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1.
Small ; : e2406319, 2024 Sep 02.
Artículo en Inglés | MEDLINE | ID: mdl-39221550

RESUMEN

In the domain of heterogeneous catalytic activation of peroxymonosulfate (PMS), high-valent metal-oxo (HVMO) species are widely recognized as potent oxidants for the abatement of organic pollutants. However, the generation selectivity and efficiency of HVMO are often constrained by stringent requirements for catalyst adsorption sites and electron transfer efficiency. In this study, a single-atom catalyst, CuSA/CNP&S, is synthesized featuring multiple types (planar/axial) of heteroatom coordination via an H-bond-assisted self-assembly strategy. It is confirmed that CuN3 active centers with axial S coordination are uniformly distributed in a carbon matrix modified by planar P atoms. CuSA/CNP&S activated PMS to selectively generate Cu(III)═OH species as the primary reactive oxygen species (ROS). The pseudo-first-order kinetic rate for bisphenol A degradation reached 1.51 min-1, a 17.57-fold increase compared to the unmodified CuSA/CN catalyst. Additionally, the CuSA/CNP&S catalyst demonstrates high efficiency and durability in removing contaminants from various aqueous matrices. Theoretical calculations and experimental results indicate that the intrinsic electric field generated by distal planar P atoms enhances electron transfer efficiency within the carbon matrix. Meanwhile, axial S coordination elevates the d-band center and tunes the eg * band broadening of Cu, thereby enhancing the adsorption selectivity for the terminal oxygen of PMS. This multitype coordination synergistically mitigates the issues of low selectivity and yield of HVMO species.

2.
Environ Sci Technol ; 58(33): 14718-14725, 2024 Aug 20.
Artículo en Inglés | MEDLINE | ID: mdl-39110125

RESUMEN

Cadmium (Cd) contamination poses a significant global threat to human health, primarily through dietary intake, with rice serving as a major source. While Cd predominantly resides in bound states in soil, the physiological processes by which rice facilitates Cd absorption in the rhizosphere remain largely elusive. This study delves into the mechanisms governing Cd uptake by rice plants in the rhizosphere, emphasizing the impact of daytime and nighttime fluctuations in microenvironmental conditions. Employing a microfluidic chip setup, the research reveals that radial oxygen loss from rice roots triggers dissolution of Cd in the rhizosphere. Notably, Cd mobility exhibits distinct diurnal fluctuations, peaking at 44.0 ± 4.1 nM during the daytime and dropping to 8.3 ± 1.3 nM during the nighttime. Further investigations reveal that variations in dissolved oxygen and hydroxyl radical concentrations influence Cd release, while pH changes and microbial reduction reactions play crucial roles in Cd immobilization. These findings provide insights into the intricate processes governing Cd mobilization in the rice rhizosphere, highlighting the importance of regulating these processes for effective Cd adsorption control in rice crops and safeguarding public health.


Asunto(s)
Cadmio , Oryza , Oxígeno , Rizosfera , Oryza/metabolismo , Cadmio/metabolismo , Oxígeno/metabolismo , Contaminantes del Suelo/metabolismo , Raíces de Plantas/metabolismo
3.
Sci Total Environ ; 951: 175640, 2024 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-39168322

RESUMEN

Silicon within Si-rich biochars (sichar) plays a crucial role in immobilizing heavy metals and providing slow-releasing bioavailable silicon for silicophilic plants. However, the impact of heating rate on the silicon properties and carbon­silicon interactions in sichars remains unclear. In this study, rice husk was used as a silicon-rich biomass to prepare sichars at different heating rates (10, 30 and 60 °C per minute, and ultra-fast-pyrolysis), then experiments such as silicon concentration measurement, Raman and XRD characterization were conducted. The results showed that a faster heating rate reduced the carbon content during pyrolysis while promoted the formation of amorphous silica, resulting in a threefold increase in dissolved silicon in sichars prepared at 400 °C. Additionally, we observed the formation of a meta-stable SiO2 polymorph (tridymite) in rice husk-derived biochars under fast heating, differing from the previously observed quartz generated at slow heating rates. Regarding the CSi relationship, a faster heating rate facilitated the removal of the surface carbon layer, exposing the underlying silicon layer. This led to more soluble silicon species and less encapsulated silicon, resulting in a continuous release and cumulative silicon dissolution amount 1.2 times and 1.6-1.9 times higher, respectively, than those in slow heating rate-derived sichars. Consequently, this enhanced silicon uptake in rice seedlings. Our findings indicate that beyond pyrolysis temperature, the heating rate significantly affects the silicon species, silicon dissolution behavior, and carbon­silicon relationships of biochar, ultimately determines the properties and applications of sichars.

