Carbon slow-release and enhanced nitrogen removal performance of plant residue-based composite filler and ecological mechanisms in constructed wetland application.

Stable carbon release and coupled microbial efficacy of external carbon source solid fillers are the keys to enhanced nitrogen removal in constructed wetlands. The constructed wetland plant residue Acorus calamus was cross-linked with poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) to create composite solid carbon source fillers (Ac-BDPs). The study demonstrated the slow release of carbon sources from Ac-BDPs with 35.27 mg/g under an average release rate of 0.88 mg/(g·d). Excellent denitrification was also observed in constructed wetlands with Ac-BDPs. Moreover, the average removal rate of nitrate nitrogen (NO3--N) was increased by 1.94 and 3.85 times of the blank groups under initial NO3--N inputs of 5 and 15 mg/L, respectively. Furthermore, the relatively high abundances of nap, narG, nirKS, norB, qnorZ and nosZ guaranteed efficient denitrification performance in constructed wetlands with Ac-BDPs. The study introduced a reliable technique for biological nitrogen removal by using composite carbon source fillers in constructed wetlands.

Inhibit or promote? Trade-off effect of dissolved organic matter on the laccase-mediator system.

A biocatalytic system comprising fungal laccase and mediators can generate phenol radicals and efficiently eliminate various triarylmethane dyes. This study systematically explores the kinetic impact of dissolved organic matter (DOM), represented by humic substance (HS consisting of 90% fulvic acid, from lignite), on the decolorization of seven typical triarylmethane dyes by Trametes versicolor laccase and twenty natural mediators. Among these, 4-hydroxybenzyl alcohol (4-HA) and methyl violet (MV) undergo in-depth investigation regarding degradation products, pathways, and reaction mechanisms. In instances where HS hampers laccase-alone decolorization, such as malachite green, Coomassie brilliant blue, bromophenol blue, and acid magenta, this inhibition may persist despite mediator introduction. Conversely, in cases where HS facilitates decolorization, such as crystalline violet and ethyl violet, most laccase-mediator systems (LMSs) can still benefit. For MV decolorization by laccase and 4-HA, HS's kinetic effect is controlled by concentration and reaction time. A 5 mg/L HS increased the decolorization rate from 50% to 67% within the first hour, whereas 10 mg/L HS only achieved 45%. After 16 h of reaction, HS's impact on decolorization rate diminishes. Furthermore, the addition of HS enhances precipitation production, probably due to its involvement in polymerization with MV and mediator. Computational simulations and spectral monitoring reveal that low HS concentrations accelerate laccase-mediated demethylation by disrupting the chromophores bound to MV, thus promoting the decolorization of MV. Conversely, inhibition by high HS concentrations stems from the competitive binding of the enzyme pocket to the mediator, and the reduction of phenol free radicals in the system. Molecular docking and kinetic simulations revealed that laccase forms complexes with both the mediator and MV. Interestingly, the decolorization of MV occurred through a non-radical mechanism in the presence of HS. This work provided a reference for screening of high catalytic performance mediators to remove triarylmethane dyes in the actual water environment.

Efficient photochemical conversion of naproxen by butanedione: Role of energy transfer.

Photochemical active species generated from photosensitizers, e.g., dissolved organic matter (DOM), play vital roles in the transformation of micropollutants in water. Here, butanedione (BD), a redox-active moiety in DOM and widely found in nature, was employed to photo-transform naproxen (NPX) with peracetic acid (PAA) and H2O2 as contrasts. The results obtained showed that the BD exhibited more applicable on NPX degradation. It works in the lake or river water under UV and solar irradiation, and its NPX degradation efficiency was 10-30 times faster than that of PAA and H2O2. The reason for the efficient transformation of pollutants is that the BD system was proved to be a non-free radical dominated mechanism. The quantum yield of BD (Ф254 nm) was calculated to be 0.064, which indicates that photophysical process is the dominant mode of BD conversion. By adding trapping agents, direct energy transfer from 3BD* to NPX (in anoxic environment) or dissolved oxygen (in aerobic environment) was proved to play a major role (> 91 %). Additionally, the BD process reduces the toxicity of NPX and promotes microbial growth after irradiation. Overall, this study significantly deepened the understanding of the transformation between BD and micropollutants, and provided a potential BD-based process for micropollutants removal under solar irradiation.

