Changyin Zhu

Mechanism of hydroxyl radical generation from biochar suspensions: Implications to diethyl phthalate degradation

This paper investigated hydroxyl radical (OH) generation from biochar suspensions for diethyl phthalate (DEP) degradation in the presence of oxygen. Electron paramagnetic resonance (EPR) coupled with a salicylic acid trapping method were used to detect free radicals in biochar and verify OH generation from biochar suspensions. Free radicals (FRs) in biochar could induce OH generation, and ≈12 spins of FRs were consumed to produce one trapped [OH] molecule. The proposed mechanism of OH generation was that FRs in biochar transferred electrons to O2 to produce the superoxide radical anion and hydrogen peroxide, which reacted further with FRs to produce OH. Free radical-quenching studies utilizing superoxide dismutase, catalase, and deferoxamine as scavengers were used to testify this mechanism. Furthermore, OH generated from biochar suspensions could degrade DEP efficiently. These findings of this study provide new insights into the physicochemical properties and environmental implications of biochar.

Efficient transformation of DDTs with Persulfate Activation by Zero-valent Iron Nanoparticles: A Mechanistic Study

In this study, persulfate (PS) activation by nano-Fe(0) was used to degrade dichlorodiphenyltrichloroethane (DDT), and the mechanism of this process was elucidated with EPR, GC-MS and free-radical quenching studies. It was found that DDT was degraded efficiently in PS/nano-Fe(0), and GC-MS analysis showed that benzoic acid, benzyl alcohol, dichlorobenzophenone and 2,2-bis(p-chlorophenyl)-ethane were the dominant products of DDT degradation, while only dechlorination products (DDD and DDE) were observed in nano-Fe(0) without persulfate. EPR results showed that persulfate activation by nano-Fe(0) led to the production of more sulfate radicals and hydroxyl radicals, which accounted for DDT degradation. But the free radical quenching studies suggested that the addition of ethanol to PS/nano-Fe(0) favored the reductive dechlorination of DDT, which was ascribed that the formed ethanol radical (CH(CH3)OH) enhanced the reductive dechlorination of DDT. Furthermore, the nano-Fe(0) loading not only affected the degradation efficiency of DDT, but also influenced the intermediate product distribution of DDT degradation in the PS/nano-Fe(0) process.

Comparison of Persulfate Activation and Fenton Reaction in Remediating an Organophosphorus Pesticides-Polluted Soil

Abstract Organophosphorus pesticides (OPs) are one of the most regular pollutants and frequently detected in the contaminated sites, so developing an efficient method for the treatment of OPs is highly required. The aim of the present study was to compare the effectiveness of persulfate (PS) activation and Fenton reaction in remediating the soil polluted with OPs. The polluted soil used in this study was sampled from an abandoned insecticide factory in Nantong, Jiangsu Province of China, mainly containing chloropyrifos (CP) and 4-bromo-2-chlorophenol (BCP, the raw material of profenofos) with total concentration of about 30 000 mg kg−1. The results showed that both BCP and CP were efficiently degraded by base activation of PS, and increasing the ratio of NaOH/PS enhanced CP degradation, but slightly decreased BCP degradation. The greatest degradation rates for CP and BCP were 92% and 97%, respectively, with 7.0 mol L−1 NaOH and 0.21 mol L−1 PS and a soil-to-liquid ratio of 1:1. Furthermore, ferrous iron activation of PS also degraded BCP efficiently, but only 60% of CP was degraded under the same reaction conditions. These results indicated that base activation of PS was more feasible than Fe2+ activation and Fenton reaction in remediating the soil polluted with OPs. The high degradation rate for CP may be linked to the initial hydrolyzation of CP by base to 3,5,6-trichloro-2-pyridinol, which can be further rapidly degraded by free radicals generated from base activation of PS.

Contribution of alcohol radicals to contaminant degradation in quenching studies of persulfate activation process

Alcohols such as ethanol (EtOH) and tert-butanol (TBA) are frequently used as quenching agents to identify the primary radical species in the persulfate (PS)-based oxidation processes. However, the contribution of alcohol radicals (ARs) to contaminant degradation in this process has rarely been assessed. In this study, trichloroacetic acid (TCA), phenol, and carbon tetrachloride were selected as probes to test the role of ARs in the thermally activated PS system. It was found that the degradation rates of these compounds were largely depended on their reactivities with ARs and the concentration of dissolved oxygen in the reaction system. In the PS/alcohol system, TCA was degraded efficiently under anaerobic conditions, while it was hardly degraded in the presence of oxygen. The results of electron paramagnetic resonance, reducing radical quenching studies, and the analysis of PS consumption suggested that ARs were the dominant reactive species contributing to TCA degradation in the PS/EtOH system under anaerobic conditions. Further studies indicated that ARs could significantly degrade CCl4 through dechlorination but not phenol. CCl4 was also degraded efficiently by ARs when oxygen in the reaction solution was completely consumed by ARs. This study highlights the important role of alcohol radicals in the degradation of contaminants during quenching studies in PS-activated processes.