4.
J Biomech ; 173: 112247, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-39053293

RESUMEN

A three-partition distributed force platform (3P-DFP) is proposed to measure the plantar pressure distribution, and foot support characteristics are evaluated with the obtained pressure distribution information. Twenty-seven young adults and 40 elderly adults were randomly recruited to perform the test in three phases: double-leg stance with eyes closed, double-leg stance with eyes opened, and single-leg stance with eyes opened. The evaluation parameters of foot support surface characteristics and support point characteristics were calculated based on the average position information of the center of pressure in the lateral of sole, media of sole, posterior of heel, and entire pelma. The results showed that the support width of the foot sole was significantly greater in the elderly group (p <0.01), but the overall support area showed a decreasing trend. The CoP excursion in the media-lateral direction was significantly higher in the elderly group from double-leg stance to single-leg stance (p <0.01). The CoP trajectory in the elderly group tends to shift in a medial direction with increasing age or postural difficulty.


Asunto(s)
Pie , Humanos , Pie/fisiología , Anciano , Femenino , Masculino , Adulto , Presión , Fenómenos Biomecánicos , Envejecimiento/fisiología , Equilibrio Postural/fisiología , Adulto Joven , Persona de Mediana Edad
5.
Environ Sci Technol ; 58(27): 12147-12154, 2024 Jul 09.
Artículo en Inglés | MEDLINE | ID: mdl-38934559

RESUMEN

Increasing worldwide contamination with organic chemical compounds is a paramount environmental challenge facing humanity. Once they enter nature, pollutants undergo transformative processes that critically shape their environmental impacts and associated risks. This research unveils previously overlooked yet widespread pathways for the transformations of organic pollutants triggered by water vapor condensation, leading to spontaneous oxidation and hydrolysis of organic pollutants. These transformations exhibit variability through either sequential or parallel hydrolysis and oxidation, contingent upon the functional groups within the organic pollutants. For instance, acetylsalicylic acid on the goethite surface underwent sequential hydrolysis and oxidation that first hydrolyzed to salicylic acid followed by hydroxylation oxidation of the benzene moiety driven by the hydroxyl radical (•OH). In contrast, chloramphenicol underwent parallel oxidation and hydrolysis, forming hydroxylated chloramphenicol and 2-amino-1-(4-nitrophenyl)-1,3-propanediol, respectively. The spontaneous oxidation and hydrolysis occurred consistently on three naturally abundant iron minerals with the key factors being •OH production capacity and surface binding strength. Given the widespread presence of iron minerals on Earth's surface, these spontaneous transformation paths could play a role in the fate and risks of organic pollutants of health concerns.


Asunto(s)
Hierro , Oxidación-Reducción , Hidrólisis , Hierro/química , Minerales/química , Vapor , Compuestos Orgánicos/química , Radical Hidroxilo/química
6.
Environ Sci Technol ; 58(23): 10287-10297, 2024 Jun 11.
Artículo en Inglés | MEDLINE | ID: mdl-38805641

