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Small molecules, including natural metabolites, organic matter decomposition products, and engineered oxidation byproducts, are widespread in aquatic environment. However, the limited understanding of the photochemical interactions of these small molecules with water pollutants hampers the development of effective environmental protection strategies. This study explores the structural features governing the photochemical transformation of toxic oxyanions by α- and β-dicarbonyl compounds. By integrating experimental observations with quantum chemical calculations, a robust correlation network was constructed. The correlation network reveals that the reactivity of small organic molecules with oxyanions could be quantitively predicted by their intrinsic properties, such as electronic transition energy, bond dissociation energy, molecular softness, molecular orbital gap, atomic charge, and molecular surface local ionization energy. This network maps the relationship between the molecular architecture of chemicals and their photochemical behaviors. This perspective offers fresh insights into the photochemical behaviors of small molecules in diverse environmental and chemical contexts and are helpful for developing advanced water treatment strategies toward a sustainable future., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Indirect photodegradation is an important pathway for the reduction of steroid estrogens in sunlit surface waters. Nevertheless, the kinetics and mechanisms governing the interaction between coexisting carbonyl compounds and estrogens under visible light (Vis) remain unexplored. This study systematically investigates the Vis-induced photodegradation of 17β-estradiol (E2) in the presence of five specific carbonyl compounds-biacetyl (BD), acetone, glyoxal, pyruvic acid, and benzoquinone. The results demonstrate that, among these compounds, only BD significantly enhanced the photodegradation of E2 under Vis irradiation (λ > 400 nm). The pseudo-first order photodegradation rate constants (k 1 ) of E2 in the Vis/BD system were 0.025 min -1 and 0.076 min -1 in ultrapure water and river water, respectively. The enhancing effect of BD was found to be pH-dependent, increasing the pH from 3.0 to 11.0 resulted in a 76% reduction in the k 1 value of E2 in the Vis/BD system. Furthermore, the presence of humic acid, NO 3 - , or HCO 3 - led to an increase of more than 35% in the k 1 value of E2, while NO 2 - exerted a pronounced inhibitory effect, resulting in a 92% decrease. Peroxyacetyl and peroxymethyl radicals, derived from BD in a yield ratio of 9, played a crucial role in the degradation of E2. These peroxyl radicals primarily targeted electron-rich hydroxyl sites of E2, initiating hydroxylation and ring-opening reactions that culminated in the formation of acidic byproducts. Notably, toxicity evaluation indicates that these hydroxylated and acidic products exhibited lower toxicity than the parent compound E2. This study highlights the important role of peroxyl radicals in estrogen degradation within aquatic environment, and also helps to design efficient visible light-responsive photo-activators for the treatment of estrogen-contaminated waters., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Amine-modified wheat straw (AMWS) has already been reported as a promising adsorbent for nitrate (NO 3 ) removal due to its cost-effectiveness and high efficiency. However, the NO 3 removal mechanism has not been well understood, especially in the presence of co-existing ions. Here, the effect of co-existing anions on NO 3 removal by AMWS was investigated and the underlying mechanisms were revealed using a combination of in-situ infrared (IR) spectroscopy and computational modeling. The in-situ IR results indicated that NO 3 , sulfate (SO 4 ), and phosphate (PO 4 ) are all adsorbed as outer-sphere complexes on AMWS. The two-dimensional-correlation spectroscopy analysis implied the adsorption sequence of SO 4  > PO 4  > NO 3 . The adsorption energies obtained from density functional theory calculation range from -0.24 to 0.51 eV (-23.2 to 49.2 kJ/mol), confirming that these anions adsorb on AMWS as outer-sphere complexes. For the first time, this study provides direct spectroscopic evidence of the outer-sphere adsorption of NO 3 on AMWS, as well as identifies the adsorption sequence, confirmed by computational modeling. The competitive mechanism of NO 3, SO 4 , and PO 4 revealed in this study is helpful to understand and predict the applications of AMWS., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Organoarsenical antibiotics pose a severe threat to the