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In this study, nano‐CaO2 (nCaO2) was successfully synthesized and constituted the nCaO2/Fe(II) system applying to remediate BTEX, which are typical mixed pollutants in contaminated groundwater. The particle size of the synthesized nCaO2 was 108.91 nm, and it displayed better BTEX remediation performance than that of commercial CaO2. The innovative generation pattern of hydroxyl radicals (HO·) in the nCaO2/Fe(II) system has been investigated using benzoic acid as the HO· probe, and the proper molar ratio of nCaO2/Fe(II) was optimized as 1/1. Over 90% of BTEX was removed in 180 min with the nCaO2/Fe(II)/BTEX molar ratio of 40/40/1. Further experiments evaluated the influence of co‐existence of mixed pollutants chlorinated hydrocarbon compounds (CHCs) or surfactant constituents on BTEX remediation performance. The experimental results suggested that CHCs have limited influence on BTEX removal rate and surfactants have negative effects on BTEX remediation performance in the experimental conditions. In conclusion, the findings in this study could give some inspirations to apply the nCaO2/Fe(II) process in remediating co‐existing pollutants in contaminated groundwater. Practitioner points nCaO2/Fe(II) system applied to remediate mixed contaminants. HO· generation pattern of the nCaO2/Fe(II) system has been investigated. The influence of chloride hydrocarbon compounds have been studied. The effects of surfactants were evaluated.

The chlorobenzene (CB) degradation performances by various oxidants, including hydrogen peroxide (H2O2), nanoscale calcium peroxide (nCaO2) and sodium percarbonate (SPC), activated with ferrous iron (Fe(II)) were investigated and thoroughly compared. The results showed that all tested systems had strong abilities to degrade CB. The CB removal rate increased with increasing dosages of oxidants or Fe(II) because the generation of reactive oxygen species could be promoted with the chemical dosages' increase. Response surface and contour plots showed that CB could achieve a better removal performance at the same H2O2 and Fe(II) molar content, but the Fe(II) dosage was higher than that of oxidants in the nCaO2 and SPC systems. The optimal molar ratios of H2O2/Fe(II)/CB, nCaO2/Fe(II)/CB and SPC /Fe(II)/CB were 5.2/7.6/1, 8/8/1, and 4.5/8/1, respectively, in which 98.1%, 98%, and 96.4% CB removals could be obtained in 30 min reaction. The optimal pH condition was around 3, while CB removal rates were less than 20% in all three systems when the initial pH was adjusted to 9. The oxidative hydroxyl radicals (HO•) and singlet oxygen (1O2) had been detected by the electron paramagnetic resonance test. Based upon the results of liquid chromatograph-mass spectrometer analysis, the pathways of CB degradation were proposed, in which 1O2 roles were elaborated innovatively in the CB degradation mechanism. The CB degradation performance was significantly affected in actual groundwater, while increasing the molar ratio of oxidant/Fe(II)/CB was an effective way to overcome the adverse effects caused by the complex of actual groundwater matrix.

Benzene, toluene, ethylbenzene and xylene (BTEX) possess a negative impact on the environment and human being due to their highly toxic and carcinogenic properties. In this study, persulfate (PS) activated by nano zero-valent iron (nZVI) coupled with chelated L-cysteine (L-cys) process was investigated for BTEX degradation in contaminated groundwater. BTEX degradation had a significant acceleration and improvement with the removal from 62.7 to 100% along with the increasing dosage of L-cys from 0.12 to 0.27 M in 24 h. Further, the compact nZVI catalytic cylinder and nZVI encapsulated L-cys catalytic cylinder were successfully manufactured by encapsulating nZVI, and nZVI and L-cys together with additives of cement, river sand, stearic acid (SA) and zeolite. The SEM image, XRD patterns and FTIR spectra showed that the manufactured catalytic cylinder had a porous structure and encapsulated nZVI and L-cys successfully. Six successive cycles of BTEX degradation were completed and the degradation rate decreased gradually in each cycle. The catalytic activity of nZVI encapsulated L-cys catalytic cylinder was superior to nZVI catalytic cylinder in each cycle. The electron paramagnetic resonance (EPR) results indicated that HO• was the dominant active species in the BTEX degradation process. Benzoic acid (BA) scavenge experiments showed that L-cys could increase the yield of HO• in the PS/nZVI system. The HO• yields of PS/nZVI encapsulated L-cys catalytic cylinder system were 3.2 to 4.8 folds higher than those of PS/nZVI catalytic cylinder system. The possible mechanisms of PS activation by nZVI encapsulated L-cys catalytic cylinder were supposed. Homogeneous Fenton reaction and heterogeneous catalysis on the nZVI surface are two co-existence mechanisms in the PS/nZVI encapsulated L-cys catalytic cylinder system. The findings of this study provide new insights into the mechanism of nZVI encapsulated L-cys catalytic cylinder activating PS, showing its potential applications for the remediation of groundwater.