RESUMEN

Though long recognized as synthetic precursors to other poly- and perfluoroalkyl substances (PFASs), most poly- and perfluoroalkyl sulfonyl halides (PASXs) cannot be directly measured and have generally received minimal attention. Inspired by the redox reaction between sulfonyl halide groups and p-toluenethiol in organic chemistry, we developed a novel nontarget analysis strategy for PASXs by intergrating derivatization and specific fragment-based liquid chromatography-high resolution mass spectrometry screening for m/z 82.961 [SO2F-] and m/z 95.934 [S2O2-]. By using this strategy, we discovered 11 PASXs, namely, perfluoroalkyl sulfonyl fluorides (5), polyfluoroalkyl sulfonyl fluorides (2), unsaturated perfluoroalkyl sulfonyl fluoride (1), and perfluoroalkyl sulfonyl chlorides (3) in soil samples collected from an abandoned fluorochemical manufacturing park. These average ∑PASXs concentrations were 1120 µg kg-1 (range: 9.7-9860 µg kg-1), which were very likely to be the key intermediates and undesired byproducts of electrochemical fluorination processes. Spatial variation in the mass ratio of ∑PASXs to ∑PFSAs (range: 0.7-795%) also indicates their different transportation pathways. More importantly, the decline of PASXs and increase of perfluoroalkyl sulfonates (when compared to a prior study at this site) suggest the continued hydrolysis of PASXs and the relatively fast environmental transformation rates in the abandoned fluorochemical park soils. Overall, these findings demonstrated the utility of a novel nontarget analysis strategy, which may change most PASXs from inferred precursors to measured intermediates and further could be adapted for structures, distribution, and transformation studies of PFASXs in other matrices.


Asunto(s)
Espectrometría de Masas , Contaminantes del Suelo , Suelo , Cromatografía Liquida , Contaminantes del Suelo/química , Suelo/química , Fluorocarburos/química , Monitoreo del Ambiente/métodos
7.
Environ Sci Technol ; 58(23): 10072-10083, 2024 Jun 11.
Artículo en Inglés | MEDLINE | ID: mdl-38810213

RESUMEN

The oxygen reduction process generating H2O2 in the photoelectrochemical (PEC) system is milder and environmentally friendly compared with the traditional anthraquinone process but still lacks the efficient electron-oxygen-proton coupling interfaces to improve H2O2 production efficiency. Here, we propose an integrated active site strategy, that is, designing a hydrophobic C-B-N interface to refine the dearth of electron, oxygen, and proton balance. Computational calculation results show a lower energy barrier for H2O2 production due to synergistic and coupling effects of boron sites for O2 adsorption, nitrogen sites for H+ binding, and the carbon structure for electron transfer, demonstrating theoretically the feasibility of the strategy. Furthermore, we construct a hydrophobic boron- and nitrogen-doped carbon black gas diffusion cathode (BN-CB-PTFE) with graphite carbon dots decorated on a BiVO4 photoanode (BVO/g-CDs) for H2O2 production. Remarkably, this approach achieves a record H2O2 production rate (9.24 µmol min-1 cm-2) at the PEC cathode. The BN-CB-PTFE cathode exhibits an outstanding Faraday efficiency for H2O2 production of ∼100%. The newly formed h-BN integrative active site can not only adsorb more O2 but also significantly improve the electron and proton transfer. Unexpectedly, coupling BVO/g-CDs with the BN-CB-PTFE gas diffusion cathode also achieves a record H2O2 production rate (6.60 µmol min-1 cm-2) at the PEC photoanode. This study opens new insight into integrative active sites for electron-O2-proton coupling in a PEC H2O2 production system that may be meaningful for environment and energy applications.


Asunto(s)
Electrodos , Electrones , Peróxido de Hidrógeno , Oxígeno , Protones , Oxígeno/química , Peróxido de Hidrógeno/química , Técnicas Electroquímicas
8.
Environ Sci Technol ; 58(20): 8610-8630, 2024 May 21.
Artículo en Inglés | MEDLINE | ID: mdl-38720447

RESUMEN

Solar desalination, a green, low-cost, and sustainable technology, offers a promising way to get clean water from seawater without relying on electricity and complex infrastructures. However, the main challenge faced in solar desalination is salt accumulation, either on the surface of or inside the solar evaporator, which can impair solar-to-vapor efficiency and even lead to the failure of the evaporator itself. While many ideas have been tried to address this ″salt accumulation″, scientists have not had a clear system for understanding what works best for the enhancement of salt-rejecting ability. Therein, for the first time, we classified the state-of-the-art salt-rejecting designs into isolation strategy (isolating the solar evaporator from brine), dilution strategy (diluting the concentrated brine), and crystallization strategy (regulating the crystallization site into a tiny area). Through the specific equations presented, we have identified key parameters for each strategy and highlighted the corresponding improvements in the solar desalination performance. This Review provides a semiquantitative perspective on salt-rejecting designs and critical parameters for enhancing the salt-rejecting ability of dilution-based, isolation-based, and crystallization-based solar evaporators. Ultimately, this knowledge can help us create reliable solar desalination solutions to provide clean water from even the saltiest sources.