Modeling, optimization and understanding of adsorption process for pollutant removal via machine learning: Recent progress and future perspectives.

It is crucial to reduce the concentration of pollutants in water environment to below safe levels. Some cost-effective pollutant removal technologies have been developed, among which adsorption technology is considered as a promising solution. However, the batch experiments and adsorption isotherms widely employed at present are inefficient and time-consuming to some extent, which limits the development of adsorption technology. As a new research paradigm, machine learning (ML) is expected to innovate traditional adsorption models. This reviews summarized the general workflow of ML and commonly employed ML algorithms for pollutant adsorption. Then, the latest progress of ML for pollutant adsorption was reviewed from the perspective of all-round regulation of adsorption process, including adsorption efficiency, operating conditions and adsorption mechanism. General guidelines of ML for pollutant adsorption were presented. Finally, the existing problems and future perspectives of ML for pollutant adsorption were put forward. We highly expect that this review will promote the application of ML in pollutant adsorption and improve the interpretability of ML.

Antimony (Sb) pollution control by coagulation and membrane filtration in water/wastewater treatment: A comprehensive review.

Antimony (Sb) pollution in the water environment caused by the large-scale mining of Sb ore and the wide use of Sb-containing products seriously endangers human health and poses a great threat to the ecological environment. Coagulation is one of the most cost-effective technologies for Sb pollution control in water/wastewater treatment and has been widely used. However, a comprehensive understanding of Sb pollution control by coagulation, from fundamental research to practical applications, is lacking. In this work, based on the current status of Sb pollution in the water environment, a critical review of the Sb removal performance and mechanism by coagulation and related combined processes was carried out. The influencing factors of Sb removal performance by coagulation are introduced in detail. The internal mechanisms and improvement strategies of Sb removal by oxidation/reduction-coagulation and coagulation-membrane filtration technologies are emphasized. Moreover, given the development of Sb-removing coagulants and the resource utilization of Sb-containing sludge, future perspectives of coagulation for Sb removal are discussed. As the first review in this field, this work will illuminate avenues of basic research and practical applications for Sb and Sb-like pollution control in water/wastewater treatment.

Heterogeneous catalysis mediated by light, electricity and enzyme via machine learning: Paradigms, applications and prospects.

Energy crisis and environmental pollution have become the bottleneck of human sustainable development. Therefore, there is an urgent need to develop new catalysts for energy production and environmental remediation. Due to the high cost caused by blind screening and limited valuable computing resources, the traditional experimental methods and theoretical calculations are difficult to meet with the requirements. In the past decades, computer science has made great progress, especially in the field of machine learning (ML). As a new research paradigm, ML greatly accelerates the theoretical calculation methods represented by first principal calculation and molecular dynamics, and establish the physical picture of heterogeneous catalytic processes for energy and environment. This review firstly summarized the general research paradigms of ML in the discovery of catalysts. Then, the latest progresses of ML in light-, electricity- and enzyme-mediated heterogeneous catalysis were reviewed from the perspective of catalytic performance, operating conditions and reaction mechanism. The general guidelines of ML for heterogeneous catalysis were proposed. Finally, the existing problems and future development trend of ML in heterogeneous catalysis mediated by light, electricity and enzyme were summarized. We highly expect that this review will facilitate the interaction between ML and heterogeneous catalysis, and illuminate the development prospect of heterogeneous catalysis.

An all-in-one approach for synthesis and functionalization of nano colloidal gold with acetylacetone.

