Hydrogen peroxide lifetime as an indicator of the efficiency of 3-chlorophenol Fenton's and Fenton-like oxidation in soils

In this work the possibility of using the hydrogen peroxide lifetime as indicator of the oxidation efficiency of Fenton's and Fenton-like processes for soil treatment was explored. A reactivity scale, in terms of the oxidizing power in the different tested operating conditions (pH, iron sulfate concentration and stabilizer concentration) was built for each soil as a function of the hydrogen peroxide lifetime. Its validity was then confirmed through 3-chlorophenol Fenton's and Fenton-like slurry-phase oxidation experiments. The proposed reactivity scale proved to be effective for comparing the different operating conditions for the same soil, but failed when used to compare the oxidation performances for different soils, since the different adsorptive behavior of the tested soils may have influenced the contaminant removal rate.     

The mechanism and applicability of in situ oxidation of trichloroethylene with Fenton's reagent

Fenton's reagent is the result of reaction between hydrogen peroxide (H(2)O(2)) and ferrous iron (Fe(2+)), producing the hydroxyl radical (-*OH). The hydroxyl radical is a strong oxidant capable of oxidizing various organic compounds. The mechanism of oxidizing trichloroethylene (TCE) in groundwater and soil slurries with Fenton's reagent and the feasibility of injecting Fenton's reagent into a sandy aquifer were examined with bench-scale soil column and batch experiment studies. Under batch experimental conditions and low pH values ( approximately 3), Fenton's reagent was able to oxidize 93-100% (by weight) of dissolved TCE in groundwater and 98-102% (by weight) of TCE in soil slurries. Hydrogen peroxide decomposed rapidly in the test soil medium in both batch and column experiments. Due to competition between H(2)O(2) and TCE for hydroxyl radicals in the aqueous solutions and soil slurries, the presence of TCE significantly decreased the degradation rate of H(2)O(2) and was preferentially degraded by hydroxyl radicals. In the batch experiments, Fenton's reagent was able to completely dechlorinate the aqueous-phase TCE with and without the presence of soil and no VOC intermediates or by-products were found in the oxidation process. In the soil column experiments, it was found that application of high concentrations of H(2)O(2) with addition of no Fe(2+) generated large quantities of gas in a short period of time, sparging about 70% of the dissolved TCE into the gaseous phase with little or no detectable oxidation taking place. Fenton's reagent completely oxidized the dissolved phase TCE in the soil column experiment when TCE and Fenton's regent were simultaneously fed into the column. The results of this study showed that the feasibility of injecting Fenton's reagent or H(2)O(2) as a Fenton-type oxidant into the subsurface is highly dependent on the soil oxidant demand (SOD), presence of sufficient quantities of ferrous iron in the application area, and the proximity of the injection area to the zone of high aqueous concentration of the target contaminant. Also, it was found that in situ application of H(2)O(2) could have a gas-sparging effect on the dissolved VOC in groundwater, requiring careful attention to the remedial system design.     

Application of persulfate to remediate petroleum hydrocarbon-contaminated soil: feasibility and comparison with common oxidants

In this study, batch experiments were conducted to evaluate the feasibility of petroleum-hydrocarbon contaminated soil remediation using persulfate oxidation. Various controlling factors including different persulfate and ferrous ion concentrations, different oxidants (persulfate, hydrogen peroxide, and permanganate), and different contaminants (diesel and fuel oil) were considered. Results show that persulfate oxidation is capable of treating diesel and fuel oil contaminated soil. Higher persulfate and ferrous ion concentrations resulted in higher diesel degrading rates within the applied persulfate/ferrous ion molar ratios. A two-stage diesel degradation was observed in the batch experiments. In addition, treatment of diesel-contaminated soil using in situ metal mineral activation under ambient temperature (e.g., 25°C) may be a feasible option for site remediation. Results also reveal that persulfate anions could persist in the system for more than five months. Thus, sequential injections of ferrous ion to generate sulfate free radicals might be a feasible way to enhance contaminant oxidation. Diesel oxidation efficiency and rates by the three oxidants followed the sequence of hydrogen peroxide>permanganate>persulfate in the limited timeframes. Results of this study indicate that the application of persulfate oxidation is a feasible method to treat soil contaminated by diesel and fuel oil.     