environment and human health. In aquatic environment, dissolved organic matter (DOM)-mediated photochemical transformation is one of the main processes in the fate of organoarsenics. Dicarbonyl is a typical redox-active moiety in DOM. However, the knowledge on the photoconversion of organoarsenics by DOM, especially the contributions of dicarbonyl moieties is still limited. Here, we systematically investigated the photochemical transformation of three organoarsenics with the simplest β-diketone, acetylacetone (AcAc), as a model dicarbonyl moiety of DOM. The presence of AcAc significantly enhanced the photochemical conversion of roxarsone (ROX), whereas only minor effects were observed for 3-amino-4-hydroxyphenylarsonic acid (HAPA) and arsanilic acid (ASA), because the latter two (with an amino (-NH 2 ) group) are more photoactive than ROX (with a nitro (-NO 2 ) group). The results demonstrate that AcAc was a potent photo-activator and the reduction of -NO 2 to -NH 2 might be a rate-limiting step in the phototransformation of ROX. At a 1:1 M ratio of AcAc to ROX, the photochemical transformation rate of ROX was increased by 7 folds. In O 2 -rich environment, singlet oxygen, peroxide radicals, and ·OH were the main reactive species that led to the breakage of the C-As bond in ROX and the oxidation of the released arsono group to arsenate, whereas the triplet-excited state of AcAc ( 3 AcAc*) and carbon-centered radicals from the photolysis of AcAc dominated in the reductive transformation of ROX. In anoxic environment, 3-amino-4-hydroxyphenylarsonic acid was one of the main reductive transformation intermediates of ROX, whose photolysis rate was about 35 times that of ROX. The knowledge obtained here is of great significance to better understand the fate of organoarsenics in natural environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

In surface waters, photogenerated transients (e.g., hydroxyl radicals, carbonate radicals, singlet oxygen and the triplet states of dissolved organic matter) are known to play a role in the transformation of biorecalcitrant carbamazepine (CBZ). Small diketones, such as acetylacetone (AcAc) and butanedione (BD), are naturally abundant and have been proven to be effective precursors of carbon and oxygen centered radicals. However, the photochemical kinetics and mechanisms of coexisting diketones and CBZ are barely known. Herein, the effects of AcAc and BD on the photochemical conversion of CBZ were investigated compared with H 2 O 2 which was the main ·OH precursor in the environment. An enhancing effect was observed for the degradation of CBZ by the addition of diketones. The enhancing effect of diketones was pH-dependent and much more significant than H 2 O 2 under simulated solar irradiation. On the basis of the identification of transient species and the competition kinetic model, organic peroxyl radicals were found to play a dominant role in CBZ photodegradation, and the second-order rate constants of the reaction between CBZ and peroxyl radicals were determined to be approximately 10 7 -10 8  M -1 s -1 . Furthermore, mutagenic acridine was found to be the major cumulative intermediate with a yield of > 30% in the presence of diketones, which might be an environmental concern. This work indicates that the coexistence of diketones and persistent organic pollutants might lead to some detrimental effects on aquatic environments if the water is exposed to sunlight., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Acetylacetone (AA) has proven to be a potent photo-activator for the decolorization of dyes. However, there is very limited information on the quantitative structure-activity relationship (QSAR) and the mechanisms of dye degradation by UV/AA. Herein, the photolysis of 65 aromatic compounds (dyes and dye precursors) was investigated at three pH values (4.0, 6.0, 9.0) by UV/AA and UV/H 2 O 2 . The obtained pseudo-first-order photodegradation rate constants (k 1 ) were processed using statistical analysis. The correlation between the k 1 values and the number of photons absorbed by AA, together with the observed pH effect, suggested that the protonated enol structure of AA plays a crucial role in the photodecolorization of dyes. According to quantum chemical computation, photo-induced direct electron transfer between the excited state of AA and the dye was the main mechanism in the UV/AA process. QSAR models demonstrated that the molecular size and stability were the key factors that determined the efficiency of UV/H 2 O 2 for dye degradation. Statistically, the UV/AA process was target-selective and suffered less from the inner filter effect, which made it more effective than the