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1.
Water Res ; 247: 120785, 2023 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-37931360

RESUMO

Visible light photocatalysis is widely considered a sustainable approach to break down micropollutants without chemical addition. To promote the output of photogenerated carriers under visible light, a Z-scheme plasmonic photocatalyst Bi-CeO2/Ag0/BiO2 was designed and fabricated to activate dissolved oxygen in water for micropollutant degradation. The doped Bi not only improved the separation of electron-hole, but also narrowed the band gap of CeO2 to enhance its absorption of visible light. Notably, metallic silver (Ag0) works as an electronic transmission vehicle from Bi-CeO2 to BiO2 in a Z-scheme mechanism. Likewise, the surface plasmon resonance effect of Ag0 also enhanced the absorption of visible light. Furthermore, the Bi doping induced abundant surface oxygen vacancies on CeO2 for enhanced capability and selectivity towards O2 adsorption and activation, which favored the generation of O2•- by photogenerated electrons to degrade sulfamethoxazole, enrofloxacin, and bisphenol A. Theoretical calculation results also confirmed the O2•--driven degradation pathway for sulfamethoxazole. Therefore, the Z-scheme Bi-CeO2/Ag0/BiO2 not only extends the photocatalytic reactivity of CeO2-based catalysts to the visible light range, but also provides a chemical-free method to effectively degrade micropollutants.


Assuntos
Luz , Sulfametoxazol , Catálise
2.
Environ Res ; 237(Pt 2): 117013, 2023 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-37648190

RESUMO

Given that the spontaneous precipitation of minerals caused by urea hydrolysis and abundant organic compounds, membrane fouling became a major obstacle for urine recovery by membrane distillation (MD). Herein, this study developed a combined system (TAP-MD) by integrating thermally activated peroxydisulfate (TAP) and MD process to inhibit membrane fouling and improve separation efficiency. Based on the TAP-MD system, the separation performance was improved significantly, improving nutrient recovery efficiency and quality of reclaimed water. More than 80% of water could be recovered from urine, and about 94.13% of total ammonia nitrogen (TAN), 99.02% of total nitrogen (TN), 100% of total phosphate (TP), and 100% of K+ were rejected. The mechanism for alleviating urine-induced fouling was systematically and intensively studied. With TAP pretreatment, the TAN concentration of pretreated urine was kept at a low level steadily and the pH was at neutral or weakly acidic. Hence, inorganic scaling represented by carbonate and phosphate precipitates were significantly inhibited by creating unfavorable solvent environment for crystallization with TAP pretreatment. Additionally, aromatic proteins were found as the main organic foulants. According to the secondary structure of protein, the proteins were degraded by the cleavage of peptide bonds by TAP pretreatment. Meanwhile, the hydrophilicity of protein increased, which reduced the hydrophobic interaction of protein and membrane surface and thus alleviated protein-induced membrane fouling. This study revealed the inorganic and organic foulants in urine that caused membrane fouling and demonstrated the mechanism of membrane fouling alleviation by TAP-MD system. The experimental results will be instrumental in better understanding the mechanisms of membrane fouling induced by urine and optimize MD process for resource recovery from urine.

3.
Environ Sci Technol ; 57(33): 12153-12179, 2023 08 22.
Artigo em Inglês | MEDLINE | ID: mdl-37535865

RESUMO

Urbanization and industrialization have exerted significant adverse effects on water quality, resulting in a growing need for reliable and eco-friendly treatment technologies. Persulfate (PS)-based advanced oxidation processes (AOPs) are emerging as viable technologies to treat challenging industrial wastewaters or remediate groundwater impacted by hazardous wastes. While the generated reactive species can degrade a variety of priority organic contaminants through radical and nonradical pathways, there is a lack of systematic and in-depth comparison of these pathways for practical implementation in different treatment scenarios. Our comparative analysis of reaction rate constants for radical vs. nonradical species indicates that radical-based AOPs may achieve high removal efficiency of organic contaminants with relatively short contact time. Nonradical AOPs feature advantages with minimal water matrix interference for complex wastewater treatments. Nonradical species (e.g., singlet oxygen, high-valent metals, and surface activated PS) preferentially react with contaminants bearing electron-donating groups, allowing enhancement of degradation efficiency of known target contaminants. For byproduct formation, analytical limitations and computational chemistry applications are also considered. Finally, we propose a holistically estimated electrical energy per order of reaction (EE/O) parameter and show significantly higher energy requirements for the nonradical pathways. Overall, these critical comparisons help prioritize basic research on PS-based AOPs and inform the merits and limitations of system-specific applications.