Advanced oxidation processes applied to tannery wastewater containing Direct Black 38--elimination and degradation kinetics

The application of advanced oxidation processes (H(2)O(2)/UV, TiO(2)/H(2)O(2)/UV and TiO(2)/UV) to treat tannery wastewater was investigated. The experiments were performed in batch and continuous UV reactors, using TiO(2) as a catalyst. The effect of the hydrogen peroxide concentration on the degradation kinetics was evaluated in the concentration range 0-1800 mg L(-1). We observed that the degradation rate increased as the hydrogen peroxide increased, but excessive H(2)O(2) concentration was detrimental because it acted as a hydroxyl radical scavenger since it can compete for the active sites of the TiO(2). In the H(2)O(2)/UV treatment, the COD removal reached around 60% in 4 h of reaction, indicating that the principal pollutants were chemically degraded as demonstrated by the results for BOD, COD, nitrate, ammonium and analysis of the absorbance at 254 nm. Artemia salina toxicity testing performed in parallel showed an increase in toxicity after AOP treatment of the tannery wastewater.     

Chemical oxidation of chlorinated non-aqueous phase liquid by hydrogen peroxide in natural sand systems

This study explored the Fenton-like oxidation of trichloroethylene (TCE) existing as dense non-aqueous phase liquid (DNAPL) in natural silica sand (iron=0.04 g/kg) and the sand from an aquifer (iron=2.01 g/kg). Glass bead containing no iron mineral was used as the control. Batch oxidation experiments were conducted to assess interactions between oxidant and TCE DNAPL. Column experiments were performed to evaluate dynamics of TCE and H(2)O(2) during oxidation. The pH was not altered. In the batch system, a single application of 3% H(2)O(2) to the aquifer sand oxidized 40% of the added TCE DNAPL in 1 h, which was four times of that by dissolution with the gas purge procedure. This demonstrated the ability of mineral-catalyzed Fenton-like reaction to directly oxidize TCE in non-aqueous liquid. In the column experiments, after passing 7 pore volumes (PVs) of 1.5 and 3% H(2)O(2) solution, the residual TCE in aquifer sand column was 12.0 and 2.6% of the initial added, respectively. On the other hand, 28.4% of the added TCE still remained in the silica sand column by 7 PVs of 3% H(2)O(2). The distribution of TCE in column and effluent indicated the occurring of direct oxidation of TCE DNAPL and the increased solubilization, which probably due to size reduction of DNAPL droplets, followed by water-phased TCE oxidation.     

Application of potassium permanganate as an oxidant for in situ oxidation of trichloroethylene-contaminated groundwater: a laboratory and kinetics study

The objectives of this bench-scale study were to (1) determine the optimal operational parameters and kinetics when potassium permanganate (KMnO4) was applied to in situ oxidize and remediate trichloroethylene (TCE)-contaminated groundwater and (2) evaluate the effects of manganese dioxide (MnO2) on the efficiency of TCE oxidation. The major controlling factors in the TCE oxidation experiments included molar ratios of KMnO4 to TCE (P value) and molar ratios of Na2HPO4 to Mn2+ (D value). Results show that the second-order decay model can be used to describe the oxidation when P value was less than 20, and the observed TCE decay rate was 0.8M(-1)s(-1). Results also reveal that (1) higher P value corresponded with higher TCE oxidation rate under the same initial TCE concentration condition and (2) higher TCE concentration corresponded with higher TCE oxidation rate under the same P value condition. Results reveal that significant MnO2 production and inhibition of TCE oxidation were not observed under acidic (pH 2.1) or slightly acidic conditions (pH 6.3). However, significant reduction of KMnO(4) to MnO2 would occur under alkaline condition (pH 12.5), and this caused the decrease in TCE oxidation rate. Results from the MnO2 production experiments show that MnO2 was produced from three major routes: (1) oxidation of TCE by KMnO4, (2) further oxidation of Mn2+, which was produced during the oxidation of TCE by KMnO4, and (3) reduction of MnO4(-1) to MnO2 under alkaline conditions. Up to 81.5% of MnO2 production can be effectively inhibited with the addition of Na2HPO4. Moreover, the addition of Na2HPO4 would not decrease the TCE oxidation rate.     