UV/H 2 O 2 process for dye degradation. The selectivity of the UV/AA process was mainly embodied in the substituent effects: dyes with hydroxyl groups in conjugated systems decomposed faster than those with nitro-substitution or ortho-substituted sulfonate groups. The results can be used for the selection of appropriate photochemical approaches for the treatment of dye-contaminated water., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have influenced the work reported in this paper., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The photolysis characteristics of azo dyes are critically important in environmental pollution control, dye-sensitized solar cells, and dyeing-related industries. However, there is still lack of quantitative relationship between the structures of azo dyes and their photolysis characteristics. To address this issue, the photolysis of 22 azo dyes were conducted side by side at three pH (4.0, 6.0, 9.0). The obtained pseudo-first order photodegradation rate constants (k 1 ) were processed with meta-analysis. Statistically, the hydrazone tautomer had a smaller excitation energy and was easier to undergo photolysis than the azo tautomer. The ortho-substituted sulfonate groups had an obvious protective effect on the photostability of azo dyes. The softness (s), the most positive and negative partial charge on a carbon atom (qC + , qC - ) were found to be crucial descriptors in the establishment of QSAR models for the photostability of azo dyes. The QSAR model at pH 9.0 was robust for predicting the photostability of azo dyes under UV irradiation. N 2 -purging experiments and quantum chemical computation verified that the cleavage of azo bond was not a result of direct photolysis but was caused by the attack of photoinduced reactive oxygen species. The results here are helpful for the design of more stable azo dyes or the selection of suitable approaches for the treatment of dye-contaminated water bodies., Competing Interests: Declaration of interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019. Published by Elsevier B.V.)

Ligands may increase the yields of reactive oxygen species (ROS) in zero-valent iron (ZVI)/O 2 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/O 2 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/O 2 system is helpful for the rational design of effective ZVI/ligand/O 2 systems., (Copyright © 2019. Published by Elsevier B.V.)

Water-stable PVA/PAA nanofibers were fabricated through electrospinning and evaluated for their performance in lead (Pb(II)) and cadmium (Cd(II)) removal from water in a batch experiment. The adsorption mechanism of Pb(II) was explored using the extended X-ray absorption fine structure (EXAFS) spectroscopic analysis. The PVA/PAA nanofibers showed a pH-dependent behavior for heavy metal removal, and its adsorption capacities for Pb(II) and Cd(II) could reach as high as 159 and 102 mg/g, respectively. The calcium ion (Ca(II)) had no effect on Pb(II) removal at pH 5.0 whereas it significantly reduced Cd(II) removal at pH 7.0. The adsorption of Pb(II) and Cd(II) was spontaneous and exothermic in nature with a decrease in randomness. The saturated PVA/PAA nanofibers could be regenerated using acidic solutions for reuse. The Fourier-transform infrared (FTIR) spectroscopic analysis indicated the formation of surface complexes between adsorbed Pb(II) and Cd(II) and carboxyl groups on PVA/PAA nanofibers. Moreover, EXAFS analysis suggested that a Pb(II) cation was chelated with three carboxyl groups on the nanofibers. This molecular-level adsorption structure was successfully implemented into a surface complexation model for the prediction of the macroscopic Pb(II) and Cd(II) adsorption behaviors. The results gained from this study provided complementary information on heavy metal removal by a new generation of adsorbents and improved the fundamental understanding for the removal process., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

River biofilms play fundamental roles in shaping the architecture of aquatic systems. Sorption to biofilms was thought to be a crucial mechanism controlling the fate and transport of trace emerging contaminants. This study focused on the role of in situ colonized river biofilms in the early fate of phthalate esters (PAEs) and bisphenols (BPs) at trace concentrations in a representative urban river. PAEs and BPs were readily sorbed to biofilms with uptakes of 38.2-162.5 μg/g for PAEs and 1787.7-4425.6 μg/g for BPs, respectively. The total mass and characteristics of the colonized biofilms varied in response to seasons and water qualities. The biofilm colonized in the downstream of a wastewater treatment plant