The aim of this study was to investigate the reaction behaviors of nanoscale Fe3O4 and H1/10-[Fe3O4]MgO slurry injection coupled with the electrokinectic (EK) process for remediation of NO3− and Cr6+ in saturated soil. To assure the above-mentioned nanomaterials were capable of reductively adsorbing inorganic pollutants (e.g., NO3− and Cr6+) in the acidic environment in the anode reservoir of the ek remediation system, an investigation on transformation of the concerned nanomaterials in different aqueous solutions (de-ionized water and simulated groundwater ) of different initial pHs (2 and 3.5) was conducted. Due to a high dose of nanoscale Fe3O4 and a resulting serious agglomeration while adsorbing NO3− and Cr6+, the characteristic peaks of the X-ray diffraction (XRD) analysis for nanoscale Fe3O4 remained the same after adsorption experiments. But the situations were quite different in the case of nanoscale H1/10-[Fe3O4]MgO, the characteristic peaks of £\-Fe2O3 in the XRD pattern were detected, confirming that this nanomaterial could reductively adsorb NO3− and Cr6+ in the acidic environment. The effectiveness of using polyacrylic acid (PAA) and soluble starch (SS) to stabilize nanoscale Fe3O4 and H1/10-[Fe3O4]MgO in different aqueous solutions containing humic acid was compared. It was found the former yielded a better stability. Therefore, PAA was chosen to prepare the slurries of target nanomaterials. Then slurry injection coupled with the EK process was tested for remediation of NO3- and Cr6+ in saturated soil. The results showed that the removal efficiency of NO3− was more than 90%, and the NO3− concentration in the anode reservoir was below Taiwan¡¦s Pollution Control Standards of type¢¹Groundwater for NO3−-N. Under the same test conditions, however, the removal efficiency of Cr6+ was unsatisfactory. This might be ascribed to acidification of soil near the anode resulting in high adsorption of Cr2O72− by soil. Thus, a solution to solve this problem has to seeked. The solution lies in how to enhance the contact of the above-mentioned nanomaterials with Cr6+ in the anode reservoir. One possibility is to use the nature of SS would hydrolyze in the acidic environment. Therefore, SS-stabilized nanomaterials in the acidic environment would hydrolyze resulting in the exposure of the soil nanomaterials therein. To this end, SS was used to replace PAA for nanomaterial slurry preparation for remediation of Cr6+. In addition, polarity reversal was practiced in the EK system to maintain a neutral ph of soil and increase the mobility of Cr6+ in soil. Finally, the result showed that nanoscale Fe3O4 and H1/10-[Fe3O4]MgO slurry injection coupled with the polarity reversal electrokinetic system could really enhance the removal efficiency of Cr6+ in the saturated soil. In summary, nanoscale Fe3O4 and H1/10-[Fe3O4]MgO slurry injection coupled with the EK process has been proven to be capable of remedying NO3− and Cr6+ in saturated soil. Meanwhile, the concept of reductive adsorption was realized in this work as well.