Asunto(s)
Agua de Mar , Purificación del Agua , Purificación del Agua/métodos , Agua de Mar/química , Luz Solar , Salinidad , Sales (Química)/química , Cloruro de Sodio/química
9.
IEEE Trans Image Process ; 33: 3227-3241, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-38691435

RESUMEN

The statistical regularities of natural images, referred to as natural scene statistics, play an important role in no-reference image quality assessment. However, it has been widely acknowledged that screen content images (SCIs), which are typically computer generated, do not hold such statistics. Here we make the first attempt to learn the statistics of SCIs, based upon which the quality of SCIs can be effectively determined. The underlying mechanism of the proposed approach is based upon the mild assumption that the SCIs, which are not physically acquired, still obey certain statistics that could be understood in a learning fashion. We empirically show that the statistics deviation could be effectively leveraged in quality assessment, and the proposed method is superior when evaluated in different settings. Extensive experimental results demonstrate the Deep Feature Statistics based SCI Quality Assessment (DFSS-IQA) model delivers promising performance compared with existing NR-IQA models and shows a high generalization capability in the cross-dataset settings. The implementation of our method is publicly available at https://github.com/Baoliang93/DFSS-IQA.

10.
Environ Sci Technol ; 58(24): 10623-10631, 2024 Jun 18.
Artículo en Inglés | MEDLINE | ID: mdl-38781516

RESUMEN

Iron minerals are widespread in earth's surface water and soil. Recent studies have revealed that under sunlight irradiation, iron minerals are photoactive on producing reactive oxygen species (ROS), a group of key species in regulating elemental cycling, microbe inactivation, and pollutant degradation. In nature, iron minerals exhibit varying crystallinity under different hydrogeological conditions. While crystallinity is a known key parameter determining the overall activity of iron minerals, the impact of iron mineral crystallinity on photochemical ROS production remains unknown. Here, we assessed the photochemical ROS production from ferrihydrites with different degrees of crystallinity. All examined ferrihydrites demonstrated photoactivity under irradiation, resulting in the generation of hydrogen peroxide (H2O2) and hydroxyl radical (•OH). The photochemical ROS production from ferrihydrites increased with decreasing ferrihydrite crystallinity. The crystallinity-dependent photochemical •OH production was primarily attributed to conduction band reduction reactions, with the reduction of O2 by conduction band electrons being the rate-limiting key process. Conversely, the crystallinity of iron minerals had a negligible influence on photon-to-electron conversion efficiency or surface Fenton-like activity. The difference in ROS productions led to a discrepant degradation efficiency of organic pollutants on iron mineral surfaces. Our study provides valuable insights into the crystallinity-dependent ROS productions from iron minerals in natural systems, emphasizing the significance of iron mineral photochemistry in natural sites with abundant lower-crystallinity iron minerals such as wetland water and surface soils.


Asunto(s)
Hierro , Minerales , Especies Reactivas de Oxígeno , Hierro/química , Especies Reactivas de Oxígeno/química , Minerales/química , Radical Hidroxilo/química , Peróxido de Hidrógeno/química
11.
Environ Sci Technol ; 58(15): 6763-6771, 2024 Apr 16.
Artículo en Inglés | MEDLINE | ID: mdl-38572777