exhibited the highest sorption capacity among the tested sites, possibly attributed to the higher organic contents of biofilms owing to the elevated availability of nutrients. Correlation analysis indicates that certain water qualities, e.g., TN and NH 3 N, and biofilm properties, e.g., organic and polysaccharide fractions could be selected to predict the sorption capacities of river biofilms. Hydrophobic partitioning into organic matter appears to be the dominant sorption mechanism and biofilm polysaccharides were probably responsible for the adhesion of tested compounds. The contaminant partitioning into biofilm and sediment at mass/volume ratios typical for small rivers suggests that the biofilm could serve as an important sorbing matrix for the trace organic contaminants as compared to the sediments. Our work yields new insights into the early uptake and accumulation of trace plasticizers by natural biofilms, which is of significance in understanding the subsequent transport of trace organic contaminants in fluvial systems., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Research efforts on advanced oxidation processes (AOPs) have long been focused on the fundamental chemistry of activation processes and free radical reactions. Little attention has been paid to the chemistry of the precursor oxidants. Herein, we found that the precursor oxidants could lead to quite different outcomes. A counterintuitive result was observed in the photoreduction of bromate/iodate: the combination of H 2 O 2 and UV enhanced the reduction of bromate/iodate, whereas the addition of persulfate to the UV system led to an inhibitory effect. Thermodynamic and kinetic evidence suggests that the reduction of bromate in UV/H 2 O 2 was attributable to the direct reaction between HOBr and H 2 O 2 . Both experimental determination and kinetic simulation demonstrate that the reaction between HOBr and H 2 O 2 dominated over the • OH-mediated reactions. These results suggest that H 2 O 2 possesses some particular redox properties that distinguish it from other peroxides. The prototypical UV/H 2 O 2 process is not always an AOP: it can also be an enhanced reduction process for chemicals with intermediates that are reducible by H 2 O 2 . Considering the increasing interest in persulfate-based AOPs, the results of this study identify some novel advantages of the classical H 2 O 2 -based AOPs.

Biodegradability and toxicity are two important indexes in considering the feasibility of a chemical process for environmental remediation. The acetylacetone (AA) mediated photochemical process has been proven as an efficient approach for dye decolorization. Both AA and its photochemical degradation products had a high bioavailability. However, the biocompatibility and ecotoxicology of the UV/AA treated solutions are unclear yet. In the present work, we evaluated the biocompatibility and toxicity of the UV/AA treated solutions at both biochemical and organismal levels. The biodegradability of the treated solution was evaluated with the ratio of 5-d biological oxygen demand (BOD 5 ) to chemical oxygen demand (COD) and a 28-d activated sludge assay (Zahn-Wellens tests). The UV/AA process significantly improved the biodegradability of the tested dye solutions. Toxicity was assessed with responses of microorganisms (microbes in activated sludge and Daphnia magna) and plants (bok choy, rice seed, and Arabidopsis thaliana) to the treated solutions, which showed that the toxicity of the UV/AA treated solutions was lower or comparable to that of the UV/H 2 O 2 counterparts. The results are helpful for us to determine whether the UV/AA process is applicable to certain wastewaters and how the UV/AA process could be effectively combined into a sequential chemical-biological water treatment., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The redox conversion of arsenite and nitrate has direct effects on their potential environment risks. Due to the similar reduction potentials, there are few technologies that can simultaneously oxidize arsenite and reduce nitrate in one process. Here, we demonstrate that a diketone-mediated photochemical process could efficiently do this. A combined experimental and theoretical investigation was conducted to elucidate the mechanisms behind the redox conversion in the UV/acetylacetone (AA) process. Our key finding is that UV irradiation significantly changed the redox potential of AA. The excited AA, 3 (AA)*, acted as a semiquinone radical-like electron shuttle. For arsenite oxidation, the efficiency of 3 (AA)* was 1-2 orders of magnitude higher than those of quinone-type electron shuttles, whereas the consumption of AA was 2-4 orders