Assuntos
Poluentes Químicos da Água , Purificação da Água , Poluentes Químicos da Água/análise , Oxirredução , Águas Residuárias , Purificação da Água/métodos
4.
Environ Sci Technol ; 57(26): 9832-9842, 2023 07 04.
Artigo em Inglês | MEDLINE | ID: mdl-37327199

RESUMO

Photochemical transformation is an important process that involves trace organic contaminants (TrOCs) in sunlit surface waters. However, the environmental implications of their self-photosensitization pathway have been largely overlooked. Here, we selected 1-nitronaphthalene (1NN), a representative nitrated polycyclic aromatic hydrocarbon, to study the self-photosensitization process. We investigated the excited-state properties and relaxation kinetics of 1NN after sunlight absorption. The intrinsic decay rate constants of triplet (31NN*) and singlet (11NN*) excited states were estimated to be 1.5 × 106 and 2.5 × 108 s-1, respectively. Our results provided quantitative evidence for the environmental relevance of 31NN* in waters. Possible reactions of 31NN* with various water components were evaluated. With the reduction and oxidation potentials of -0.37 and 1.95 V, 31NN* can be either oxidized or reduced by dissolved organic matter isolates and surrogates. We also showed that hydroxyl (•OH) and sulfate (SO4•-) radicals can be generated via the 31NN*-induced oxidation of inorganic ions (OH- and SO42-, respectively). We further investigated the reaction kinetics of 31NN* and OH- forming •OH, an important photoinduced reactive intermediate, through complementary experimental and theoretical approaches. The rate constants for the reactions of 31NN* with OH- and 1NN with •OH were determined to be 4.22 × 107 and 3.95 ± 0.01 × 109 M-1 s-1, respectively. These findings yield new insights into self-photosensitization as a pathway for TrOC attenuation and provide more mechanistic details into their environmental fate.


Assuntos
Hidrocarbonetos Policíclicos Aromáticos , Poluentes Químicos da Água , Nitratos , Fotólise , Compostos Orgânicos , Radical Hidroxila/química , Cinética , Poluentes Químicos da Água/análise
5.
Chemosphere ; 328: 138614, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37023899

RESUMO

In this study, SiO2-composited biochar decorated with Fe/Mn was prepared by co-pyrolysis method. The degradation performance of the catalyst was evaluated by activating persulfate (PS) to degrade tetracycline (TC). The effects of pH, initial TC concentration, PS concentration, catalyst dosage and coexisting anions on degradation efficiency and kinetics of TC were investigated. Under optimal conditions (TC = 40 mg L-1, pH = 6.2, PS = 3.0 mM, catalyst = 0.1 g L-1), the kinetic reaction rate constant could reach 0.0264 min-1 in Fe2Mn1@BC-0.3SiO2/PS system, which was 12 times higher than that in the BC/PS system (0.00201 min-1). The electrochemical, X-ray diffractometer (XRD), Fourier transform infrared spectrum (FT-IR) and X-ray photoelectron spectroscopy (XPS) analysis showed that both metal oxides and oxygen-containing functional groups provide more active sites to activate PS. The redox cycle between Fe(II)/Fe(III) and Mn(II)/Mn(III)/Mn(IV) accelerated the electron transfer and sustained the catalytic activation of PS. Radical quenching experiments and electron spin resonance (ESR) measurements confirmed that surface sulfate radical (SO4•-) play a key role in TC degradation. Three possible degradation pathways of TC were proposed based on high-performance liquid chromatography coupled with high-resolution mass spectrometry (HPLC-HRMS) analysis, the toxicity of TC and its intermediates was analyzed by bioluminescence inhibition test. In addition to the enhanced catalytic performance, the presence of silica also improved the stability of the catalyst, as confirmed by cyclic experiment and metal ion leaching analysis. The Fe2Mn1@BC-0.3SiO2 catalyst, derived from low-cost metals and bio-waste materials, offer an environmentally friendly option to design and implement heterogenous catalyst system for pollutant removal in water.


