stability of catalysts, leading to excellent catalytic activity and application potential. We believe this work will lay the foundation for designing excellent Fenton catalysts for practical applications since developing a heterogeneous Fenton system with the highest oxidation efficiency has always been the long-term goal in this field.

20.
J Hazard Mater ; 441: 129956, 2023 01 05.
Artigo em Inglês | MEDLINE | ID: mdl-36108497

RESUMO

The threat of tetracycline antibiotics to the environment and human health is attracting widespread attention. The development of morphological analysis and quantitative techniques of multiple tetracyclines is of great significance for the evaluation of biochemical toxicity, wide-spectrum antibacterial property and degradation cycle between different tetracyclines. In this study, the white fluorescent Eu/Tb@CDs was synthesized and applied successfully to the identification and detection of the most widely used tetracycline antibiotics (tetracycline (TC), oxytetracycline (OC), chlortetracycline (CC) and doxycycline (DC)) with detection limits all below 1 nM. For the actual water samples with coexistence of the above 4 tetracyclines, their simultaneous morphology identification and accurate quantitative detection can also be realized through simple spectrometric measurement. In addition, the selective and competitive experiments have been carried out on the pollutants widely present in water, and the results have also confirmed that other pollutants could not interfere with the detection of the above 4 tetracyclines. It is undeniable that this work will conveniently and visually reveal the existence information and geographical distribution characteristics of different tetracycline antibiotics in the environment and their action mechanism on organisms.


Assuntos
Clortetraciclina , Oxitetraciclina , Antibacterianos/análise , Doxiciclina/análise , Corantes Fluorescentes/análise , Humanos , Oxitetraciclina/análise , Tetraciclina/análise , Tetraciclinas/análise , Água
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