The objective of this research was to evaluate the treatment efficiency of a trichloroethylene (TCE) contaminated soil by combined technologies of the suspension of palladized nanoiron and electrokinetic remediation process. First, nanoiron and palladized nanoiron were prepared using the chemical reduction method. Then they were characterized by various methods. Micrographs of scanning electron microscopy have shown that a majority of these nanoparticles were in the range of 50-80 nm. Specific surface areas were determined to be 76.88 m2/g and 100.61 m2/g for the former and latter, respectively. Results of X-ray diffractometry have shown that both types of nanoiron were poor in crystallinity. Three anionic dispersants were employed for evaluating their performance in stabilizing various nanoiron. Results have demonstrated that an addition of 1 wt% of Dispersant E during nanoiron preparation would result in a good stabilization of nanoiron. If the system pH was adjusted to 2.99, nanoparticles would settle rapidly. Batch tests were carried out to investigate the effects of various operating parameters on degradation of TCE in aqueous solutions. Experimental results have indicated that palladized nanoiron outperformed nanoiron in treatment of TCE in this study. The employment of Dispersant E would enhance the treatment efficiency further. Test results also showed that a linear increase of reaction rate constant was found with an increasing dose of palladium from 0.05 wt% to 1 wt% based on the mass of nanoiron. Further, an exponential increase of reaction rate constant would be obtained with an increasing pH. As for mixing intensity, it was found to be insignificant to the treatment efficiency of TCE in aqueous solutions. The final stage of this study was to evaluate the treatment efficiency of combined technologies of the suspension of palladized nanoiron and electrokinetic remediation process in treating a TCE-contaminated soil. Test conditions used were given as follows: (1) initial TCE concentration: 160-181 mg/kg; (2) electric potential gradient: 1 V/cm; (3) daily addition of 20 mL of suspension of palladized nanoiron (2.5 g/L) to the electrode reservoir; and (4) reaction time: 6 days. Test results have shown that addition of palladized iron suspension to the cathode reservoir yielded the lowest residual TCE concentration in soil. Namely, about 92.5% removal of TCE from soil. On the other hand, addition of palladized iron suspension to the anode reservoir would enhance the degradation of TCE therein. Based on the above findings, the treatment method employed in this work was proven to be a novel and efficient one in treating TCE-contaminated soil.

Abstract This research was to evaluate the treatment efficiency for in-situ treatment of pentachlorophenol (PCP) contaminated soil by electrokinetics-Fenton process combined with biodegradation. An electric gradient of 1V/cm, and graphite electrodes were employed in all experiments. Soil types, catalyst types and dosage, hydrogen peroxide concentration, cathode reservoir liquid species and reaction time were employed as the experimental factors in this study. In this study, no matter electrokinetics-Fenton process or the electrokinetics-biodegradation in the latter, prolong the reaction time can promote the removal and destruction efficiency (DRE) of target pollutant from soil. By using 0.0196 M FeSO4 with 3.5% H2O2, the DRE was only lower 2% than 0.098 M FeSO4 with 3.5% H2O2.It showed that using 0.0196 M FeSO4 can provide enough Fe2+ to react with H2O2. By increasing H2O2 concentration from 0.35% to 3.5%, a DRE rised from 68.34% to 79.77%. When iron powder was used as catalyst, the residual pentachloroplenol concentration near to anode reservoir lower than 0.0196 M FeSO4 was used. But the DRE was 56.58% lower than the 68.34% of using 0.0196 M FeSO4.As the influences of soil types to electrokinetics-Fenton process, the residual concentration of pollutant for Soil No. 2 was higher than Soil No. 1. A DRE of only 59.22% was obtained. It is postulated that a much higher content of organic matter with Soil No. 2 whereas lower the treatment efficiency because of consumption of hydroxyl radicals by the organic matter of soil. For the influence of different reservoir liquid species, in this study 0.1M acetic buffer solution was used as cathode reservoir liquid, expected to promote the removal efficiency. From the result of experiment that could not reach the expected treatment efficiency of increasing the removal efficiency from soil. From the experiment of electrokinetics process combined with cometabolism, a treatment efficiency of only 25.67% was obtained. The content of pollutant within every section of soil column were still higher than predict. But by using electrokinetics-Fenton process to pretreat the pollutant within soil first, the increasing efficiency of biodegradation was found. Even when reaction time was prolonged, the pollutant could be completely eliminated from soil. If only used iron minerals to proceed electrokinetics-Fenton process naturally exited in the soil, a DRE of only 20