RESUMEN

Understanding interfacial interactions of graphene oxide (GO) is important to evaluate its colloidal behavior and environmental fate. Single-layer GO is the fundamental unit of GO colloids, and its interfacial aqueous layers critically dictate these interfacial interactions. However, conventional techniques like X-ray diffraction are limited to multilayer systems and are inapplicable to single-layer GO. Therefore, our study employed atomic force microscopy to precisely observe the in situ dynamic behaviors of interfacial aqueous layers on single-layer GO. The interfacial aqueous layer height was detected at the subnanometer level. In real-time monitoring, the single-layer height increased from 1.17 to 1.70 nm within 3 h immersion. This sluggish process is different from the rapid equilibration of multilayer GO in previous studies, underscoring a gradual transition in hydration kinetics. Ion strength exhibited negligible influence on the single-layer height, suggesting a resilient response of the interfacial aqueous layer to ion-related perturbations due to intricate ion interactions and electrical double-layer compression. Humic acid led to a substantial increase in the interfacial aqueous layers, improving the colloidal stability of GO and augmenting its potential for migration. These findings hold considerable significance regarding the environmental behaviors of the GO interfacial aqueous layer in ion- and organic-rich water and soil.


Asunto(s)
Grafito , Agua , Microscopía de Fuerza Atómica , Coloides
12.
J Mater Chem B ; 12(17): 4208-4216, 2024 May 01.
Artículo en Inglés | MEDLINE | ID: mdl-38595308

RESUMEN

The primary focal point in the fabrication of microfiltration membranes revolves around mitigating issues of low permeability stemming from the initial design as well as countering biofouling tendencies. This work aimed to address these issues by synthesizing an antibacterial capsaicin derivative (CD), which was then grafted to the poly(vinylidene fluoride-co-chlorotrifluoroethylene)-g-polymethacrylic acid (P(VDF-CTFE)-g-PMAA) matrix polymer, resulting in an antibacterial polymer (PD). Notably, both CD and PD demonstrated low cytotoxicities. Utilizing PD, a microfiltration membrane (MA) was successfully prepared through non-solvent-induced phase inversion. The pore sizes of the MA membrane were mainly concentrated at around 436 nm, while the pure water flux of MA reached an impressive value of 62 ± 0.17 Lm-2 h-1 at 0.01 MPa. MA exhibited remarkable efficacy in eradicating both Gram-negative (E. coli) and Gram-positive bacteria (Bacillus subtilis) from its surface. Compared with M1 prepared from P(VDF-CTFE), MA exhibited a lower flux decay rate (41.00% vs. 76.03%) and a higher flux recovery rate (84.95% vs. 46.54%) after three cycles. Overall, this research represents a significant step towards the development of a microfiltration membrane with inherent stable anti-biofouling capability to enhance filtration.


Asunto(s)
Antibacterianos , Bacillus subtilis , Incrustaciones Biológicas , Capsaicina , Escherichia coli , Membranas Artificiales , Incrustaciones Biológicas/prevención & control , Antibacterianos/farmacología , Antibacterianos/química , Antibacterianos/síntesis química , Escherichia coli/efectos de los fármacos , Capsaicina/química , Capsaicina/farmacología , Bacillus subtilis/efectos de los fármacos , Pruebas de Sensibilidad Microbiana , Filtración , Propiedades de Superficie , Tamaño de la Partícula
13.
J Hazard Mater ; 470: 134115, 2024 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-38626676

RESUMEN

EDTA has been widely utilized as a chelating agent in soil heavy metal remediation, due to its strong coordination capability. Electrochemical deposition is a promising avenue to treat soil washing effluent. However, the impact of advanced electrochemical techniques on EDTA remains incompletely understood. Herein, we present a pioneering approach, utilizing a dual-chamber electrolytic cell and alternating current (AC) power supply. This approach achieves concurrent removal of M-EDTA while efficiently recovering heavy metal and recycling EDTA. Results demonstrate AC displays superior heavy metal removal capability for Cu, Pb, and Cd compare to direct current (DC), with EDTA decomposition mainly occurring in the anolyte. Substituting DC with AC and employing the dual-chamber electrolytic cell significantly enhances EDTA recovery efficiency from 47% to an impressive 96.8%. XPS and Raman spectra reveal an enhanced oxidative surface of the graphite anode under AC, which diminishes the decomposition of EDTA. Long-term experiments validate that this strategy boosts EDTA cyclability to 20 cycles with an outstanding 84% recovery efficiency and negligible electrode corrosion, surpassing the 8 cycles under the traditional strategy. This study innovatively combines cell design and electrochemical techniques, remarkably improving the reusability of EDTA and anode, offering valuable insights for chelate-related applications.

