Hiba Shaghaleh,Yousef Alhaj Hamoud,Qin Sun,Mohamed S. Sheteiwy,Hamada AbdElgawad
Soil flushing and adsorption-based soil remediation are promising options for removing heavy metals in agricultural soil. However, they encounter limitations in low removal efficiency, secondary pollution potential, or the need for a purification/recovery process. Optimizing flushing solutions or the functional properties of adsorbents could fundamentally eliminate the drawbacks of these methods. Yet, their practical application remains a formidable challenge. Herein, a new combined remediation strategy of multiple-pulse water soil flushing (MF) with novel aminated cellulose nanofibers (A-NFCs)/AEM/AM@MIL-100(Fe) nanocomposite hydrogel adsorbent (ANCMH) was adopted to remove Cr(VI) from agricultural soil. The characteristic analyses approved Cr(VI) adsorption-coupled reduction/swelling-based mechanisms on ANCMH with the maximum theoretical adsorption capacity of 338.24 mg g −1 at pH 6.8 governed by pseudo-second-order and Freundlich models. Instead of conventional MF application using environmentally problematic extractant fluids, a 5-day soil column simulation trial of MF coupled with ANCMH adsorbent layers (MF@ANCMH) was applied in medium-to-highly Cr(VI)-contaminated soil followed by easy ANCMHs separation, preventing secondary pollution. Innovatively, the water flushing-stop flux events favorably decreased the pH of neutral soil by 0.83 folds and allowed Cr(VI) release from the soil matrix to be adsorbed by ANCMHs, achieving a high Cr(VI) removal efficiency of 98.9 %. Compared to the soil treated with ANCMH individually and soil flushed with water or Na 2 EDTA, the MF@ANCMH-treated soil reached the corresponding regulation of permissible levels for Cr(VI) residential scenarios in agricultural soil of 5.6 ppm with 3-cycles of ANCMH reuse. The residual Cr in MF@ANCMH-remediated soil displayed minimal bioavailability at root-zoon soil of ≤4.2 ppm and a 97.66 % reduction in its exchangeable-carbonate fraction compared to untreated soil, corresponding to a risk assessment code score below 1 %. Also, the application of MF@ANCMH resulted in Cr bioaccumulation below 0.1 ppm in cultivated wheat plants, prevented the physiological phytotoxicity symptoms, and elevated their antioxidant enzyme activity, photosynthesis, growth, and yielding indicators compared to that grown in untreated soil. Furthermore, it improved soil organic matter, microbial community, diversity, and microecological functions. This study provides a promising alternative remediation strategy for neutral soil that can maintain soil/crop quality and soil health with high chemical/environmental stability of pollutants after remediation, demonstrating its sustainability and feasibility in agricultural soil.
Various flushing solutions that contain hydrophobic organic compounds and surfactants are generated during surfactant-enhanced soil flushing processes. How to effectively remove the target pollutants while minimizing the degradation of surfactants for reuse of the flushing solutions has become a major problem. A series of batch experiments were conducted to investigate the preferential degradation mechanisms of naphthalene by sodium dodecyl sulfate (SDS) as well as the effect of SDS concentration on the degradation efficiency using a competitive kinetic method. In addition, the effects of persulfate (PS) dosage, temperature, and pH on the degradation efficiency of naphthalene were also studied, and a prediction model based on response surface methodology (RSM) was built to optimize the preferential degradation of naphthalene. One-dimensional column flushing experiments were performed to evaluate the feasibility of reusing soil flushing solutions at the predicted PS dosage. Results show that: (i) SDS inhibited naphthalene degradation owing to competitive oxidation and micellar protection, with a decreasing degradation rate constant as SDS concentration increased. However, naphthalene was still degraded by reactive oxygen species (ROS) at a higher rate than SDS, indicating the preferential degradation of naphthalene. When the concentration of SDS increased from 5 to 10 times of critical micelle concentration (CMC; 8.2 mM), the ratio for rate constants of naphthalene to SDS ( k NAP / k SDS ) decreased significantly from 31.61 to 3.38, illustrating the obvious effect of SDS concentration on preferential degradation of naphthalene; (ii) The formation of single-chambered vesicles with a higher thermodynamic stability was observed at 10 CMC, compared to the spherical micelles formed at 5 CMC. The accessibility of naphthalene to ROS was greatly reduced at 10 CMC, resulting in a significant reduction in k NAP / k SDS value. Moreover, the method in which ROS attacked naphthalene in surfactant micelles varied with SDS concentration, which also impacted the preferential degradation of naphthalene; (iii) Under the optimal PS dosage predicted by the RSM model, a good reusability of SDS was observed in the soil flushing solutions after thermally activated PS oxidation, with a significant reduction on the toxic risk of soil after flushing.
Although surfactant foams enhanced-remediation for PAHs-contaminated soil has been proved to be an effective method, lack of simple/economic surfactant recovery methods from the eluent solutions limit its further remediation application for organic contaminated soil. Here, we prepared a electrochemically reversible ferrocene surfactant FcCH 2 N + (CH 3 )C 12 H 25 (Fc12), then investigated the foaming ability and foam stability of Fc12 under its reduced (active state) and oxidation (inactive state) states and explored the flushing efficiency of reduced Fc12 foam for PAHs-contaminated soil and the recovery efficiency of collected eluent solution. The results showed that the foaming ability and foam stability of reduced Fc12 are greatly higher than those of oxidized Fc12, which is indicative of a well reversibly switchable characteristic of Fc12. The contaminated soil flushing efficiencies of reduced Fc12 for phenanthrene and pyrene were 65.28% and 46.45%. The respective desorption efficiency of phenanthrene and pyrene from collected eluent solutions were calculated to be 74.94% and 72.75% by electrochemical oxidation control, which indicates that Fc12 can be well recovered by simple electrochemical control. This study provides a feasible method for the recovery of surfactants from surfactant-enhanced remediation processes by simply electrochemical control.
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