The objective of this research was to evaluate the treatment efficiency of a nitrate-contaminated soil by combined technologies of the injection of palladized nanoiron slurry and electrokinetic remediation process. First, nanoiron was prepared by two synthesis processes based on the same chemical reduction principle yielding products of NZVI-A and NZVI-B, respectively. Then they were characterized by various methods. Micrographs of scanning electron microscopy have shown that a majority of these nanoparticles were in the range of 50-80 nm and 30-40 nm, respectively. Results of nitrogen gas adsorption-desorption show that NZVI-A and NZVI-B are mesorporous (ca. 30-40 Å) with BET surface areas of 128 m2/g and 77 m2/g, respectively. Results of X-ray diffractometry have shown that both types of nanoiron were poor in crystallinity. Results of zeta-potential measurements indicated that NZVI-A and NZVI-B had the same isoelectric point at pH 6.0. Although NZVI-A and NZVI-B were found to be superparamagnetic, their magnetization values were low. Poly acrylic acid (PAA), an anionic dispersant, was employed for stabilizing various types of nanoiron. Then Palladium¡]ca. 1 wt% of iron¡^ was selected as catalysis to form palladized nanoiron¡]Pd/Fe¡^. Results have demonstrated that an addition of 1 vol. % of PAA during the nanoiron preparation process would result in a good stabilization of nanoiron and nanoscale Pd/Fe slurry. Batch tests were carried out to investigate the effects of pH variation on degradation of nitrate aqueous solutions. Experimental results have indicated that palladized nanoiron outperformed nanoiron in treatment of nitrate in this study. Apparently, an employment of catalyst would enhance the treatment efficiency. Further, an exponential increase of the reaction rate was found for the systems at low pH. The final stage of this study was to evaluate the treatment efficiency of combined technologies of the injection of palladized nanoiron¡]Pd/Fe¡^ slurry and electrokinetic remediation process in treating a nitrate-contaminated soil. Test conditions used were given as follows: (1) slurry injection to four different positions in the soil matrix; (2) electric potential gradient: 1 V/cm; (3) daily addition of 20 mL of palladized nanoiron (4 g/L) slurry to the injection position; and (4) reaction time: 6 days. Test results have shown that addition of palladized nanoiron slurry to the anode reservoir yielded the lowest residual nitrate concentration in soil. Namely, about 99.5% removal of nitrate from soil. On the other hand, the acidic condition of soil matrix around the anode reservoir would enhance the degradation of nitrate therein. Based on the above findings, the treatment method employed in this work was proven to be a novel and efficient one in treating nitrate contaminated soil.

This research was aimed to investigate the enhancement of electrokinetic (EK) remediation arsenate-contaminated soil by permeable reaction barrier (PRB). All experiments, which experimental parameters included the position, materials, and quantity of PRB, processing fluid types, potential gradients, and treatment time, were conducted in two types of EK systems. One was Pyrex glass cylindrical cells with dimension of 4.2 cm (£r) ¡Ñ 12 cm (L) and the other was a small pilot-scale modulus with dimension of 36cm (L) ¡Ñ18cm (W) ¡Ñ18cm cm (H). The PRBs were composed of four kinds of reaction materials, which included commercial zero valent iron (Fe(0)C), manufactured zero valent iron (Fe(0)M), commercial hydrous ferric oxide (FeOOHC), and manufactured hydrous ferric oxide (FeOOHM), mixed with ottawa sand in a ratio of 1:2,respectively, and installed in the anode, middle, and cathode side of the EK systems. For 5-day EK cylindrical cell tests, the results showed that the PRB installation would result in a lower electroosmosis permeability (Ke) and a higher removal efficiency of arsenate. The arsenate removal efficiency of EK system with PRB was in the range of 43.89-70.25%, which was 1.5~2.6 times greater than that without PRB, and the value of Ke was in the range of 4.30-12.61¡Ñ10-6 cm2/V-s. The soil pH after EK/PRB treatment was much closer to natural and more arsenate was collected in the anode