•The review about speciation analysis of HMCs is important but scarce.•Prevalent methods for aqueous HMC mitigation were introduced.•Technologies for aqueous HMC analysis were summarized and ...discussed.•The importance role of species transformation in HMC decomplexation was elucidated.•Outlook and perspective were provided based on current challenges.
Efficient mitigation of toxic and recalcitrant heavy metal complexes (HMCs) from water and wastewater is critical to guarantee the environmental health and safety, but still faces many challenges. Although a number of techniques have been developed to deal with HMCs laden water/wastewater, there is still a lack of comprehensive and insightful understanding of the relevant mechanisms. One of the main reasons is the complicated heavy metal speciation in water/wastewater, which masks the speciation distribution and coordination circumstance of heavy metals. In this review, prevalent methods for HMC elimination (e.g., physical separation and chemical decomplexation) are briefly presented and evaluated. Especially, the characterization methods of HMCs, which afford to provide valuable information on the speciation distribution of heavy metals, are underlined and discussed. Furthermore, typical cases are provided to elucidate the essential role of species transformation in the decomplexation of HMCs and the implications for enhanced mitigation of HMCs are also discussed. Finally, the current challenges and perspectives for future study in this field are proposed.
The Fenton system generates reactive species with high oxidation potential such as hydroxyl radicals (HO(•)) or ferryl via the reaction between Fe (II) and H₂O₂. However, a number of drawbacks limit ...its widespread application including the accumulation of Fe (III) and the narrow pH range limits, etc. The aim of this study is to propose a much more efficient Fenton-HA system which is characterized by combining Fenton system with hydroxylamine (NH₂OH), a common reducing agent, to relieve the aforementioned drawbacks, with benzoic acid (BA) as the probe reagent. The presence of NH₂OH in Fenton's reagent accelerated the Fe (III)/Fe (II) redox cycles, leading to relatively steady Fe (II) recovery, thus, increased the pseudo first-order reaction rates and expanded the effective pH range up to 5.7. The HO(•) mechanism was confirmed to be dominating in the Fenton-HA system, and the generation of HO(•) was much faster and the amount of HO(•) formed was higher than that in the classical Fenton system. Furthermore, the major end products of NH₂OH in Fenton-HA system were supposed to be NO₃(-) and N₂O.
The UV/chlorine process, which forms several reactive species including hydroxyl radicals (HO) and reactive chlorine species (RCS) to degrade contaminants, is being considered to be an advanced ...oxidation process. This study investigated the kinetics and mechanism of the degradation of trimethoprim (TMP) by the UV/chlorine process. The degradation of TMP was much faster by UV/chlorine compared to UV/H2O2. The degradation followed pseudo first-order kinetics, and the rate constant (k′) increased linearly as the chlorine dosage increased from 20 μM to 200 μM and decreased as pH rose from 6.1 to 8.8. k′ was not affected by chloride and bicarbonate but decreased by 50% in the presence of 1-mg/L NOM. The contribution of RCS, including Cl, Cl2− and ClO, to the degradation removal rate was much higher than that of HO and increased from 67% to 87% with increasing pH from 6.1 to 8.8 under the experimental condition. The increasing contribution of RCS to the degradation with increasing pH was attributable to the increase in the ClO concentration. Kinetic modeling and radical scavenging tests verified that ClO mainly attacked the trimethoxybenzyl moiety of TMP. RCS reacted with TMP much faster than HOCl/OCl− to form chlorinated products (i.e., m/z 325) and chlorinated disinfection byproducts such as chloroform, chloral hydrate, dichloroacetonitrile and trichloronitromethane. The hydroxylation and demethylation of m/z 325 driven by HO generated m/z 327 and m/z 341. Meanwhile, reactions of m/z 325 with HO and RCS/HOCl/OCl− generated dichlorinated and hydroxylated products (i.e., m/z 377). All the chlorinated products could be further depleted to produce products with less degree of halogenation in the UV/chlorine process, compared to dark chlorination. The acute toxicity to Vibrio fischeri by UV/chlorine was lower than chlorination at the same removal rate of TMP. This study demonstrated the importance of RCS, in particular, ClO, in the degradation of micropollutants in the UV/chlorine process.