Controllable synthesis, proper dispersion, and feasible functionalization are crucial requirements for the application of nanomaterials in many scenarios. Here, we report an all-in-one approach for the synthesis and functionalization of gold nanoparticles (AuNPs) with the simplestß-diketone, acetylacetone (AcAc). With this approach, the particle size of the resultant AuNPs was tunable by simply adjusting the light intensity or AcAc dosage. Moreover, owing to the capping role of AcAc, the resultant AuNPs could be stably dispersed in water for a year without obvious change in morphology and photochemical property. Formation of ligand to metal charge transfer complexes was found to play an important role in the redox conversion of Au with AcAc. Meanwhile, the moderate complexation ability enables the surface AcAc on the AuNPs to undergo ligand exchange reactions (LER). With the aid of Ag+, the AuNPs underwent LER with glutathione and exhibited enhanced photoluminescence (PL) with a maximum of 22-fold increase in PL intensity. The PL response was linear to the concentration of glutathione in the range of 0-500µM. Such a LER makes the obtained AuNPs being good imaging probes. To the best of our knowledge, this is the first work on illustrating the roles of AcAc as a multifunctional ligand in fabrication of NPs, which sheds new light on the surface modulation in synthesis of nanomaterials.

[Fabrication of Supported Titanium Xerogel Adsorbent and Performance Evaluation for Arsenite Removal].

Although the adsorption capacity of titanium xerogel(TAX) for arsenite(As(Ⅲ)) is high(254 mg·g-1), the adsorption rate is slow. Therefore, TAX was loaded onto activated carbon, sponge, and resin to fabricate a supported adsorbent, and the arsenite removal performance was evaluated. Except sponge, activated carbon and resin could successfully load TAX. The results showed that resin and activated carbon loaded TAX improved the As(Ⅲ) removal performance, and more significantly by the resin-based materials. Through wet digestion and adsorption kinetics experiments, the amount of titanium loaded was approximately 1.4% and 5% in the activated carbon-based(TAX@AC) and resin-based(TAX@resin) materials, respectively. For the initial concentration of 1.0 mg·L-1 As(Ⅲ) solution, the adsorption rate constant of TAX@D201 was 0.85 mg·(g·min) -1, which was 21 times higher than that of unloaded TAX[0.04 mg·(g·min) -1]. Columns packed with TAX@resin could effectively lower arsenite concentration for up to 560 bed volumes, which is 2.8 times greater than that of the iron-based composites with the same metal mass. Therefore, loading TAX on macroporous resin is an effective strategy and provides an effective approach for the application of TAX in arsenite-containing groundwater.

Photochemical Synthesis of Selenium Nanospheres of Tunable Size and Colloidal Stability with Simple Diketones.

Temporal and spatial segregations are two fundamental requirements for the successful synthesis of nanoparticles (NPs). To obtain colloidally stable selenium nanospheres (SeNSs), surfactants or polymers are generally needed as structure-directing agents or stabilizers in the reduction approaches for SeNP synthesis. The addition of such chemicals sacrifices the purity of the obtained SeNPs and, therefore, is detrimental to the applications. Here, for the first time, we report that low-molecular weight (less than six carbons) diketones are excellent photoreductants for green and tunable synthesis of SeNPs, owing to their merits in temporal and spatial control. With simple diketones as the photoreductants, the resultant SeNPs were pure and colloidally stable with nice photoelectronic properties. This finding not only provides a useful strategy for the synthesis of SeNPs but also might be a milestone in the development of ketone photochemistry.

Role of complexation in the photochemical reduction of chromate by acetylacetone.

Organic ligands can alter the redox behavior of metal species through the generation of metal-ligand complexes. Photo-induced complexation between ligands and metals is an important, but under-appreciated, aspect of process. Acetylacetone (AA) is a good chelating agent due to keto-enol tautomerization. In the presence of AA, photoreduction of Cr(VI) is accelerated; however, it is unclear exactly how complexation is involved in UV/AA mediated Cr(VI) reduction. On the basis of spectral and kinetic analyses, this study shows that the formation of {Cr(VI)-AA}* complexes is the main mechanism of Cr(VI) reduction by UV/AA. Evidence for this includes (1) the formation rate constant of Cr(III)-AA complexes in the UV system was 2-3 orders of magnitude greater than that in the thermal system; (2) there was a linear relationship between the photons absorbed by AA and the reduction rate constants of Cr(VI); and (3) the reaction appeared initially zero-order in Cr(VI) and turned to first-order as the pool of available Cr(VI) ran out. The results presented here are not only important for the better understanding of the complexation effects in the reduction of Cr(VI), but also crucial for the possible application of the UV/AA process in many other scenarios.