14.
J Hazard Mater ; 466: 133641, 2024 Mar 15.
Artículo en Inglés | MEDLINE | ID: mdl-38309157

RESUMEN

Manganese (Mn) redox cycling and phase variation reactions play a crucial role in natural water settings. Rhodochrosite (MnCO3), a mineral commonly found in oxygen-deprived environments, develops a surface oxide film upon exposure to oxygen. This Mn oxide film significantly influences the fate of nanoparticles within its proximity. Employing atomic force microscopy (AFM), this study examined the growth of the Mn oxide film on MnCO3 and the encapsulation of cadmium sulfide nanoparticles (CdS-NPs). Results revealed the gradual development of a nanometer-thick oxide film on MnCO3 over time in aerobic conditions, with the rate of film formation correlated to the solution's ionic strength. The oxide film on MnCO3 encapsulated pre-adsorbed CdS-NPs, either through embedding or covering. Intriguingly, CdS-NPs were found to enhance the growth of the Mn oxide film, contributing to the fixation of CdS-NPs. Furthermore, an ultrasonic desorption protocol verified the stability of CdS-NPs encapsulated by the Mn oxide film on MnCO3. This study elucidates a novel mechanism for immobilizing CdS-NPs in aqueous oxidizing conditions, providing valuable insights into the behavior and distribution of toxic nanoparticles in environmental contexts. ENVIRONMENTAL IMPLICATION: This study classifies cadmium sulfide nanoparticles (CdS-NPs) as "hazardous material" due to the inherent toxicity of cadmium, posing risks to both ecological and human health. The research addresses environmental concerns by exploring the interaction between CdS-NPs and manganese (Mn) redox cycling. The formation of a Mn oxide film, encapsulating CdS-NPs, suggests a mechanism for limiting the dispersion of these hazardous nanoparticles in oxidizing water. This provides valuable insights for managing the environmental impact of CdS-NPs, offering a proactive strategy to mitigate their adverse effects in natural systems.

15.
Environ Sci Technol ; 58(8): 3838-3848, 2024 Feb 27.
Artículo en Inglés | MEDLINE | ID: mdl-38351523

RESUMEN

Substantial natural chlorination processes are a growing concern in diverse terrestrial ecosystems, occurring through abiotic redox reactions or biological enzymatic reactions. Among these, exoenzymatically mediated chlorination is suggested to be an important pathway for producing organochlorines and converting chloride ions (Cl-) to reactive chlorine species (RCS) in the presence of reactive oxygen species like hydrogen peroxide (H2O2). However, the role of natural enzymatic chlorination in antibacterial activity occurring in soil microenvironments remains unexplored. Here, we conceptualized that heme-containing chloroperoxidase (CPO)-catalyzed chlorination functions as a naturally occurring disinfection process in soils. Combining antimicrobial experiments and microfluidic chip-based fluorescence imaging, we showed that the enzymatic chlorination process exhibited significantly enhanced antibacterial activity against Escherichia coli and Bacillus subtilis compared to H2O2. This enhancement was primarily attributed to in situ-formed RCS. Based on semiquantitative imaging of RCS distribution using a fluorescence probe, the effective distance of this antibacterial effect was estimated to be approximately 2 mm. Ultrahigh-resolution mass spectrometry analysis showed over 97% similarity between chlorine-containing formulas from CPO-catalyzed chlorination and abiotic chlorination (by sodium hypochlorite) of model dissolved organic matter, indicating a natural source of disinfection byproduct analogues. Our findings unveil a novel natural disinfection process in soils mediated by indigenous enzymes, which effectively links chlorine-carbon interactions and reactive species dynamics.