Assuntos
Esgotos , Dióxido de Silício , Compostos Férricos/química , Espectroscopia de Infravermelho com Transformada de Fourier , Tetraciclina/química , Antibacterianos/química , Carvão Vegetal/química
6.
Water Res ; 235: 119829, 2023 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-36958219

RESUMO

Advanced oxidation/reduction of PFAS is challenged and concerned by the formation of toxic, short-chain intermediates during water treatments. In this study, we investigated the complete defluorination of PFOA by ultrasound/persulfate (US/PS) with harmless end-products of CO2, H2O, and F‒ ions. We observed 100% defluorination after 4 h of US treatment alone with a power input of 900 W. PS addition, however, suppressed defluorination. We demonstrated by kinetics-fitted Langmuir-type adsorption modeling, the added PS increased competition with PFOA for adsorption sites on the bubble-water interface where radical oxidation and pyrolysis may occur. Providing sulfate (SO4•-) and hydroxyl (•OH) radicals by means other than US did not defluorinate PFOA, indicating that pyrolysis likely contributes to the high defluorination performance. Bond dissociation energies for CC and CF were independent of pressure but decreased at elevated temperatures within cavitation bubbles (i.e., 5000 K) favoring the pyrolysis reactions. Furthermore, bond length calculations indicated that PFOA cleavage only begins to occur at temperatures in excess of those generated at the bubble interface (i.e., >1500 K) at the femtosecond level. This suggests that PFOA vaporizes or injects by nanodrops upon attachment to the cavitation bubble, enters the bubble, and is then cleaved within the bubble by pyrolysis. Our research in low-frequency ultrasonic horn system challenges the previous founding that defluorination of PFOA initiates and occurs at the bubble-water interface. We describe here that supplementing US-based processes with complementary treatments may have undesired effects on the efficacy of US. The mechanistic insights will further promote the implementation of US technology for PFAS treatment in achieving the zero fluoro-pollution goal.


Assuntos
Fluorocarbonos , Pirólise , Ultrassom , Fluorocarbonos/química , Caprilatos/química
7.
Water Res ; 235: 119838, 2023 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-36921358

RESUMO

Electro-Fenton (EF) process represents an energy-efficient and scalable advanced oxidation technology (AOT) for micropollutants removal in wastewaters. However, mechanistic profiling and quantitation of contribution of each subprocess (i.e., adsorption at electrode, coagulation, radical oxidation, electrode oxidation/reduction, and H2O2 oxidation) to the overall degradation are substantially unclear, resulting in difficulty in tunability and optimization for different treatment scenarios. In this study, we investigated degradation kinetics of a target micropollutant in an EF system. The contribution of all possible subprocesses was elucidated by comparing the observed degradation rate in the EF system with the sum of the kinetics in each subprocess. The results indicated that the overall degradation can be attributed to the synergistic action of the above-mentioned subprocesses. The radical oxidation accounts for 87% elimination, followed by electrode reoxidation/reduction of 7.7%. These results not only advance the fundamental understanding of synergistic effect in EF system, but also open new possibilities to optimize these techniques for better scalability. In addition, the methodology in this study could potentially boost the in-depth exploration of subprocess contribution in other Fenton-like systems.


Assuntos
Poluentes Químicos da Água , Purificação da Água , Peróxido de Hidrogênio , Águas Residuárias , Purificação da Água/métodos , Oxirredução , Poluentes Químicos da Água/análise , Eletrodos
8.
J Hazard Mater ; 444(Pt A): 130328, 2023 02 15.
Artigo em Inglês | MEDLINE | ID: mdl-36402107