of magnitude less than those of benzonquinones. The oxidation of arsenite and reduction of nitrate could be both accelerated when they existed together in UV/AA process. The results indicate that small diketones are some neglected but potent electron shuttles of great application potential in regulating aquatic redox reactions with the combination of UV irradiation., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Acetylacetone (AcAc) has proven to be a potent photo-activator in the degradation of color compounds. The effects of AcAc on the photochemical conversion of five colorless pharmaceuticals were for the first time investigated in both pure and natural waters with the UV/H 2 O 2 process as a reference. In most cases, AcAc played a similar role to H 2 O 2 . For example, AcAc accelerated the photodecomposition of carbamazepine, oxytetracycline, and tetracycline in pure water. Meanwhile, the toxicity of tetracyclines and carbamazepine were reduced to a similar extent to that in the UV/H 2 O 2 process. However, AcAc worked in a way different from that of H 2 O 2 . Based on the degradation kinetics, solvent kinetic isotope effect, and the inhibiting effect of O 2 , the underlying mechanisms for the degradation of pharmaceuticals in the UV/AcAc process were believed mainly to be direct energy transfer from excited AcAc to pharmaceuticals rather than reactive oxygen species-mediated reactions. In natural waters, dissolved organic matter (DOM) played a crucial role in the photoconversion of pharmaceuticals. The role of H 2 O 2 became negligible due to the scavenging effects of DOM and inorganic ions. Interestingly, in natural waters, AcAc first accelerated the photodecomposition of pharmaceuticals and then led to a dramatic reduction with the depletion of dissolved oxygen. Considering the natural occurrence of diketones, the results here point out a possible pathway in the fate and transport of pharmaceuticals in aquatic ecosystems., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Octyl-dimethyl-p-aminobenzoic acid (ODPABA), one of the most commonly used organic UV filters, can undergo considerable transformation in water when entering into the disinfection process. The impacts of bromide on degradation kinetics, formation and speciation of transformation products, regulated disinfection by-products (DBPs) as well as genotoxicity changes during ODPABA chlorination were investigated in this study. Results indicated that the reaction of ODPABA with chlorine followed pseudo-first-order and second-order kinetics. Adding bromide noticeably enhanced the degradation rate of ODPABA, but reduced the impact of chlorine dose. Four halogenated transformation products (Cl-ODPABA, Br-ODPABA, Cl-Br-ODPABA and Br 2 -ODPABA) were detected by LC-MS/MS. Mono-halogenated products were stable during 24-h chlorination, while di-halogenated products constantly increased. The total yields of trihalomethanes (THMs) and haloacetic acids (HAAs) were both low, but predominated by bromine substitution at high levels of bromide. In addition, SOS/umu tests showed that genotoxicity was generated after ODPABA chlorination, which was increased at least 1.5 times in the presence of bromine. Whereas, no significant genotoxicity variation was observed following bromide concentration change., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Nitrogen (N) runoff from paddy fields serves as one of the main sources of water pollution. Our aim was to reduce N runoff from paddy fields by fertilizer management and inoculation with arbuscular mycorrhizal fungi (AMF). In northeast China, Shuangcheng city in Heilongjiang province, a field experiment was conducted, using rice provided with 0%, 20%, 40%, 60%, 80%, and 100% of the local norm of fertilization (including N, phosphorus and potassium), with or without inoculation with Glomus mosseae. The volume, concentrations of total N (TN), dissolved N (DN) and particulate N (PN) of runoff water were measured. We found that the local norm of fertilization led to 18.9kg/ha of N runoff during rice growing season, with DN accounting for 60%-70%. We also found that reduction in fertilization by 20% cut down TN runoff by 8.2% while AMF inoculation decreased N runoff at each fertilizer level and this effect was inhibited by high fertilization. The combination of inoculation with AMF and 80% of the local norm of fertilization was observed to reduce N runoff by 27.2%. Conclusively, we suggested that the contribution of AMF inoculation combined with decreasing fertilization should get more attention to slow down water eutrophication by reducing N runoff from paddy fields., (Copyright © 2016. Published by Elsevier B.V.)