Asunto(s)
Contaminantes Químicos del Agua , Purificación del Agua , Desinfección , Cloro/química , Cloro/metabolismo , Halogenación , Peróxido de Hidrógeno , Suelo , Ecosistema , Antibacterianos , Catálisis
16.
Sci Total Environ ; 916: 170414, 2024 Mar 15.
Artículo en Inglés | MEDLINE | ID: mdl-38272084

RESUMEN

Sunlight-induced photochemical transformations greatly affect the persistence of organic pollutants in natural environment. Whereas sunlight intensity is well-known to affect pollutant phototransformation rates, the reliance of pollutant phototransformation kinetics on sunlight spectrum remains poorly understood, which may greatly vary under different spatial-temporal, water matrix, and climatic conditions. Here, we systematically assessed the wavelength-dependent direct and indirect phototransformations of 12 organic pollutants. Their phototransformation rates dramatically decreased with light wavelength increasing from 375 to 632 nm, with direct photolysis displaying higher wavelength-dependence than indirect photolysis. Remarkably, UV light dominated both direct (90.4-99.5 %) and indirect (64.6-98.7 %) photochemical transformations of all investigated organic pollutants, despite its minor portion in sunlight spectrum (e.g., 6.5 % on March 20 at the equator). Based on wavelength-dependent rate constant spectrum, the predicted phototransformation rate of chloramphenicol (4.5 ± 0.7 × 10-4 s-1) agreed well with the observed rate under outdoor sunlight irradiation (4.3 ± 0.0 × 10-4 s-1), and there is no significant difference between the predicted rate and the observed rate (p-value = 0.132). Moreover, rate constant and quantum yield coefficient (QYC) spectrum could be applied for facilely investigate the influence of spectral changes on the phototransformation of pollutants under varying spatial-temporal (e.g., season, latitude) and climatic conditions (e.g., cloud cover). Our study highlights the wavelength-dependence of both direct and indirect phototransformation of pollutants, and the UV part of natural sunlight plays a decisive role in the phototransformation of pollutants.

17.
Environ Sci Technol ; 58(6): 2808-2816, 2024 Feb 13.
Artículo en Inglés | MEDLINE | ID: mdl-38227742

RESUMEN

Hydroxyl radical (•OH) is a powerful oxidant abundantly found in nature and plays a central role in numerous environmental processes. On-site detection of •OH is highly desirable for real-time assessments of •OH-centered processes and yet is restrained by a lack of an analysis system suitable for field applications. Here, we report the development of a flow-injection chemiluminescence analysis (FIA-CL) system for the continuous field detection of •OH. The system is based on the reaction of •OH with phthalhydrazide to generate 5-hydroxy-2,3-dihydro-1,4-phthalazinedione, which emits chemiluminescence (CL) when oxidatively activated by H2O2 and Cu3+. The FIA-CL system was successfully validated using the Fenton reaction as a standard •OH source. Unlike traditional absorbance- or fluorescence-based methods, CL detection could minimize interference from an environmental medium (e.g., organic matter), therefore attaining highly sensitive •OH detection (limits of detection and quantification = 0.035 and 0.12 nM, respectively). The broad applications of FIA-CL were illustrated for on-site 24 h detection of •OH produced from photochemical processes in lake water and air, where the temporal variations on •OH productions (1.0-12.2 nM in water and 1.5-37.1 × 107 cm-3 in air) agreed well with sunlight photon flux. Further, the FIA-CL system enabled field 24 h field analysis of •OH productions from the oxidation of reduced substances triggered by tidal fluctuations in coastal soils. The superior analytical capability of the FIA-CL system opens new opportunities for monitoring •OH dynamics under field conditions.


Asunto(s)
Radical Hidroxilo , Luminiscencia , Radical Hidroxilo/análisis , Radical Hidroxilo/química , Peróxido de Hidrógeno , Oxidación-Reducción , Agua
18.
ChemSusChem ; 17(6): e202301284, 2024 Mar 22.
Artículo en Inglés | MEDLINE | ID: mdl-37934454