RESUMO

Hydroxylamine (NH2OH), nitrite (NO2-) and nitric oxide (NO), intermediates enzymatically formed during biological nitrogen removal processes, can engage in chemical (abiotic) transformations of antibiotics. This study determined the kinetics, mechanisms and pathways of abiotic transformations of the antibiotic sulfamethoxazole (SMX) by NH2OH, NO2- and NO in a series of batch tests under different pH and oxygen conditions. While NH2OH was not able to directly transform SMX, NO2- (with HNO2 as the actual reactant) and NO can chemically transform SMX primarily through hydroxylation, nitration, deamination, nitrosation, cleavage of S-N, N-C and C-S bonds, and coupling reactions. There were substantial overlaps in transformation product formations during abiotic transformations by HNO2- and NO. The second order rate constants of SMX with NO2- and NO were determined in the range of 1.5 × 10-1 - 4.8 × 103 M-1 s-1 and 1.0 × 102 - 3.1 × 104 M-1 s-1, respectively, under varying pH (4 - 9) and anoxic or oxic conditions. Acidic pH significantly enhanced abiotic transformation kinetics, and facilitated nitration, nitrosation, and cleavage of S-N and N-C bonds. The findings advance our understanding of the fate of antibiotics during biological nitrogen removal, and highlight the role of enzymatically formed reactive nitrogen species in the antibiotic degradation.


Assuntos
Nitritos , Sulfametoxazol , Hidroxilamina , Óxido Nítrico , Águas Residuárias , Dióxido de Nitrogênio , Hidroxilaminas , Nitrogênio , Antibacterianos , Concentração de Íons de Hidrogênio
9.
Chemosphere ; 300: 134495, 2022 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-35390412

RESUMO

"Concentrate-and-degrade" is an effective strategy to promote mass transfer and degradation of pollutants in photocatalytic systems, yet suitable and cost-effective photocatalysts are required to practice the new concept. In this study, we doped a post-transition metal of Indium (In) on a novel composite adsorptive photocatalyst, activated carbon-supported titanate nanotubes (TNTs@AC), to effectively degrade perfluorooctanoic acid (PFOA). In/TNTs@AC exhibited both excellent PFOA adsorption (>99% in 30 min) and photodegradation (>99% in 4 h) under optimal conditions (25 °C, pH 7, 1 atm, 1 g/L catalyst, 0.1 mg/L PFOA, 254 nm). The heterojunction structure of the composite facilitated a cooperative adsorption mode of PFOA, i.e., binding of the carboxylic head group of PFOA to the metal oxide and attachment of the hydrophobic tail to AC. The resulting side-on adsorption mode facilitates the electron (e‒) transfer from the carboxylic head to the photogenerated hole (h+), which was the major oxidant verified by scavenger tests. Furthermore, the presence of In enables direct electron transfer and facilitates the subsequent stepwise defluorination. Finally, In/TNTs@AC was amenable to repeated uses in four consecutive adsorption-photodegradation runs. The findings showed that adsorptive photocatalysts can be prepared by hybridization of carbon and photoactive semiconductors and the enabled "concentrate-and-degrade" strategy is promising for the removal and degradation of trace levels of PFOA from polluted waters.


Assuntos
Fluorocarbonos , Nanotubos de Carbono , Trinitrotolueno , Caprilatos/química , Fluorocarbonos/química , Índio , Titânio/química
11.
Chem Commun (Camb) ; 58(16): 2666-2669, 2022 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-35107448

RESUMO

This study reported the reactivity and mechanisms of superoxide radical (O2˙-)-mediated transformation of pentachlorophenate. Our results indicated that O2˙- alone exhibits limited effects on its degradation, and bimolecular nucleophilic substitution is the dominant reaction pathway.