Metal-free generation of hydroxyl radicals by benzoate-mediated decomposition of peroxides.

A type of metal-free organic photo-Fenton-like reaction was developed, which was realized by a combination of UV with benzoates and peroxides. The findings here not only provide a novel ˙OH production pathway, but also shed new light on the accurate quantification, better use or prevention of ˙OH in many scenarios.

Sludge reduction and cost saving in removal of Cu(II)-EDTA from electroplating wastewater by introducing a low dose of acetylacetone into the Fe(III)/UV/NaOH process.

Cu(II)-EDTA is highly stable in a wide pH range (3.0∼12.0) and hard to be removed by the conventional precipitation method. Fe(III) displacement/UV photolysis/alkaline precipitation [Fe(III)/UV/NaOH] has been proposed as a promising method for the removal of Cu(II)-EDTA. Nevertheless, a high dose of Fe(III) is needed in this combined process, resulting in the production of a large amount of hazardous sludge. The photochemistry of Fe(III) is known to be ligand-dependent. Fe(III)-oxalate complexes are strongly photoactive. However, the addition of oxalic acid to the Fe(III)/UV/NaOH process was of little help. Acetylacetone (AA) is a good chelating ligand for many metals and has been proved as an efficient photo-activator. By introducing a low dose of AA ([AA]/[Cu] = 1.5) into the Fe(III)/UV/NaOH process, the Fe(III) dosage ([Fe]/[Cu]) was reduced from 10.4 to 3.2. As a result, the chemical cost was reduced from 13.9 to 7.6 kW h/m3. Meanwhile, the energy cost in the UV photolysis was reduced from 1066.5 to 752.4 kW h/m3. Most importantly, the sludge yields were reduced from 8.3 to 2.7 kg/m3 in a simulated wastewater and from 101.8 to 30.8 kg/m3 in a real electroplating wastewater. Such a sludge reduction is of great significance in mitigating the load of landfill.

Reduction of chromate with UV/diacetyl for the final effluent to be below the discharge limit.

Reduction of Cr(VI) to Cr(III) is helpful to lower the toxicity risk and also necessary for the removal of chromium from waste streams through alkaline precipitation. We compared the reduction of Cr(VI) in six UV systems with oxalic acid (OA), ethylenediaminetetraacetic acid (EDTA), salicylic acid (SA), hydroquinone (HQ), acetylacetone (AA) and diacetyl (BD) as chelating or non-chelating photo-activators. Overall, HQ, AA and BD were much more efficient than the carboxylic acids for the photo-reduction of Cr(VI). By introduction of UV to HQ system, the pseudo-first-order rate constant of Cr(VI) reduction at pH 5.1 was increased about 50 times. However, due to the formation of colloidal polymers, the UV/HQ treated solutions were dark in color and had a high turbidity (82 NTU). The effects of AA and BD on the photoreduction of Cr(VI) were similar. The UV/BD treated solution was colorless and clear with a turbidity lower than 1 NTU and a residual Cr less than 0.1 mg/L. The results demonstrate that UV/BD is a promising approach for the treatment of Cr(VI)-laden wastewater. The findings here also suggest that utilization of diketones in redox conversion of contaminants is a topic deserving further research.

Ligand effects on arsenite removal by zero-valent iron/O2: Dissolution, corrosion, oxidation and coprecipitation.