A highly stable and efficient biocatalyst was fabricated by encapsulating Trametes versicolor laccase within a chitosan grafted polyacrylamide hydrogel (denoted as Lac-PAM-CTS). Scanning electron microscopy and nitrogen adsorption-desorption tests demonstrated that channels of diameter of 10-20 μm were regularly distributed throughout the sponge-like Lac-PAM-CTS. Besides, there were massive mesopores and macropores in the lamellar walls of the hydrogel. Such a network structure reduced the diffusion resistance of the hydrogel to the target substrates. The recovered activity of the obtained Lac-PAM-CTS was 40.8%. As compared to free laccase, the Lac-PAM-CTS showed enhanced thermal and chemical stability. The positive surface charge of the Lac-PAM-CTS endowed it with a pre-enrichment effect in the treatment of anionic dyes. In a continuous six-cycle batch decoloration of Malachite Green, the Lac-PAM-CTS showed much better durability than the free laccase. The results here suggest that sponge-like hydrogel is a good supporting matrix for laccase., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Low-cost and environmentally friendly mediators could facilitate the application of laccase (EC 1.10.3.2) in variant biotechnological processes. Acetylacetone (AA) represents an inexpensive and low toxic small molecular diketone that has been proven as an effective mediator for laccase in free radical polymerization. However, the potential of AA as a mediator for laccase in pollutant detoxification and/or degradation is still unknown. In this work, the roles of AA in laccase-induced polymerization and transformation were investigated. AA was demonstrated to be a highly efficient mediator in the laccase-induced grafting copolymerization of acrylamide and chitosan. The efficacy of AA in the laccase-induced decoloration of malachite green (MG) was compared with that of the widely used 1-hydroxybenzotriazole (HBT). The laccase-AA system had the highest turnover number (TON, 39.1 μmol/U), followed by the laccase-only system (28.5 μmol/U), while the TON of the laccase-HBT system was the lowest (14.9 μmol/U). The pseudo-first-order transformation rate constant (k 1) of MG in the laccase-AA system was up to 0.283 h(-1) under the given conditions, while the k 1 of AA caused by laccase was only 0.008 h(-1). In the five-cycle run, the concentration of AA remained stable. The larger TON of the laccase-AA system and the stability of AA in the cycling runs demonstrate that AA was more recyclable than HBT in the LMS, leading to a prolonged serving life of laccase. These results suggest that AA might be a potential redox mediator for laccase.

The acetylacetone (AA) mediated photochemical process has been proven as an efficient approach for decoloration. For azo dyes, the UV/AA process was several to more than ten times more efficient than the UV/H2O2 process. Iron is one of the most common elements on the earth. It is well known that iron can improve the UV/H2O2 process through thermal Fenton and photo-Fenton reactions. What will be the role of iron in the UV/AA process? Could iron-AA complexes act as photocatalysts in environmental remediation? To answer these questions, the photo-degradation of an azo dye, Acid Orange 7 (AO7), was conducted under the variant combinations of AA with iron species in both ionic (Fe2+, Fe3+) and complex (Fe(AA)3) forms. The pseudo-first-order decoloration rate constants of AO7 in these photochemical processes followed such an order: UV/Fe(II)/AA

Our study sought to assess how much phosphorus (P) runoff from paddy fields could be cut down by fertilizer management and inoculation with arbuscular mycorrhizal fungi. A field experiment was conducted in Lalin River basin, in the northeast China: six nitrogen-phosphorus-potassium fertilizer levels were provided (0, 20%, 40%, 60%, 80%, and 100% of the recommended fertilizer supply), with or without inoculation with Glomus mosseae. The volume and concentrations of particle P (PP) and dissolved P (DP) were measured for each runoff during the rice growing season. It was found that the seasonal P runoff, including DP and PP, under the local fertilization was 3.7 kg/ha, with PP, rather than DP, being the main form of P in runoff water. Additionally, the seasonal P runoff dropped only by 8.9% when fertilization decreased by 20%; rice yields decreased with declining fertilization. We also found that inoculation increased rice yields and decreased P runoff at each fertilizer level and these effects were lower under higher fertilization. Conclusively, while rice yields were guaranteed arbuscular mycorrhizal inoculation and fertilizer management would play a key role in reducing P runoff from paddy fields., (Copyright © 2015. Published by Elsevier B.V.)