12.
Sci Total Environ ; 818: 151787, 2022 Apr 20.
Artigo em Inglês | MEDLINE | ID: mdl-34808190

RESUMO

Pressurized vertical electro-osmotic dewatering (PVEOD) has been regarded as a feasible method to achieve sludge deep-dewatering, but the dewatering efficiency is still challenged by high electric resistance. This study employed cationic polyacrylamide (CPAM) as a skeleton builder to enhance electro-osmotic flow in PVEOD. The sludge dewatering efficiency and synergistic effect of CPAM and PVEOD were elucidated. The sludge morphology, surface property, extracellular polymeric substances (EPS) destruction and migration, spatial distributions of proteins and polysaccharides, and current changes were investigated. After the addition of optimal CPAM dose, the sludge formed a uniform and porous structure that provided water channels and enhanced electric transport, thus promoting EPS destruction. The sludge moisture content (MC) analysis indicated the more liberation of bound water due to EPS destruction. Besides, the re-flocculation of disintegrated sludge flocs improved the sludge filtration and thus dewaterability. Instantaneous energy consumption (Et,0.5) was optimized and two-step synergistic mechanism was thus proposed. These findings indicated that the combination of CPAM and PVEOD is a promising strategy to broaden the scope of industrial application of sludge deep-dewatering.


Assuntos
Resinas Acrílicas , Esgotos , Resinas Acrílicas/química , Matriz Extracelular de Substâncias Poliméricas , Floculação , Esgotos/química , Eliminação de Resíduos Líquidos/métodos , Água/química
13.
J Hazard Mater ; 424(Pt A): 127370, 2022 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-34879566

RESUMO

In the application of various magnetic materials for water treatment, control of surface resistance to acid and alkali corrosion remains largely overlooked, which could greatly extend their service life. We herein prepare amino grafted magnetic graphene oxide composites using a simple one-step cross-link reaction between the graphene oxide and magnetic Fe3O4/C nanoparticles. The as-prepared magnetic graphene oxide composites have long-term stability under acid and alkali solutions and shows an excellent performance in removing Ho(III), a representative rare earth element (REE) from water. The observed adsorption capacity of 72.1 mg Ho(III)/g exceeded that of most magnetic materials previously reported. Regeneration of the magnetic composites was realized in acid and alkali solutions but their structural integrity and physicochemical properties retained even after 18 adsorption-desorption cycles. The current adsorbent also shows excellent adsorption performance for other heavy REEs, such as Er(III), Eu(III), Lu(III), Tm(III), Y(III) and Yb(III). This work can provide a new strategy for constructing an acid and base resistance magnetic graphene oxide for the high-efficient recovery of heavy REEs from aqueous solution.

14.
Environ Sci Technol ; 56(1): 624-633, 2022 01 04.
Artigo em Inglês | MEDLINE | ID: mdl-34919383

RESUMO

Perfluorocarboxylic acids (PFCAs) exhibit strong persistence in sunlit surface waters and in radical-based treatment processes, where superoxide radical (O2•-) is an important and abundant reactive oxygen species. Given that the role of O2•- during the transformation of PFCAs remains largely unknown, we investigated the kinetics and mechanisms of O2•--mediated PFCAs attenuation through complementary experimental and theoretical approaches. The aqueous-phase rate constants between O2•- and C3-C8 PFCAs were measured using a newly designed in situ spectroscopic system. Mechanistically, bimolecular nucleophilic substitution (SN2) is most likely to be thermodynamically feasible, as indicated by density functional theory calculations at the CBS-QB3 level of theory. This pathway was then investigated by ab initio molecular dynamics simulation with free-energy samplings. As O2•- approaches PFCA, the C-F bond at the alpha carbon is spontaneously stretched, leading to the bond cleavage. The solvation mechanism for O2•--mediated PFCA degradation was also elucidated. Our results indicated that although the less polar solvent enhanced the nucleophilicity of O2•-, it also decreased the desolvation process of PFCAs, resulting in reduced kinetics. With these quantitative and mechanistic results, we achieved a defined picture of the O2•--initiated abatement of PFCAs in natural and engineered waters.


Assuntos
Fluorocarbonos , Poluentes Químicos da Água , Purificação da Água , Ácidos Carboxílicos/química , Fluorocarbonos/química , Superóxidos , Água/química , Poluentes Químicos da Água/química , Purificação da Água/métodos
15.
J Hazard Mater ; 416: 125825, 2021 08 15.
Artigo em Inglês | MEDLINE | ID: mdl-34492787