Ozonation of trichloroethylene in acetic acid solution with soluble and solid humic acid

The combined flushing and oxidation process using acetic acid and ozone has been used successfully to remove trichloroethylene (TCE) completely from contaminated soil. In this study, the effects of humic acid, a fraction of the organic matter in soil, over the performance of TCE decomposition was evaluated. TCE decomposition by ozone was enhanced by the presence of humic acid at concentrations lower than 8mgCL(-1) and then inhibited at higher concentrations. It is possible that the presence of the soluble humic acid fraction during the ozonation of TCE in acetic acid solutions produces hydroxyl radicals during the TCE ozonation which appears to be the reason for the enhanced TCE decomposition rate. Solid humic acid reduced TCE decomposition rate by acting as an ozone scavenger. Similarly, sorbed TCE reduced the amount of TCE available for decomposition by ozone in solution.     

A kinetic study on the degradation of p-nitroaniline by Fenton oxidation process

A detailed kinetic model was developed for the degradation of p-nitroaniline (PNA) by Fenton oxidation. Batch experiments were carried out to investigate the role of pH, hydrogen peroxide and Fe(2+) levels, PNA concentration and the temperature. The kinetic rate constants, k(ap), for PNA degradation at different reaction conditions were determined. The test results show that the decomposition of PNA proceeded rapidly only at pH value of 3.0. Increasing the dosage of H(2)O(2) and Fe(2+) enhanced the k(ap) of PNA degradation. However, higher levels of H(2)O(2) also inhibited the reaction kinetics. The k(ap) of PNA degradation decreased with the increase of initial PNA concentration, but increased with the increase of temperature. Based on the rate constants obtained at different temperatures, the empirical Arrhenius expression of PNA degradation was derived. The derived activation energy for PNA degradation by Fenton oxidation is 53.96 kJ mol(-1).     

Application of surfactant enhanced permanganate oxidation and bidegradation of trichloroethylene in groundwater

The industrial solvent trichloroethylene (TCE) is among the most ubiquitous chlorinated solvents found in groundwater contamination. The main objectives of this study were to evaluate the feasibility of using non-ionic surfactant Simple Green™ (SG) to enhance the oxidative dechlorination of TCE by potassium permanganate (KMnO₄) employing a continuous stir batch reactor system (CSBR) and column experiments. The effect of using surfactant SG to enhance the biodegradation of TCE via aerobic cometabolism was also examined. Results from CSBR experiments revealed that combination of KMnO₄ with surfactant SG significantly enhanced contaminant removal, particularly when the surfactant SG concentrated at its CMC. TCE degradation rates ranged from 74.1% to 85.7% without addition of surfactant SG while TCE degradation rates increased to ranging from 83.8% to 96.3% with presence of 0.1 wt% SG. Furthermore, results from column experiments showed that TCE was degraded from 38.1 μM to 6.2 μM in equivalent to 83.7% of TCE oxidation during first 560 min reaction. This study has also demonstrated that the addition of surfactant SG is a feasible method to enhance bioremediation efficiency for TCE contaminated groundwater. The complete TCE degradation was detected after 75 days of incubation with both 0.01 and 0.1 wt% of surfactant SG addition. Results revealed that surfactant enhanced chemical oxidation and bioremediation technology is one of feasible approaches to clean up TCE contaminated groundwater.     