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•Trimethoprim degradation by the UV/chlorine process was studied.•Reactive chlorine species (i.e., Cl, Cl2− and ClO) greatly contributed to the degradation.•The contribution of ClO increased with increasing pH and chlorine dosage.•Reactive chlorine species reacted much faster than chlorine to form chlorinated products.•Products with less halogenation degree were formed in UV/chlorine compared to chlorination.
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•Cr(VI) was efficiently reduced to Cr(III) at alkaline pHs by UV/sulfite process.•Common ions and organic matters interfered with Cr(VI) reduction slightly.•Spontaneous precipitation ...of Cr(III) occurred in the presence of Ca2+ (>2ppm).•eaq− was identified as the dominant reactive species in UV/sulfite process.
Chemical reduction of Cr(VI) to Cr(III) followed by Cr(III) precipitation is a widely employed strategy to mitigate Cr(VI) pollution from industrial effluents. Nevertheless, most of the available reduction processes are feasible at acidic pHs only, and very few technologies are capable of reducing Cr(VI) at alkaline pHs. Herein, we demonstrated that the UV/sulfite process is very promising for alkaline Cr(VI) remediation, including the Cr(VI) reduction to Cr(III) and simultaneous Cr(III) precipitation. In this process Cr(VI) reduction followed near zero-order kinetics, declining with an increase of pH (5–10) but boosting with increasing sulfite concentration. The co-existing Cl− and SO42− in water exerted negligible effect on Cr(VI) reduction, whereas the reduction kinetics was improved in the presence of citrate, EDTA or humic acid possibly due to their complexation with Cr(III). Similarly, the presence of borate buffer would significantly inhibit Cr(VI) reduction to Cr(III) as well as the final Cr(III) removal during precipitation. Fortunately, the presence of calcium ions even at trace level would favor Cr(III) precipitation and result in one-step removal of the total Cr at alkaline pH. The mechanism of Cr(VI) reduction was probed through irradiation manipulation and N2O addition, and the results suggested that excitation of sulfite is essential for alkaline Cr(VI) reduction, and eaq− is the dominant reactive species in the UV/sulfite process.
The degradation of pharmaceuticals and personal care products (PPCPs) by the UV/H2O2 and UV/chlorine processes was compared at practical concentrations in simulated drinking water and wastewater. In ...pure water, the UV/chlorine process performed better than the UV/H2O2 process for the degradation of 16 PPCPs among the investigated 28 PPCPs under neutral conditions. Interestingly, the UV/chlorine approach was superior to the UV/H2O2 approach for the removal of all PPCPs in simulated drinking water and wastewater at the same molar oxidant dosage. The radical sink by oxidants and/or H2O was 2–3 orders of magnitude higher in UV/chlorine than UV/H2O2 in pure water. Thus, the UV/chlorine process was less affected by the water and wastewater matrices than UV/H2O2. In UV/chlorine, the concentration of ClO• was calculated to be ∼3 orders of magnitude greater than that of HO• in pure water, and the reactivities of ClO• with some PPCPs were as high as > 108 M−1 s−1. ClO• was mainly scavenged by the effluent organic matter (EfOM) with a rate constant of 1.8 × 104 (mg L−1)−1 s−1 in wastewater. Meanwhile, secondary radicals such as Br•, Br2•-, ClBr•- and CO3•- further contributed to PPCP degradation by the UV/chlorine process in wastewater, whose concentrations were at least 2 orders of magnitude higher than that in UV/H2O2. Compared with the UV/H2O2 process, the UV/chlorine process saved 3.5–93.5% and 19.1%–98.1% electrical energy per order (EE/O) for PPCP degradation in simulated drinking water and wastewater, respectively.