RESUMEN

Na superionic conductor (NASICON) materials hold promise as solid-state electrolytes due to their wide electrochemical stability and chemical durability. However, their limited ionic conductivity hinders their integration into sodium-ion batteries. The conventional approach to electrolyte design struggles with comprehending the intricate interactions of factors impacting conductivity, encompassing synthesis parameters, structural characteristics, and electronic descriptors. Herein, we explored the potential of machine learning in predicting ionic conductivity in NASICON. We compile a database of 211 datasets, covering 160 NASICON materials, and employ facile descriptors, including synthesis parameters, test conditions, molecular and structural attributes, and electronic properties. Random forest (RF) and neural network (NN) models were developed and optimized, with NN performing notably better, particularly with limited data (R2=0.820). Our analysis spotlighted the pivotal role of Na stoichiometric count in ionic conductivity. Furthermore, the NN algorithm highlighted the comparable significance of synthesis parameters to structural factors in determining conductivity. In contrast, the impact of electronegativity on doped elements appears less significant, underscoring the importance of dopant size and quantity. This work underscores the potential of machine learning in advancing NASICON electrolyte design for sodium-ion batteries, offering insights into conductivity drivers and a more efficient path to optimizing materials.

19.
Environ Sci Technol ; 58(1): 432-439, 2024 Jan 09.
Artículo en Inglés | MEDLINE | ID: mdl-38111081

RESUMEN

Reactive oxygen species (ROS) are widespread in nature and play central roles in numerous biogeochemical processes and pollutant dynamics. Recent studies have revealed ROS productions triggered by electron transfer from naturally abundant reduced iron minerals to oxygen. Here, we report that ROS productions from pyrite oxidation exhibit a high facet dependence. Pyrites with various facet compositions displayed distinct efficiencies in producing superoxide (O2• -), hydrogen peroxide (H2O2), and hydroxyl radical (•OH). The 48 h •OH production rates varied by 3.1-fold from 11.7 ± 0.4 to 36.2 ± 0.6 nM h-1, showing a strong correlation with the ratio of the {210} facet. Such facet dependence in ROS productions primarily stems from the different surface electron-donating capacities (2.2-8.6 mmol e- g-1) and kinetics (from 1.2 × 10-4 to 5.8 × 10-4 s-1) of various faceted pyrites. Further, the Fenton-like activity also displayed 10.1-fold variations among faceted pyrites, contributing to the facet depedence of •OH productions. The facet dependence of ROS production can greatly affect ROS-driven pollutant transformations. As a paradigm, the degradation rates of carbamazepine, phenol, and bisphenol A varied by 3.5-5.3-fold from oxidation of pyrites with different facet compositions, where the kinetics were in good agreement with the pyrite {210} facet ratio. These findings highlight the crucial role of facet composition in determining ROS production and subsequent ROS-driven reactions during iron mineral oxidation.


Asunto(s)
Contaminantes Ambientales , Peróxido de Hidrógeno , Especies Reactivas de Oxígeno/química , Especies Reactivas de Oxígeno/metabolismo , Peróxido de Hidrógeno/química , Peróxido de Hidrógeno/metabolismo , Hierro/química , Oxidación-Reducción , Oxígeno
20.
Environ Sci Technol ; 57(51): 21855-21865, 2023 Dec 26.
Artículo en Inglés | MEDLINE | ID: mdl-38086098

RESUMEN

Per- and polyfluoroalkyl substances (PFAS) represent significant stress to organisms and are known to disrupt microbial community structure and function. Nevertheless, a detailed knowledge of the soil microbial community responding to PFAS stress at the metabolism level is required. Here we integrated UPLC-HRMS-based metabolomics data with 16S rRNA and ITS amplicon data across soil samples collected adjacent to a fluoropolymer production facility to directly identify the biochemical intermediates in microbial metabolic pathways and the interactions with microbial community structure under PFAS stress. A strong correlation between metabolite and microbial diversity was observed, which demonstrated significant variations in soil metabolite profiles and microbial community structures along with the sampling locations relative to the facility. Certain key metabolites were identified in the metabolite-PFAS co-occurrence network, functioning on microbial metabolisms including lipid metabolism, amino acid metabolism, and secondary metabolite biosynthesis. These results provide novel insights into the impacts of PFAS contamination on soil metabolomes and microbiomes. We suggest that soil metabolomics is an informative and useful tool that could be applied to reinforce the chemical evidence on the disruption of microbial ecological traits.


Asunto(s)
Ácidos Alcanesulfónicos , Fluorocarburos , Microbiota , Suelo/química , ARN Ribosómico 16S/genética , Fluorocarburos/análisis , Polímeros de Fluorocarbono
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