Shuhui Sun,Chao Shan,Zhichao Yang,Shu Wang,Bingcai Pan
Phosphonate is an important category of highly soluble organophosphorus in contaminated waters, and its oxidative transformation into phosphate is usually a prerequisite step to achieve the in-depth removal of the total phosphorus. Currently, selective oxidation of phosphonate into phosphate is urgently desired as conventional advanced oxidation processes suffer from severe matrix interferences. Herein, we employed 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) as a model phosphonate and demonstrated its efficient and selective oxidation by the Cu(II)/H2O2 process at alkaline pH. In the presence of trace Cu(II) (0.020 mM), 90.8% of HEDP (0.10 mM) was converted to phosphate by H2O2 in 30 min at pH 9.5, whereas negligible conversion was observed by UV/H2O2 or a Fenton reaction (pH = 3.0). The oxidation of HEDP by Cu(II)/H2O2 was insignificantly affected by natural organic matters (10.0 mg TOC/L) and various anions including chloride, sulfate, and nitrate (10.0 mM). The complexation of Cu(II) with HEDP coupling Cu(III) produced in situ enabled an intramolecular electron transfer process, which features high selective oxidation. Selective degradation of HEDP was further validated by adding stoichiometric H2O2 into an industrial effluent, where the existing Cu(II) could serve as the catalyst. This study also provides a successful case to trigger selective oxidation of trace pollutants of concern upon synergizing with the nature of the contaminated water.
Xue Han,Zhixin Qin,Mengyao Zhao,Jiajia Song,Fei Qu,Fengli Qu,Rong-Mei Kong
The illegal adulteration of melamine in dairy products for false protein content increase is a strong hazard to human health. Herein, a simple and sensitive colorimetric method was developed for the quantification of melamine in dairy products based on a Cu2+-hydrogen peroxide (H2O2)-3,3′,5,5′-tetramethylbenzidine (TMB) system. In this strategy, Cu2+ exhibits peroxidase-like activity and can catalyze the oxidation of TMB to oxidized TMB (oxTMB) in the presence of H2O2 with a blue colour change of the solution. However, the presence of melamine quickly interacts with H2O2 leading to the consumption of H2O2 and thus strongly hinders the oxidation of TMB. Under the optimal conditions, the absorbance change of oxTMB has a linear response to the concentration of melamine from 1 to 100 μM with a detection limit of 0.5 μM for melamine. The proposed method has many merits including more simplicity, good selectivity, and more cost-effectiveness without using any nanomaterials. The method was further successfully applied to detect melamine in dairy products including milk and infant formula powder.
Without extra adjustment of pH, the effects of cupric ions (Cu(II)) and hydrogen peroxide (H 2 O 2 ) alone or in combination on sludge dewatering were studied. It showed good dewatering capability after treated by Cu(II) and Cu(II)/H 2 O 2 , which indicated by the capillary suction times (CST) decreased from 120.8 ± 4.7 s (control) to about 40 s, and the water content (Wc) of sludge cake dropped by about 10%. The results showed that the extracellular polymeric substances (EPS) were destroyed, which characterized by a significant decrease in the biopolymers’ concentrations in tightly-bound EPS. Meanwhile, more rough and porous microstructures and higher zeta potentials were obtained after conditioned. Based on the changes of physicochemical properties of sludge, the variations of EPS, and the identification of reactive species, two distinct mechanisms of improved sludge dewatering were postulated. As for Cu(II) treatment, it was mainly due to the surface charge neutralization, strong cytotoxicity of Cu(I) produced by intracellular reduction of Cu(II), and pH decline caused by Cu(II) hydrolysis that improved sludge dewatering performance, which could be noted as a “non-radical pathway”. When in combination with H 2 O 2 , hydroxyl radicals (·OH) produced by Cu(II)-catalyzed Fenton-like process played a dominant role in degrading sludge flocs and EPS, which could be regarded as a “radical pathway”.
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