Comparison of radical and non-radical activated persulfate systems for the degradation of imidacloprid in water.

The study focuses on degradation efficiency of non-radical activation and radical activation systems of persulfate (PS) to degrade imidacloprid (IMI) by using sodium persulfate (SPS) as PS source. Copper oxide (CuO)-SPS and CuO/biochar (BC)-SPS were selected as PS non-radical activation systems, and pyrite (PyR)-SPS was selected as PS radical activation system. The degradation by CuO-SPS, CuO/BC-SPS and PyR-SPS systems was investigated from acidic to basic conditions (pH 3.0-11.0). Highest degradation by CuO-SPS and CuO/BC-SPS systems was achieved over pH 11.0. In contrast, highest degradation by PyR-SPS system was achieved over pH 3.0, however, PyR-SPS system was also found effective up to pH 9.0. It was found that degradation was more efficient in PS radical activation system, indicating that IMI could be oxidized by radicals rather than by activated PS. Electron paramagnetic resonance (EPR) analysis was carried out to investigate the generation of sulfate (SO4-) and hydroxyl (OH) radicals, which indicated the presence of SO4- and OH in CuO-SPS, CuO/BC and PyR-SPS systems. However, free radical quenching analysis indicated that radicals were main reactive oxygen species for degradation. The lower degradation in PS non-radical activation systems was probably resulted from radicals existed as minor reactive oxygen species. The findings indicated that non-radical oxidation systems showed low reality for degradation and good degradation could be achieved by radical oxidation system. The degradation was also carried out in real waters to investigate the potential applicability of applied systems, which supported PyR-SPS system for effective degradation.

Arsenic removal from aqueous solutions and groundwater using agricultural biowastes-derived biosorbents and biochar: a column-scale investigation.

In this study, column-scale laboratory experiments were performed to evaluate the arsenic (As) removal efficiency of different agricultural biowastes-derived biosorbents (orange peel, banana peel, rice husk) and biochar, using As-containing solutions and As-contaminated groundwater. All the biosorbents and biochar efficiently removed (50-100%) As from groundwater (drinking well water). Arsenic removal potential of biosorbents varied with their type, As concentration, contact time, and As solution type. After 1 h, the As removal efficiency of all the biosorbents was 100%, 100% and 90% for 5, 10, and 50 µg/L As-contaminated groundwater samples, respectively; and it was 50%, 90%, and 90% for 10, 50, and 100 µg/L As solutions, respectively. After 2 h, all the biosorbents and biochar removed 100% As from aqueous solutions except for 100 µg/L As solution. This showed that the biosorbents and biochar could be used to reduce As contents below the WHO safe limit of As in drinking water (10 µg/L). Fourier transform infrared (FTIR) spectroscopy indicated possible role of various surface functional moieties on biosorbents/biochar surface to remove As from solution and groundwater. This pilot-scale column study highlights that the biosorbents and biochar can be effectively used in remediation of As-contaminated groundwater, although the soluble salts in groundwater increased after treatment with biochar.

Degradation of ronidazole by electrochemically simultaneously generated persulfate and ferrous ions.

Nitroimidazoles are found in pharmaceuticals and personal care products (PPCPs) and, when discharged into the environment, have adverse effects on human health and survival. Advanced oxidation technologies (AOTs) based on persulfate (PS) can rapidly and efficiently degrade organic pollutants via strong oxidizing radicals under activation conditions. This study investigated the degradation of ronidazole (RNZ) by indirect electrolytic generation of PS and its activator, ferrous ion (Fe2+). An electrochemical system was developed, with a high concentration of PS generated at the anode while the activator Fe2+ was produced at the cathode. It showed that ammonium polyphosphate (APP) could effectively promote the electrolysis of PS. A high current efficiency (88%) at the anode could be obtained after 180 min at a high current density (300 mA cm-2). However, Fe2+ was inhibited at the cathode due to material control. The degradation of RNZ in the Fe2+/PS system generated from the electrochemical system was also explored. Increasing PS concentration and Fe2+/PS ratio were beneficial to the RNZ degradation. In homogeneous reactions, the degradation efficiency of RNZ could be improved by decreasing the Fe2+ addition rate through a peristaltic pump. Five intermediates were also detected and the degradation pathways were proposed. These findings provide a new method and mechanism for rapid and efficient degradation of RNZ.

Effect of pyrite on enhancement of zero-valent iron corrosion for arsenic removal in water: A mechanistic study.

In this study, the enhanced effect of pyrite (FeS2) on zero-valent iron (Fe0) corrosion for arsenic (As) removal was investigated in a combined-Fe0/FeS2 system. The effects of different Fe0/FeS2 composition, dosage and initial pH were evaluated by batch experiments. Results showed that the best combination ratio of Fe0:FeS2 (w/w) was 1:1 and the optimal dosage of mixture was 2.0 g/L. The combination of Fe0 and FeS2 in a system significantly enhanced the reactivity of Fe0 for effective As removal within a broad pH range (3.0-9.0). The effective As removal in the combined-Fe0/FeS2 system was primarily ascribed to being enhanced corrosion of Fe0 by addition of FeS2. SEM and XRD characterizations strongly verified this point. Specifically, the mechanism study (the releases of Fe2+ and total Fe ion, variations of pH values as well as XPS characterization) suggested that FeS2 in the combined-Fe0/FeS2 system could alleviate the passivation of Fe0 (pHini 3.0-5.0) and accelerate the dissolution of pristine oxide film that coated on Fe0 surface (pHini 6.8-9.0). Besides, FeS2 in combined-Fe0/FeS2 system could also accelerate the reactions between Fe0 to O2 at pHini 3.0-9.0. These phenomena were well explained by a galvanic couple between Fe0 and FeS2, where FeS2 was a cathode and Fe0 was an anode. Consequently, electrons released from Fe0 that mediated by FeS2 to oxide film, passivation layer and O2 were accelerated in combined-Fe0/FeS2 system and thereby enhanced the corrosion of Fe0 for efficient As removal. Our findings suggest that utilizing FeS2 to enhance the corrosion of Fe0 would be a promising technology for remediation of As-contaminated water.

Comparative effect of organic amendments on physio-biochemical traits of young and old bean leaves grown under cadmium stress: a multivariate analysis.

The current study investigated the influence of organic amendments on cadmium (Cd) uptake and its effects on biochemical attributes of young and old leaves of bean. Bean seedlings were exposed to two levels of Cd (25 and 100 µM) in the presence and absence of different levels of ethylenediaminetetraacetic acid (EDTA) and citric acid (CA). An increase in Cd concentration in growth medium significantly enhanced Cd accumulation in bean roots and shoot. Cadmium stress increased the production of H2O2 which resulted in lipid peroxidation and decreased chlorophyll contents. The presence of organic amendments significantly affected Cd accumulation and toxicity to bean plants. Application of EDTA alleviated Cd toxicity in terms of chlorophyll contents, H2O2 contents, and lipid peroxidation possibly by chelating toxic Cd ions, and as such forming Cd-EDTA complexes. The presence of CA decreased Cd toxicity by decreasing its uptake. The biochemical responses (H2O2 contents, lipid peroxidation, and chlorophyll contents) of bean plants were more severely affected by Cd treatments in old leaves compared to young leaves. This study shows that the effect of CA and EDTA on biochemical behavior of Cd varies greatly with applied levels of Cd and amendments as well as the age of leaves. Based on the results, it is proposed that the presence of organic amendments can greatly affect biogeochemical behavior of Cd in the soil-plant system (ecosystem).