Remediation of TCE contaminated soils by in situ EK-Fenton process

The treatment performance and cost analysis of in situ electrokinetic (EK)-Fenton process for oxidation of trichloroethylene (TCE) in soils were evaluated in this work. In all experiments, an electric gradient of 1V/cm, de-ionized water as the cathode reservoir fluid and a treatment time of 10 days were employed. Treatment efficiencies of TCE were evaluated in terms of the electrode material, soil type, catalyst type, and catalyst dosage and granular size if applicable. Test results show that graphite electrodes are superior to stainless steel electrodes. It was found that the soil with a higher content of organic matter would result in a lower treatment efficiency (e.g. a sandy loam is less efficient than a loamy sand). Experimental results show that the type of catalyst and its dosage would markedly affect the reaction mechanisms (i.e. "destruction" and "removal") and the treatment efficiency. Aside from FeSO4, scrap iron powder (SIP) in the form of a permeable reactive wall was also found to be an effective catalyst for Fenton reaction to oxidize TCE. In general, the smaller the granular size of SIP, the lower the overall treatment efficiency and the greater the destruction efficiency. When a greater quantity of SIP was used, a decrease of the overall treatment efficiency and an increase of percent destruction of TCE were found. Experimental results have shown that the quantity of electro-osmotic (EO) flow decreased as the quantity of SIP increased. It has been verified that the treatment performances are closely related to the corresponding EO permeability. Results of the cost analysis have indicated that the EK-Fenton process employed in this work is very cost-effective with respect to TCE destruction.     

Effect of contaminant hydrophobicity on hydrogen peroxide dosage requirements in the Fenton-like treatment of soils

A homologous series of n-alcohols was used as model contaminants to investigate the effect of hydrophobicity on the hydrogen peroxide concentration necessary in Fenton-like treatment for near-complete (>99%) destruction of compounds sorbed to soil. These probe compounds were selected because they exhibit equal reactivities with hydroxyl radicals, but have varied hydrophobicities. The standard Fenton reaction was first used to confirm equal hydroxyl radical reactivity for the n-alcohols. Central composite rotatable design experiments were then used to determine the conditions in an iron(III)-hydrogen peroxide system that resulted in 99% degradation of each of the probe compounds when sorbed to soil. The hydrogen peroxide concentrations required for 99% destruction of the sorbed compounds increased with probe compound hydrophobicity. Furthermore, hydrogen peroxide concentration requirements were directly proportional to the log octanol-water partition coefficients (logK(OW)) of each probe compound. This quantitative relationship may not be directly applicable to other organic contaminants, but a strong correlation between logK(OW) and hydrogen peroxide requirements for other contaminants will likely be found. These results confirm that hydrogen peroxide requirements for soil treatment increase as a function of contaminant hydrophobicity and provide a basis for the development of an algorithm for hydrogen peroxide requirements when modified Fenton's reagent is used for in situ chemical oxidation (ISCO).     

Modification of clay barriers with a cationic surfactant to improve the retention of pesticides in soils

In this work, the efficiency of reactive clay barriers in the immobilisation of organic pesticides in a sandy soil was studied. Reactive barriers were prepared by modification of montmorillonite, kaolinite and palygorskite clay minerals, and of a clayey soil with the cationic surfactant octadecyltrimethylammonium bromide (ODTMA). Percolation curves of the pesticides linuron, atrazine and metalaxyl of different hydrophobic character, were obtained in columns packed with a natural sandy soil with these barriers intercalated under saturated flow conditions. The cumulative curves in the unmodified soil indicated a leaching of pesticides greater than 85% of the total amount of compound added. After barrier intercalation, the breakthrough curves (BTC) indicated a dramatic decrease in the amounts of linuron leached in all columns and a significant modification of the leaching kinetics of atrazine and metalaxyl. Retardation factors, R, of the pesticides in the columns were significantly correlated with the organic matter content (OM) derived from the ODTMA of the organo clay/soil barriers (r2>or=0.78). Significant correlations were also found between these R factors and the pore volume values corresponding to the maximum peaks of the BTCs (r2=0.83; p<0.01) or the total volumes leached (r2=0.44; p<0.05) for the pesticides atrazine and metalaxyl. The results obtained point to the interest in the use of reactive clay barriers for almost complete immobilisation of hydrophobic pesticides or for decreasing the leaching of moderately hydrophobic pesticides coming from point-like sources of pollution. These barriers would avoid the generation of elevated concentrations of these compounds in the soils due to their rapid washing.     