Ligands may increase the yields of reactive oxygen species (ROS) in zero-valent iron (ZVI)/O2 systems. To clarify the relationship between the properties of ligands and their effects on the oxidative removal of contaminants, five common ligands (formate, acetate, oxalate, ethylenediaminetetraacetic acid (EDTA), and phosphate) as well as acetylacetone (AA) were investigated with arsenite (As(III)) as the target contaminant at three initial pH values (3.0, 5.0, and 7.0). The addition of these ligands to the ZVI/O2 system resulted in quite different effects on As(III) removal. EDTA enhanced the oxidation of As(III) to arsenate (As(V)) but inhibited the removal of As(V). Oxalate was the only ligand in this work that accelerated both the removal of As(III) and As(V). By analyzing the ligand effects from the four aspects: dissolution of surface iron (hydr)oxides, corrosion of ZVI, reaction with ROS, and interference with precipitation, the following properties of ligands were believed to be important: ability to provide dissociable protons, complexation ability with iron, and reactivity with ROS. The complexation ability is a double-edged sword. It could enhance the generation of ROS by reducing the reduction potential of the Fe(III)/Fe(II) redox couple, but also could inhibit the removal of arsenic by coprecipitation. The elucidated relationship between the key property parameters of ligands and their effects on the ZVI/O2 system is helpful for the rational design of effective ZVI/ligand/O2 systems.

Enhanced Photooxidation of Hydroquinone by Acetylacetone, a Novel Photosensitizer and Electron Shuttle.

Quinones are important electron shuttles as well as micropollutants in the nature. Acetylacetone (AA) is a newly recognized electron shuttle in aqueous media exposed to UV irradiation. Herein, we studied the interactions between AA and hydroquinone (QH2) under steady-state and transient photochemical conditions to clarify the possible reactions and consequences if QH2 and AA coexist in a solution. Steady-state experimental results demonstrate that the interactions between AA and QH2 were strongly affected by dissolved oxygen. In O2-rich solutions, the phototransformation of QH2 was AA-independent. Both QH2 and AA utilize O2 as the electron acceptor, but in O2-insufficient solutions, AA became an important electron acceptor for the oxidation of QH2. In all cases, the coexistence of AA increased the phototransformation of QH2, whereas the decomposition of AA in O2-saturated and oversaturated solutions was inhibited by the presence of QH2. The underlying mechanisms were investigated by a combination of laser flash photolysis (LFP) and reduction potential analysis. The LFP results show that the excited AA serves as a better electron shuttle than QH2. As a consequence, AA might regulate the redox cycling of quinones, leading to significant effects on many processes, ranging from photosynthesis and respiration to photodegradation.

Effects of acetylacetone on the thermal and photochemical conversion of benzoquinone in aqueous solution.

Quinones are components of electron transport chains in photosynthesis and respiration. Acetylacetone (AA), structurally similar to benzoquinone (BQ) for the presence of two identical carbonyl groups, has been reported as a quinone-like electron shuttle. Both BQ and AA are important chemicals in the aquatic environment. However, little information is known about their interactions if co-existed. We found here that AA significantly enhanced the conversion of BQ. By analyzing the evolution of chemical concentration, solution pH, dissolved oxygen, and the final products, the interactions between AA and BQ were elucidated. The reactions between BQ and AA generated oxygen but ultimately led to the reduction of solution pH and dissolved oxygen. The reactions proceeded faster under indoor lighting condition than in the dark. The formation of semiquinone radicals is believed as the primary step. The secondary AA-derived radicals might be strongly oxidative or reductive, depending on the concentration of dissolved oxygen. Insoluble humus was generated in the mixture of BQ and AA. These results suggest that the presence of AA might interfere with photosynthesis and respiration through the interactions with quinones.

Coagulation removal of fluoride by zirconium tetrachloride: Performance evaluation and mechanism analysis.