Understanding the aggregation and deposition behavior of carbon nanotubes (CNTs) is of great significance in terms of their fate and transport in the environment. Attachment efficiency is a widely used index for well-dispersed CNT solutions. However, in natural waters, CNTs are usually heterogeneous in particle size. The attachment efficiency method is not applicable to such systems. Describing the dispersion stability of CNTs in natural aquatic systems is still a challenge. In this work, a settling curve modeling (SCM) method was developed for the description of the aggregation and deposition behavior of CNTs in aqueous solutions. The effects of water chemistry (natural organic matter, pH, and ionic strength) on the aggregation and deposition behavior of pristine and surface-functionalized multi-walled carbon nanotubes (MWCNTs) were systematically studied to evaluate the reliability of the SCM method. The results showed that, as compared to particle size and optical density, the centrifugal sedimentation rate constant (ks) from the settling curve profile is a practical, useful and reliable index for the description of heterogeneous CNT suspensions. The SCM method was successfully applied to MWCNT in three natural waters. The constituents in water, especially organic matter, determine the dispersion stability of MWCNTs in natural water bodies., (Copyright © 2015. Published by Elsevier B.V.)

Acetylacetone (AcAc) was employed as a photo-activator for the degradation of Acid Orange 7 (AO7) under UV irradiation. The feasibility of this process (named as UV/AcAc) was evaluated through comparison with the well-established UV/H2O2 process in terms of absorption spectrum and the biodegradability of the solutions. A complete decoloration of the AO7 solution could be fulfilled with AcAc at mM level. A self-acceleration phenomenon was observed for the UV/AcAc process. The pseudo first-order decoloration rate constant of AO7 in the UV/AcAc process was several times higher than that in the UV/H2O2 process, depending on the irradiation conditions. The BOD to COD ratio of the solutions increased from below 0.1 to above 0.3, along with a slight mineralization. Based on degradation product analysis, the possible pathways for AO7 degradation in the UV/AcAc process were proposed., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

To reveal how the distribution of nanoscale zero-valent iron (nZVI) affect their reduction efficiency of its polymer-based composites and to further develop a simple strategy to tune the structure of the composites, we prepared four nZVI-polymerstyrene anion exchanger composites with similar nZVI loadings (13.5-14.4 Fe % in mass) but different distributions just through varying the concentration of NaBH(4) (0.9, 1.8, 3.6, and 7.2% in mass) solution during reduction of nZVI precursor (FeCl(4)(-) anions). As observed by SEM-EDX images, increasing the NaBH(4) concentration resulted in a more uniform nZVI distribution within the polymer, and thereto higher NH(4)(+)N production, faster reaction rate and more gaseous products during its reduction of nitrate and nitrite. nZVI distribution of the composites was suggested to greatly depend upon two processes, the hydrolyzation of anionic FeCl(4)(-) into cationic Fe(3+) and the reduction of both Fe(III) species by NaBH(4). Higher NaBH(4) concentration favored its faster diffusion into the inside polymer and in situ reduction of Fe(III) species into nZVI, causing a more uniform nZVI distribution. The results reported herein suggest that adjusting the NaBH(4) concentration was a simple and effective method to control the nZVI distribution in the supporting polymers, and indirectly tune the reactivity of the resultant nZVI hybrids., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Effect of effluent organic matter (EfOM) on the adsorption of perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) onto powdered activated carbon (PAC) was quantitatively investigated at environmentally relevant concentration levels. The adsorption of both perfluorinated compounds (PFCs) onto PAC followed pseudo-second order kinetics and fitted the Freundlich model well under the given conditions. Intraparticle diffusion was found to be the rate-controlling step in the PFC adsorption process onto PAC in the absence and presence of EfOM. The presence of EfOM, either in PFC-EfOM simultaneous adsorption onto fresh PAC or in PFC adsorption onto EfOM-preloaded PAC, significantly reduced the adsorption capacities and sorption rates