RESUMO

The adsorbents with high adsorption capacity for simultaneously removing Cr(VI) and Hg(II) from aqueous solutions under broad working pH range are highly desirable but still extremely scarce. Here, a novel adsorbent with multidentate ligands was facilely fabricated by covalently bonding 4-amino-3-hydrazino-5-mercapto- 1,2,4-triazole on graphene oxide via the Schiff's base reaction. The maximum adsorption capacities of Cr(VI) and Hg(II) on the current adsorbent were 734.2 and 1091.1 mg/g, which were 14.36 and 5.61 times higher than that of the pure graphene oxide, respectively, exceeding those of most adsorbents previously reported. More interestingly, Cr(VI) and Hg(II) concentrations were decreased from 2 mg/L to 0.0001 mg/L for Hg(II) and 0.004 mg/L for Cr(VI), far below the WHO recommended threshold for drinking water. Moreover, the adsorbent shows an excellent performance for simultaneous removal of Cr(VI) and Hg(II) with more than 99.9% and 98.6% removal efficiencies in aqueous solutions. Finally, the adsorbent was successfully applied in dealing with the real industrial effluent, implying huge potential in industrial application. This work offers a new possibility for the removal of the metallic contaminants by rational designing target groups and ligands.


Assuntos
Mercúrio , Poluentes Químicos da Água , Adsorção , Cromo/análise , Grafite , Concentração de Íons de Hidrogênio , Cinética , Compostos de Sulfidrila , Poluentes Químicos da Água/análise
16.
J Hazard Mater ; 419: 126479, 2021 10 05.
Artigo em Inglês | MEDLINE | ID: mdl-34216966

RESUMO

Microbially induced carbonate precipitation (MICP) could be a potential green solution to resolve the issue of heavy metal releasing from the sulfide tailings. However, detailed mechanism of heavy metal-biomineralization in sulfide tailings and impact of procedure parameters on in-situ applications remain unexplored. We systematically investigated the biomineralization process in the column tests for a better understanding of the mechanism and effects on the inhibition of cadmium (Cd) releasing from sulfide tailings. Results revealed that uniform and efficient mineralization in the tailings column occurred under bacterial concentration of 1 × 108 cfu mL-1, bacterial retention time of 3 h, concentration of mineralization solution of 0.25 mol L-1, and flow rate of 1.5 mL min-1. The leachable Cd concentration decreased 80.7% after 7 mineralization cycles. From a suit of characterizations, bacteria can adhere on the tailings and acted as the nucleation sites to induce the mineralization of Ca and Cd (to (Ca0.67, Cd0.33)CO3 and calcite phase); eventually, tailings particles were coated with the growth of mineralized carbonates, resulting in a reduction of exposure for tailings (especially sulfur). And thus, Cd release was inhibited. Results from this study will provide a fundamental basis for future in-situ applications of MICP to mitigate heavy metal pollutions.


Assuntos
Cádmio , Carbonatos , Bactérias , Carbonato de Cálcio , Sulfetos
17.
J Hazard Mater ; 417: 126015, 2021 09 05.
Artigo em Inglês | MEDLINE | ID: mdl-33992012

RESUMO

Mass transfer efficiency and catalytic reactivity are the two major hurdles for heterogeneous catalytic wet peroxide oxidation (CWPO) technologies. To address these issues, nanocomposite CuFeO2/Al2O3 was synthesized and assessed as a novel catalyst for enhanced adsorption and oxidation of anionic pollutants (catechol and reactive red 195 (RR195)) in waters. With a positive charge on the nanocomposite by introducing Al2O3, the adsorption of anionic pollutants was promoted. The surface complexation reaction on CuFeO2/Al2O3, which fits well to the Langmuir isotherm, has engined the mass transfer of pollutants to the nanocatalyst that demonstrated 96.46% and 99.75% removal of catechol and RR195 at pH 3, respectively. CuFeO2/Al2O3 also showed good performance in various reaction media including binary pollutants system and real wastewaters. The hydroxyl radical in aqueous solution played a major role in the pollutants degradation. The CWPO, which followed the Haber-Weiss mechanism, has been accelerated by the Cu and Fe redox cycles. The robustness of the catalyst was verified by negligible amount of metal leaching from the catalysts along with stable catalytic performance after five cycles. Upon the observed results, CuFeO2/Al2O3 with the synergistic effect has shown to be a promising catalyst for removal and degradation of anionic pollutants in CWPO.