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•UV/chlorine and the UV/H2O2 were compared for the abatement of 28 PPCPs at neutral pH.•The concentration of HO.• was lower in UV/chlorine, but Cl• and ClO• compensated it.•UV/chlorine was less affected by water matrices than UV/H2O2 for PPCP degradation.•The secondary radicals such as Br.•, ClBr•- and CO3•- were higher in UV/chlorine in wastewater.•EE/O was lower in UV/chlorine than UV/H2O2 in simulated drinking water and wastewater.
The reaction between ferrous iron (Fe(II)) with peroxymonosulfate (PMS) generates reactive oxidants capable of degrading refractory organic contaminants. However, the slow transformation from ferric ...iron (Fe(III)) back to Fe(II) limits its widespread application. Here, we added hydroxylamine (HA), a common reducing agent, into Fe(II)/PMS process to accelerate the transformation from Fe(III) to Fe(II). With benzoic acid (BA) as probe compound, the addition of HA into Fe(II)/PMS process accelerated the degradation of BA rapidly in the pH range of 2.0-6.0 by accelerating the key reactions, including the redox cycle of Fe(III)/Fe(II) and the generation of reactive oxidants. Both sulfate radicals and hydroxyl radicals were considered as the primary reactive oxidants for the degradation of BA in HA/Fe(II)/PMS process with the experiments of electron spin resonance and alcohols quenching. Moreover, HA was gradually degraded to N2, N2O, NO2 (−), and NO3 (−), while the environmentally friendly gas of N2 was considered as its major end product in the process. The present study might provide a promising idea based on Fe(II)/PMS process for the rapid degradation of refractory organic contaminants in water treatment.
Degradation of three lipid regulators, i.e., gemfibrozil, bezafibrate and clofibric acid, by a UV/chlorine treatment was systematically investigated. The chlorine oxide radical (ClO•) played an ...important role in the degradation of gemfibrozil and bezafibrate with second-order rate constants of 4.2 (±0.3) × 108 M−1 s−1 and 3.6 (±0.1) × 107 M−1 s−1, respectively, whereas UV photolysis and the hydroxyl radical (HO•) mainly contributed to the degradation of clofibric acid. The first-order rate constants (k′) for the degradation of gemfibrozil and bezafibrate increased linearly with increasing chlorine dosage, primarily due to the linear increase in the ClO• concentration. The k′ values for gemfibrozil, bezafibrate, and clofibric acid degradation decreased with increasing pH from 5.0 to 8.4; however, the contribution of the reactive chlorine species (RCS) increased. Degradation of gemfibrozil and bezafibrate was enhanced in the presence of Br−, whereas it was inhibited in the presence of natural organic matter (NOM). The presence of ammonia at a chlorine: ammonia molar ratio of 1:1 resulted in decreases in the k′ values for gemfibrozil and bezafibrate of 69.7% and 7%, respectively, but led to an increase in that for clofibric acid of 61.8%. Degradation of gemfibrozil by ClO• was initiated by hydroxylation and chlorine substitution on the benzene ring. Then, subsequent hydroxylation, bond cleavage and chlorination reactions led to the formation of more stable products. Three chlorinated intermediates were identified during ClO• oxidation process. Formation of the chlorinated disinfection by-products chloral hydrate and 1,1,1-trichloropropanone was enhanced relative to that of other by-products. The acute toxicity of gemfibrozil to Vibrio fischeri increased significantly when subjected to direct UV photolysis, whereas it decreased when oxidized by ClO•. This study is the first to report the transformation pathway of a micropollutant by ClO•.
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•Lipid regulators were efficiently degraded by UV/chlorine.•ClO.• primarily contributed to the degradation of gemfibrozil and bezafibrate.•ClO.• transformed gemfibrozil through hydroxylation and chlorine substitution.•Acute toxicity of the transformation products of gemfibrozil by ClO.• was lower than UV photolysis.