Hot water extraction with in situ wet oxidation: PAHs removal from soil

We are reporting the results of a small-scale batch extraction with and without in situ wet oxidation of soils polluted with polycyclic aromatic hydrocarbons (PAHs) using subcritical water (liquid water at high temperatures and pressures but below the critical point as the removal agent). Two types of soil; one spiked with four PAHs, and an aged sample were used. Experiments were carried out in a 300 ml volume reactor in the batch mode. In each experiment, the reactor was filled with 45-50 g of soil and 200-220 ml of double distilled water. For extraction without oxidation, the reactor was pressurized with nitrogen, while for those with the oxidation, an oxidizing agent (air, oxygen or hydrogen peroxide) was used.The extraction only experiments were carried out at 230, 250 and 270 degrees C for spiked soil samples, and at 250 degrees C for aged soil samples, while all of the combined extraction and oxidation experiments were carried out at 250 degrees C. Removal of PAHs from spiked soil in extraction-only experiments was from 79 to 99+% depending on the molecular weight of the PAH. This was in the range of 99.1% to excess of 99.99% for the combined extraction and oxidation. While 28-100% of extracted PAHs can be found in water phase in case of extraction alone, this reduces to a maximum of 10% if the extraction is combined with oxidation. With aged soil similar or comparable results were obtained. Based on these results, extraction with hot water, if combined with oxidation, would probably reduce the cost of post treatment for the water and can be used as a feasible alternative technique for remediation of contaminated soils and sediments.     

Removal of trichloroethylene in reduced soil columns

A continuous soil column experiment was conducted to investigate reductive dechlorination of trichloroethylene (TCE) in soil system reductively manipulated by three types of reductants (Fe(II), dithionite, and Fe(II) + dithionite (combined treatment of Fe(II) and dithionite)). The soil column reduced by Fe(II) + dithionite has the greatest bed volumes (51.8) treated to breakthrough indicating that the combined treatment of Fe(II) and dithionite is more effective for the reductive dechlorination of TCE in the reduced soil column than the separate treatment of Fe(II) or dithionite. The measured bed volumes to breakthrough in control and treated soil columns were similar to the estimated bed volumes based on the result of batch kinetic experiment, differing by a factor of 0.96-1.02. The relative concentration of bromide (non-reactive tracer) reached the approximate value of 1 between 0.87 and 1.03 bed volume. C2 hydrocarbons (acetylene, ethylene, and ethane) were observed as transformation products in the effluents of soil columns treated by the reductants. However, no chlorinated intermediates were observed at the concentrations above detection limits throughout the experiment. Chloride was observed in the effluents of soil columns reduced by dithionite and Fe(II) + dithionite.     

Decolourisation of dye solutions by oxidation with H(2)O(2) in the presence of modified activated carbons

The decolourisation of dye solutions by oxidation with H(2)O(2), using activated carbon as catalyst, is studied. For this purpose, three different samples, mainly differing in the respective surface chemistries, were prepared and characterized. Moreover, this work involved three pH levels, corresponding to acid, neutral and alkaline solutions, and six dyes belonging to several classes. The catalytic decolourisation tests were performed in a laboratorial batch reactor. Adsorption on activated carbon and non-catalytic peroxidation kinetic experiments were also carried out in the same reactor, in order to compare the efficiencies of the three processes. The non-catalytic reaction is usually inefficient and, typically, adsorption presents a low level of decolourisation. In these cases, the combination of activated carbon with hydrogen peroxide may significantly enhance the process, since the activated carbon catalyses the decomposition of H(2)O(2) into hydroxyl radicals, which are very reactive. Based on the experiments with the different activated carbon samples, which have similar physical properties, it is proved that the surface chemistry of the catalyst plays a key role, being the basic sample the most active. This is discussed considering the involvement of the free electrons on the graphene basal planes of activated carbon as active centres for the catalytic reaction. Additionally, it is shown that the decolourisation is enhanced at high pH values, and a possible explanation for this observation, based on the proposed mechanism, is given.     