reservoir. Moreover, the remediation performance of FeOOHC as PRB materials was much better than other materials. For EK pilot-scale modulus tests, it was shown that the removal efficiency of arsenate was effectively enhanced as improved experimental parameters and, however, led to increase the treatment cost. In EK modulus without PRB, the removal efficiency of arsenate, elctroosmosis permeability, and energy consumption were 27.76%, 3.30-5.39¡Ñ10-6 cm2/V-s, and 1724.81 kWh/m3, respectively. Furthermore, the treatment cost was NT 9583/m3. As increasing treatment time, graphite electrode, potential gradient, and quantity of PRB materials, the removal efficiency of arsenate increased to as high as 45.11-71.22% and the treatment cost also increased up to NT 24,800-57,730/m3. As investigated the binding form of arsenate with soil after EK/PRB treatment, it was found that the arsenate ¡Vsoil binding forms of Fe-Mn oxide bound, organically bound, and residual in the soil section behind the PRB were much easier transformed to the forms of exchangeable and carbonate bound. The transformation rate reached as high as 72.5% and it increased with treatment time. However, the Fe-Mn oxide bound was still the main binding form, 61.6-81.6%, in the soil section prior to the PRB. The removal mechanism of arsenate contaminated soil remediation was dominated by electromigration, electrolysis, and electroosmosis in EK system without PRB. And, in EK/PRB system, the removal of arsenate from soil was mainly resulted from adsorption rather than redox reaction by PRB. To sum up, the PRB can effectively enhance the electrokinetic remediation of arsenate contaminated soil by choosing the right PRB materials and operation parameters.

The purpose of this study was to evaluate the treatment efficiency of phenol contaminated soils by electrokinetic (EK) process conducted in sand boxes (60 cm¡Ñ30 cm¡Ñ30 cm; L¡ÑW¡ÑH). The electric field strength, electrode polarity reverse, and Fenton reagent were employed as the experimental factors in this study to assess the variations of soil characteristics, potential difference, and residual phenol concentration distribution during a treatment period of 20 days and after the treatment. It was found that the anode reservoir pH decreased to around 2 and the cathode reservoir pH increased to approximately 12 after 2~3 days of treatment in the no electrode polarity reverse system. However, the variation of pH in the anode and cathode reservoirs was less obvious in the case with electrode polarity reverse. No matter a constant potential system or a constant current system was employed, a general trend of a lower pH at the anode reservoir and a higher pH at the cathode reservoir would be found. The acid front generated at the anode reservoir flushed across the soil specimen toward the cathode and the base front advanced toward the anode. However, in the central region of sand box, unsaturated and saturated soil specimen maintain neutral. For EK or EK-Fenton experiments, under the constant potential conditions, the potential difference relative to the cathode versus the distance from anode was found to have a linear relationship at the beginning of the electrical potential application. As the treatment time elapsed, the potential gradient became non-linear. Nevertheless, there was no remarked potential gradient change in the case with electrode polarity reverse. Although capillarity has resulted in an increase of the moisture content of unsaturated soil (from 25.34% to 30% after 20 days), electroosmotic (EO) flow was not obvious in the unsaturated zone. For the experiments with electrode polarity reverse, they had a much greater EO flow quantity, the electroosmotic permeability coefficients for constant potential and constant current systems were 6.42¡Ñ10-6 cm2/V¡Es and 9.47¡Ñ10-6 cm2/V¡Es, respectively. It was also found that the existence of contaminants did reduce the EO flow quantity. Regardless of the employment of a constant potential or constant current system, the maximum destruction and removal efficiency (DRE) of phenol was obtained for EK-Fenton process. The maximum DRE values of phenol for both constant potential and constant current systems were found to be 78.06% and 80.11%, respectively. However, the DRE of phenol was found to be much lower for the system with electrode polarity reverse. It was postulated that the destruction efficiency of phenol was less obvious than the removal efficiency in the electrode polarity reverse system. In addition, a frequent reverse of electrode polarity also resulted in a frequent change of EO flow direction. Thus, a flow hysteresis of phenol in the soil compartment was found.