Fate of di (2-ethylhexyl) phthalate and its impact on soil bacterial community under aerobic and anaerobic conditions

In this study, we examined the influence of oxygen on the degradation of di (2-ethylhexyl) phthalate (DEHP), the accumulation of its monoester metabolite mono (2-ethylhexyl) phthalate (MEHP) and their impact on soil bacterial communities. Soil microcosms artificially contaminated with DEHP (0, 100 and 1000 mg kg-1) were incubated under aerobic and anaerobic flooded conditions, and sacrificed after 0, 21 and 42 days. The results indicated that DEHP degradation proceeded at similar rates in aerobic and anaerobic flooded soils, but accumulation of metabolite MEHP was more likely to occur in anaerobic soils. Moreover, MEHP generated from DEHP degradation seemed to be readily released into the water phase, which may arouse health concerns. Illumina Miseq sequencing showed that MEHP had a greater impact on soil bacterial community than DEHP at the same dosage, and a wide range of bacterial phylotypes were inhibited by MEHP under anaerobic conditions. High DEHP contamination (1000 mg kg-1) significantly reduced bacterial diversity and altered bacterial community structure under anaerobic conditions, but not under aerobic conditions. Firmicutes was constantly inhibited by DEHP under both aerobic (Bacillus) and anaerobic (unclassified Clostridiales Family_XVIII) conditions. On the other hand, bacterial phylotypes belonging to Actinobacteria, β-Proteobacteria and Gemmatimonadaceae were constantly enriched by DEHP in anaerobic soils, however no such a clear pattern existed in aerobic soils. This work greatly expanded our understanding of the fate of DEHP and its modifying effect on bacterial communities under different environmental conditions.

New insight into the mechanism of peroxymonosulfate activation by sulfur-containing minerals: Role of sulfur conversion in sulfate radical generation

Peroxymonosulfate (PMS) or persulfate activation by sulfur-containing minerals has been applied extensively for the degradation of contaminants; however, the role of sulfur conversion in this process has not been fully explored. In this study, pyrite (FeS2)-based PMS activation process was developed for diethyl phthalate (DEP) degradation, and its underlying mechanisms were elucidated. PMS was found to be efficiently activated by FeS2 for DEP degradation and mineralization, achieving 58.9% total organic carbon removal using 0.5 g/L FeS2 and 2.0 mM PMS. Sulfides were the dominant electron donor for PMS activation, and mediated Fe(II) regeneration to activate PMS on the surface of FeS2 particles. Meanwhile, different sulfur conversion intermediates, such as S52-, S80, S2O32-, and SO32-, were formed from the oxidation of sulfides by Fe(III) and PMS, and determined by X-ray photoelectron spectroscopy and in-situ attenuated total reflectance Fourier transform infrared spectroscopy analysis. SO32- was the dominant sulfur species responsible for sulfate radicals (SO4-) generation by activating PMS directly or activating Fe(III) to initiate a radical chain reaction, which was supported by the electron paramagnetic resonance results. This study highlights the important role of sulfur conversion in PMS activation by pyrite and provides new insights into the mechanism of oxidant activation by sulfur-containing minerals.

Fate of di (2‑ethylhexyl) phthalate in different soils and associated bacterial community changes

Di (2‑ethylhexyl) phthalate (DEHP) is a ubiquitous organic pollutant, which has caused considerable pollution in arable soils. In this study, the relationship between DEHP degradation potential and soil properties in 12 agricultural soils (S1-S12) was examined in a microcosm based experiment. Six of these soils were then selected to monitor patterns in bacterial community responses. It was found that DEHP degradation was positively correlated with bacterial counts in the original soils, suggesting a key role for bacteria in degradation. However, DEHP metabolism did not always lead to complete degradation. Its monoester metabolite, mono (2‑ethylhexyl) phthalate (MEHP), was present at appreciable levels in the two acidic soils (S1 and S2) during the incubation period of 35 days. Based on high-throughput sequencing data, we observed a greater impact of DEHP contamination on bacterial community structure in acidic soils than in the other soils. Nocardioides, Ramlibacter and unclassified Sphingomonadaceae were enriched in the two near-neutral soils where degradation was highest (S4 and S7), suggesting that these organisms might be efficient degraders. The relative abundance of Tumibacillus was greatly reduced in 50% of the six soils examined, demonstrating a high sensitivity to DEHP contamination. Furthermore, putative organic-matter decomposing bacteria (including Tumebacillus and other bacteria taxa such as members from Micromonosporaceae) were greatly reduced in the two acidic soils (S1 and S2), possibly due to the accumulation of MEHP. These results suggest a crucial role of soil acidity in determining the fate and impact of DEHP in soil ecosystems, which deserves further investigation. This work contributes to a better understanding of the environmental behavior of DEHP in soil and should facilitate the development of appropriate remediation technologies.

Reductive Hexachloroethane Degradation by S2O8•− with Thermal Activation of Persulfate under Anaerobic Conditions

Despite that persulfate radical (S2O8•-) is an important radical species formed from the persulfate (PS) activation process, its reactivity toward contaminant degradation has rarely been explored. In this study, we found that S2O8•- efficiently degrades the contaminant hexachloroethane (HCA) under anaerobic conditions, whereas HCA degradation is negligible in the presence of oxygen. We observed dechlorination products such as pentachloroethane, tetrachloroethylene, and Cl- during HCA degradation, which suggest that HCA degradation is mainly a reductive process under anaerobic conditions. Using free radical quenching and electron paramagnetic resonance (EPR) experiments, we confirmed that S2O8•- forms from the reaction between sulfate radical (SO4•-) and S2O82-, which are the dominant reactive species in HCA degradation. Density functional theory (DFT) calculations were used to elucidate the pathways of HCA degradation and S2O8•- radical decomposition. Further investigation showed that S2O8•- can efficiently degrade HCA and DDTs in soil via reduction during the thermal activation of PS under anaerobic conditions. The finding of this study provide a novel strategy for the reductive degradation of contaminant when PS-based in situ chemical oxidation used in the remediation of soil and groundwater, particularly those contaminated with highly halogenated compounds.