of PFCs. The pH of zero point of charge was found to be 7.5 for fresh PAC and 4.2 for EfOM-preloaded PAC, suggesting that the adsorbed EfOM imparted a negative charge on PAC surface. The effect of molecular weight distribution of EfOM on the adsorption of PFCs was investigated with two EfOM fractions obtained by ultrafiltration. The low-molecular-weight compounds (<1kDa) were found to be the major contributors to the significant reduction in PFC adsorption capacity, while large-molecular-weight compounds (>30kDa) had much less effect on PFC adsorption capacity., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Nanosized metal oxides (NMOs), including nanosized ferric oxides, manganese oxides, aluminum oxides, titanium oxides, magnesium oxides and cerium oxides, provide high surface area and specific affinity for heavy metal adsorption from aqueous systems. To date, it has become a hot topic to develop new technologies to synthesize NMOs, to evaluate their removal of heavy metals under varying experimental conditions, to reveal the underlying mechanism responsible for metal removal based on modern analytical techniques (XAS, ATR-FT-IR, NMR, etc.) or mathematical models, and to develop metal oxide-based materials of better applicability for practical use (such as granular oxides or composite materials). The present review mainly focuses on NMOs' preparation, their physicochemical properties, adsorption characteristics and mechanism, as well as their application in heavy metal removal. In addition, porous host supported NMOs are particularly concerned because of their great advantages for practical application as compared to the original NMOs. Also, some magnetic NMOs were included due to their unique separation performance., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Adsorption kinetics of two organic compounds on four types of carbonaceous adsorbents (a granular activated carbon [HD4000], an activated carbon fiber [ACF10], a single-walled carbon nanotube [SWNT], and a multiwalled carbon nanotube [MWNT]) was examined in aqueous solutions. The times needed for the adsorption to reach apparent equilibrium on the four carbons followed the order of ACF10 > HD4000 > SWNT > MWNT. Ultrasonication of the carbon nanotubes (CNTs) accelerated their adsorption kinetics but had no effect on their equilibrium adsorption capacities. The pseudo-second order model (PSOM) provided good fitting for the kinetic data. The fitting of kinetic data with the intraparticle diffusion model indicated that external mass transfer controls the sorption process in the organic compound-CNT systems, whereas intraparticle diffusion dominates in the sorption of organic compounds onto activated carbons., (Copyright © 2011 SETAC.)

Understanding the influence of natural organic matter (NOM) on synthetic organic contaminant (SOC) adsorption by carbon nanotubes (CNTs) is important for assessing the environmental implications of accidental CNT release and spill to natural waters, and their potential use as adsorbents in engineered systems. In this study, adsorption of two SOCs by three single-walled carbon nanotubes (SWNTs), one multi-walled carbon nanotube (MWNT), a microporous activated carbon fiber (ACF) [i.e., ACF10] and a bimodal porous granular activated carbon (GAC) [i.e., HD4000] was compared in the presence and absence of NOM. The NOM effect was found to depend strongly on the pore size distribution of carbons. Minimal NOM effect occurred on the macroporous MWNT, whereas severe NOM effects were observed on the microporous HD4000 and ACF10. Although the single-solute adsorption capacities of the SWNTs were much lower than those of HD4000, in the presence of NOM the SWNTs exhibited adsorption capacities similar to those of HD4000. Therefore, if released into natural waters, SWNTs can behave like an activated carbon, and will be able to adsorb, carry, and transfer SOCs to other systems. However, from an engineering application perspective, CNTs did not exhibit a major advantage, in terms of adsorption capacities, over the GAC and ACF. The NOM effect was also found to depend on molecular properties of SOCs. NOM competition was more severe on the adsorption of 2-phenylphenol, a nonplanar and hydrophilic SOC, than phenanthrene, a planar and hydrophobic SOC, tested in this study. In terms of surface chemistry, both adsorption affinity to SOCs and NOM effect on SOC adsorption were enhanced with increasing hydrophobicity of the SWNTs., (Copyright © 2010 Elsevier Ltd. All rights reserved.)