Reaction paths and efficiency of photocatalysis on TiO2 and of H2O2 photolysis in the degradation of 2-chlorophenol

The kinetics of 2-chlorophenol (2-CP) degradation and mineralization in the aqueous phase was investigated under irradiation at 254 nm, employing either photocatalysis in the presence of titanium dioxide, or hydrogen peroxide photolysis, to compare the efficiency of these photoinduced advanced oxidation techniques. Photocatalysis under 315-400 nm wavelength irradiation was also investigated. The concentration versus time profiles of the degradation intermediates catechol, chloro- and hydroxy-hydroquinone allowed the identification of the reaction paths prevailing under the different experimental conditions. Efficient CCl bond cleavage occurred as a consequence of direct light absorption by 2-CP, while hydroxyl radicals, photogenerated at the water-photocatalyst interface or during H(2)O(2) photolysis, were the main oxidation agents, able to attack both 2-CP and its degradation intermediates. Highest degradation and mineralization efficiencies were achieved under H(2)O(2) photolysis at 254 nm.     

Hot water extraction with in situ wet oxidation: kinetics of PAHs removal from soil

Finding environmentally friendly and cost-effective methods to remediate soils contaminated with polycyclic aromatic hydrocarbons (PAHs) is currently a major concern of researchers. In this study, a series of small-scale semi-continuous extractions--with and without in situ wet oxidation--were performed on soils polluted with PAHs, using subcritical water (i.e. liquid water at high temperatures and pressures, but below the critical point) as the removal agent. Experiments were performed in a 300 mL reactor using an aged soil sample. To find the desorption isotherms and oxidation reaction rates, semi-continuous experiments with residence times of 1 and 2 h were performed using aged soil at 250 degrees C and hydrogen peroxide as oxidizing agent. In all combined extraction and oxidation flow experiments, PAHs in the remaining soil after the experiments were almost undetectable. In combined extraction and oxidation no PAHs could be detected in the liquid phase after the first 30 min of the experiments. Based on these results, extraction with hot water, if combined with oxidation, should reduce the cost of remediation and can be used as a feasible alternative technique for remediating contaminated soils and sediments.     

Rate of dibutylsulfide decomposition by ozonation and the O3/H2O2 advanced oxidation process

A process of dibutylsulfide (DBS) oxidation using advanced methods of oxidation with ozone and hydrogen peroxide was studied. It was demonstrated that depending on pH value there are two mechanisms of DBS oxidation present: ionic and radical. The ionic mechanism predominates in acidic environment and the radical mechanism predominates in alkaline environment. At high pH ozone stability decreases and hydrogen peroxide has a deciding effect on DBS oxidation rate. At pH 9, and at high concentration of hydrogen peroxide (ranging from 0.1 to 1 mol/L), a clear increase in DBS decomposition rate was observed. That was caused by production of hydroperoxide radicals in reaction of hydrogen peroxide and ozone. In solutions pH value of which is close to 2, the rate of DBS oxidation by ozone alone is slower than in a O(3)/H(2)O(2) system, regardless the H(2)O(2) concentration. For higher H(2)O(2) concentrations (ranging from 0.1 to 1 mol/L), regardless the pH value of the solution, oxidation in a O(3)/H(2)O(2) system is faster, compared to a situation in which ozone is a sole oxidizer. For H(2)O(2) concentrations below 0.1 mol/L and when pH>2DBS oxidation in O(3)/H(2)O(2) system is slower compared to the situation in which ozone was the only oxidizer.     

Photochemical treatment of 2-chlorophenol aqueous solutions using ultraviolet radiation, hydrogen peroxide and photo-Fenton reaction

In the present work, the photochemical oxidation of 2-chlorophenol aqueous solutions in a batch recycle photochemical reactor using ultraviolet irradiation and hydrogen peroxide was studied. Specifically, the effect of hydrogen peroxide initial concentration (0-10316 mg L(-1)) and 2-chlorophenol initial concentration (150-3000 mg L(-1)) was examined. The process was attended via total organic carbon (TOC), 2-chlorophenol, chloride ion, acetic acid, formic acid and pH measurements. The conversion of 2-chlorophenol observed was always much higher than the corresponding total organic carbon removal, whereas the increase in hydrogen peroxide amount in the solution led to higher values of 2-chlorophenol conversion and total organic carbon removal. Finally, the photo-Fenton reaction was applied to the oxidation of 2-chlorophenol, leading to a higher degree of mineralization of the parent compound.