Aqueous suspensions of Microcystis aeruginosa were preoxidized with either ozone or permanganate and then subjected to chlorination under conditions simulating drinking water purification. The ...impacts of the two oxidants on the algal cells and on the subsequent production of dissolved organic matter and disinfection byproducts were investigated. Preozonation dramatically increased disinfection byproduct formation during chlorination, especially the formation of haloaldehydes, haloacetonitriles, and halonitromethanes. Preoxidation with permanganate had much less effect on disinfection byproduct formation. Preozonation destroyed algal cell walls and cell membranes to release intracellular organic matter (IOM), and less than 2.0% integrated cells were left after preozonation with the dosage as low as 0.4 mg/L. Preoxidation with permanganate mainly released organic matter adsorbed on the cells' surface without causing any damage to the cells' integrity, so the increase in byproduct formation was much less. More organic nitrogen and lower molecular weight precursors were produced in a dissolved phase after preozonation than permanganate preoxidation, which contributes to the significant increase of disinfection byproducts after preozonation. The results suggest that permanganate is a better choice than ozone for controlling algae derived pollutants and disinfection byproducts.
Vacuum-Ultraviolet (VUV), an efficient and green method to produce hydroxyl radical (•OH), is effective in degrading numerous organic contaminants in aqueous solution. Here, we proposed an effective ...and simple kinetic model to describe the degradation of organic pollutants in VUV system, by taking the •OH scavenging effects of formed organic intermediates as co-existing organic matter in whole. Using benzoic acid (BA) as a •OH probe, •OH was regarded vital for pollutant degradation in VUV system, and the thus developed model successfully predicted its degradation kinetics under different conditions. Effects of typical influencing factors such as BA concentrations and UV intensity were investigated quantitatively by the model. Temperature was found to be an important influencing factor in the VUV system, and the quantum yield of •OH showed a positive linear dependence on temperature. Impacts of humic acid (HA), alkalinity, chloride, and water matrices (realistic waters) on the oxidation efficiency were also examined. BA degradation was significantly inhibited by HA due to its scavenging of •OH, but was influenced much less by the alkalinity and chloride; high oxidation efficiency was still obtained in the realistic water. The degradation kinetics of three other typical micropollutants including bisphenol A (BPA), nitrobenzene (NB) and dimethyl phthalate (DMP), and the mixture of co-existing BA, BPA and DMP were further studied, and the developed model predicted the experimental data well, especially in realistic water. It is expected that this study will provide an effective approach to predict the degradation of organic micropollutants by the promising VUV system, and broaden the application of VUV system in water treatment.
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•A simple and effective kinetic model in VUV system was developed.•Effects of typical factors were examined quantitatively.•Quantum yield of .•OH showed a positive linear dependence on temperature.•The model predicted degradation kinetics of typical micropollutants well.
Hydrated electron (eaq−), which is listed among the most reactive reducing species, has great potential for removal and detoxification of recalcitrant contaminants. Here we provided quantitative ...insight into the availability and conversion of eaq− in a newly developed sulfite/UV process. Using monochloroacetic acid as a simple eaq−-probe, the eaq−-induced dehalogenation kinetics in synthetic and surface water was well predicted by the developed models. The models interpreted the complex roles of pH and S(IV), and also revealed the positive effects of UV intensity and temperature quantitatively. Impacts of humic acid, ferrous ion, carbonate/bicarbonate, and surface water matrix were also examined. Despite the retardation of dehalogenation by electron scavengers, the process was effective even in surface water. Efficiency of the process was discussed, and the optimization approaches were proposed. This study is believed to better understand the eaq−-induced dehalogenation by the sulfite/UV process in a quantitative manner, which is very important for its potential application in water treatment.
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•The eaq− availability in the sulfite/UV process was quantified.•A new model was proposed to describe the eaq−-induced dehalogenation kinetics.•Quantitative effects of solution chemistry were examined.•Efficiency of the sulfite/UV process was discussed.