Fluoride (F-) pollution is a worldwide issue. Coagulation with aluminum (Al) salts is an efficient and economical method for the removal of F-. However, due to the strong complexation between Al3+ and F-, the residual F- and Al after coagulation usually exceed the limits. Zirconium (Zr) coagulants have drawn increasing attention due to their excellent flocculation ability for organic matter. In this work, the performance and mechanism of ZrCl4 coagulation for F- removal were investigated with the widely used Al2(SO4)3 as a reference. The optimum pH range is 4.0-6.0 for ZrCl4 and 8.0-10.0 for Al2(SO4)3. ZrCl4 was superior to Al2(SO4)3 for F- removal as the initial F- concentration was less than 30.0 mg L-1. Coexisting substances at environmental concentration levels showed negligible effects on F- removal by ZrCl4. Besides the better F- removal, another advantage of ZrCl4 over Al2(SO4)3 was the much lower residual metal concentration in the pH range of 4.0-11.0. The hydrolysis of Al2(SO4)3 was significantly inhibited due to the formation of Al-F complexes while the hydrolysis of ZrCl4 was not influenced even under strongly acidic conditions. Therefore, F- removal by Al2(SO4)3 was mainly achieved by preliminary complexation between Al3+ and F- and subsequent hydrolysis and polymerization of these complexes, while adsorption onto hydrolysates and ion exchange with surface hydroxyl groups were the main ways of F- removal by ZrCl4. The work here provides a new method for F- removal and may shed light on the application of Zr coagulants for other pollutants.

Adsorption and Reduction of Cr(VI) Together with Cr(III) Sequestration by Polyaniline Confined in Pores of Polystyrene Beads.

The simultaneous reduction and sequestration of Cr(VI) from wastewater is desirable as a cost-effective and environmentally friendly approach. In this study, we execute a one-step facile synthesis strategy on polyaniline (PANI) composites based on aniline adsorption and polymerization on pores of millimeter-scale polystyrene balls (PANI@PS). The well-defined PANI@PS increased the removal capacity of Cr(VI) by 5.4 times, going from 43.6 (bulky PANI) to 233.7 mg g-1 near neutral pH (6.0) instead of the pH 1-3 documented in other reports, which was higher than that of many reported adsorbents due to its porous structure, numerous interaction sites, and confinement effects in the polymer. Most importantly, PANI@PS could efficiently sequester positive Cr(III) after reducing Cr(VI) to Cr(III) due to its negative surface created by confinement effects confined to the nanopores of PS. Conversely, positively charged bulky PANI repelled electrostatically positive Cr(III); thus, additional precipitation or adsorption treatments were needed in practical applications. Moreover, a coating of PANI can protect PS, as a substrate and a composite, from irreversible damage due to the strong oxidation capacity of Cr(VI), which is another major concern in adsorbing strong oxidants using polymers. A novel strategy to regenerate the exhausted PANI@PS was efficiently executed based on the electrochemical redox reversibility of PANI. Finally, the comprehensive adsorption/reduction/sequestration of Cr on PANI@PS was elucidated in detail.

Nonnegligible Generation of Hydroxyl Radicals from UVC Photolysis of Aqueous Nitrous Oxide.

Nitrous oxide (N2O) is widely used in radiation-chemistry and photochemistry as a scavenger to convert a hydrated electron ( eaq-) into a hydroxyl radical (·OH). However, few investigations pay attention to the photochemistry of dissolved N2O itself. The effects of purged N2O on photochemical processes are unclear and neglected. In the present work, the effects of N2O on the hydroxylation of terephthalic acid (TPA) were investigated with both medium-pressure and low-pressure mercury lamps as the light sources. Under short-wavelength UV (200-300 nm) irradiation, N2O accelerated the decay of TPA and the formation of 2-hydroxylterephthalic acid (hTPA). The effective quantum yield of ·OH from the photolysis of dissolved N2O at 254 nm was determined as 1.15-1.63, which was far larger than those of NO3- (0.09) and NO2- (0.046). On the basis of the kinetic analysis in N2 and N2O purged solutions, isotope fractionation with heavy oxygen water, and ·OH scavenging experiments with tert-butyl alcohol, the contribution of the ·OH radicals generated from the photolysis of N2O to the formation of hTPA (61.7%) was determined to be 1 order of magnitude higher than that from the converted eaq- (6.5%). These results demonstrate that using N2O and ·OH probes to quantify photogenerated eaq- in UVC irradiation might lead to false results. The work here is helpful for the proper design of scavenging and probing experiments by the combination of N2O and ·OH probes.