Assuntos
Poluentes Ambientais , Nanocompostos , Poluentes Químicos da Água , Óxido de Alumínio , Catálise , Peróxido de Hidrogênio , Oxirredução , Peróxidos , Poluentes Químicos da Água/análise
18.
J Hazard Mater ; 408: 124868, 2021 04 15.
Artigo em Inglês | MEDLINE | ID: mdl-33418520

RESUMO

The production of fine particles from extremely high supersaturation has challenged the application of sulfide precipitation in treating heavy metal wastewater due to the difficulty of solid-liquid separation. To this end, a gas-liquid sulfide precipitation reactor for the removal of Cu2+ was designed by controlling the mass transfer and supersaturation levels during sulfidation processes. Particularly, a computational fluid dynamics (CFD) model of the reactor, integrating sulfidation reaction kinetics with two-phase flow hydrodynamics, was first built, followed by examining the effects of H2S(g) bubble diameter and flow rate. Based on the CFD simulation, the rate-limiting step of the gas-liquid sulfide precipitation reaction is the gas-liquid mass transfer process. Either reducing H2S(g) bubble diameter or increasing H2S(g) flow rate can result in the control of reaction rate and supersaturation level in the system. In order to validate the CFD simulations, we measured Cu2+ concentrations during the sulfidation process with the batch experiments. The agreement between computational and experimental results indicated that our mechanistic model can provide a protocol for the design and optimization of the reaction system, allowing one to visualize the time-dependent reaction process and evaluate the performance of a reactor.

19.
Water Res ; 190: 116746, 2021 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-33360617

RESUMO

Interests in the kinetics of radical-induced reactions in aqueous solution have grown remarkably due to their water engineering significance (e.g., advanced oxidation processes). Although compilations of the rate constants (k) for various radicals have been documented, surprisingly a systematic review has yet to be reported on the development of reliable methods for determining k values. A knowledge gap exists to critically evaluate and screen the various methods to measure them. In this review, we summarize the direct and indirect methods under steady-state and non-steady-state conditions, followed by critical evaluations on their advantages and disadvantages. The radicals of ·OH, [Formula: see text] , [Formula: see text] , and Cl· were chosen based on their significant aquatic environmental relevance. MS excel spreadsheets that demonstrate the determination processes were provided allowing one to reproduce the data and/or to analyze the unprocessed raw data as a "template". We formulated a standard operation procedure for the k determination, although there is simply no "versatile" method fitting for all radical reactions. Finally, existing challenges and future research focus are discussed. This is the first review covering methodological approaches and considerations, aiming to provide a holistic and fundamental basis to choose an appropriate method for determining the k values for bimolecular reactions between target compounds and radicals in the aqueous phase.


Assuntos
Poluentes Químicos da Água , Água , Radical Hidroxila , Cinética , Oxirredução
20.
Environ Technol ; 42(27): 4229-4236, 2021 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32241243

RESUMO

Hexavalent chromium (Cr(VI)) is often detected in groundwater, surface water and soils. The objective of the research was to study a hybrid process of adsorption onto iron oxyhydroxide agglomerates (IOAs) and ultrafiltration (UF) for removal of Cr(VI) from aqueous solution. Initially, the adsorption of the chromium onto IOAs was characterized by SEM and Raman analyses. Next, the IOAs dosages, required to obtain the regulatory limit of Cr(VI) ≤ 0.05-0.10 mg/L, at varying initial Cr(VI) concentrations, were determined in batch beaker tests and stirred tank reactor. The UF membrane held back efficiently the IOAs, at varying IOAs dosages, transmembrane pressures, and filtration velocities. Cake filtration was determined as the predominant fouling mechanism of the UF membrane. The fouling was reversible by backwash yet, faster fouling rates were obtained in consecutive filtration/backwash cycles. The results point to the applicability of the hybrid adsorption/UF process as a potent method for chromium removal from contaminated water.


Assuntos
Água Subterrânea , Poluentes Químicos da Água , Purificação da Água , Adsorção , Cromatos , Cromo/análise , Compostos Férricos , Ultrafiltração , Poluentes Químicos da Água/análise
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