Green Synthesis of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/Cellulose/Polyvinyl Alcohol Hybride Aerogel and Its Application for Dye Removal

A novel Fe₃O₄/cellulose–polyvinyl alcohol (PVA) aerogel was successfully synthesized by an eco-friendly and facile method in this work. Cellulose/PVA matrix was prepared through an environmental friendly physical cross-linking process and further in-situ decorated with Fe₃O₄. Series of Fe₃O₄ decorated aerogels were prepared and the effects of Fe₃O₄ nanoparticles (NPs) on the aerogels were systematic investigated. As-prepared aerogels exhibited desirable properties including nanostructure, relatively high porosity, improved mechanical and superparamagnetism. The TEM results showed that Fe₃O₄ NPs were integrated in the three-dimensional matrix of cellulose/PVA with a diameter of 9–12 nm. Furthermore, the mechanical strength of the aerogels was significantly enhanced after the introduction of Fe₃O₄ NPs. Meanwhile, the obtained Fe₃O₄/cellulose/PVA aerogel exhibited excellent adsorption performance toward methyl blue dye, and can be reused through fenton-like catalysts oxidative degradation of organic dye in H₂O₂ solution. Therefore, they will have a great potential application as eco-friendly and economical adsorbents.     

Photochemical Kinetic Modeling of Degradation of Aqueous Polyvinyl Alcohol in a UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> Photoreactor

This study presents a photochemical kinetics model to describe the degradation of water-soluble PVA (Polyvinyl Alcohol) polymer in a UV/H₂O₂ batch reactor. Under the effect of UV light, the photolysis of hydrogen peroxide into hydroxyl radicals can generate a series of polymer scission reactions. For a better understanding and analysis of the UV/H₂O₂ process in the cracking of the PVA macromolecules, a chemical reaction mechanism of the degradation process and a relevant photochemical kinetics model are developed to describe the disintegration of the polymer chains. Taking into account the probabilistic fragmentation of the polymer, the statistical moment approach is used to model the molar population balance of live and dead polymer chains. The model predicts the PVA molecular weight reduction, the acidity of the solution, and hydrogen peroxide residual. In addition to previously published data collected in this laboratory, a new set of experiments were conducted using a 500 mg/L PVA aqueous for different hydrogen peroxide/PVA ratios for model validation. Measurements of average molecular weights of the polymer, hydrogen peroxide concentrations and pH of the PVA solution were determinant factors in constructing a reliable photochemical model of the UV/H₂O₂ process. Experimental data showed a decrease in the PVA molecular weight and a buildup of the solution acidity. The experimental data also served to determine the kinetics rate constants of the PVA photochemical degradation and validate the model whose predictions are in good agreement with data. The model can provide a comprehensive understanding of the impact of the design and operational variables.     

Multi-response optimization of Fenton process for applicability assessment in landfill leachate treatment

Fenton process, as a pretreatment method, was found to be effective in the primary treatment of mature/medium landfill leachate. However, the main problem of the process is the large amount of produced sludge that requires an accurate feasibility evaluation for operational applications. In this study, the response surface methodology was applied for the modeling and optimization of Fenton process in three target responses, (1) overall COD removal, (2) sludge to iron ratio (SIR) and (3) organics removal to sludge ratio (ORSR), where the latter two were new self-defined responses for prediction of sludge generation and applicability assessment of the process, respectively. The effective variables included the initial pH, [H₂O₂]/[Fe²⁺] ratio and Fe²⁺ dosage. According to the statistical analysis, all the proposed models were adequate (with adjusted R² of 0.9116–0.9512) and had considerable predictive capability (with prediction R² up to 0.9092 and appropriate adequate precision). It was found that all the variables had significant effects on the responses, specifically by their observed role in dominant oxidation mechanism. The optimum operational conditions obtained by overlay plot, were found to be initial pH of 5.7, [H₂O₂]/[Fe²⁺] ratio of 17.72 and [Fe²⁺] of 195 mM, which led to 69% COD removal, 2.4 (l sludge/consumed mole Fe²⁺) of SIR and 16.5 (gCOD removed/l produced sludge) for ORSR in verification test, in accordance with models-predicted values. Finally, it was observed that [H₂O₂]/[Fe²⁺] ratio and Fe²⁺ dosage had significant influence on COD removal, while Fe²⁺ dosage and [H₂O₂]/[Fe²⁺] ratio had remarkable effects on SIR and ORSR responses, respectively.     

Application of response surface methodology to the advanced treatment of biologically stabilized landfill leachate using Fenton’s reagent

A Fenton process that uses FeCl₂ as the alternative catalyst was employed to deal with the biologically treated landfill leachate. Data obtained revealed that this Fenton process can provide an equivalent pollutant removal as the Fenton process that uses FeSO₄ as catalyst. Central composite design (CCD) and response surface methodology (RSM) were applied to evaluate and optimize the four key factors, namely initial pH, Fe(II) dosage ([Fe²⁺]), H₂O₂/Fe(II) mole ratio ([H₂O₂]/[Fe²⁺] ratio) and reaction time, which affect the performance of the Fenton treatment. Chemical oxygen demand (COD) and color were selected as response variables. This approach provided statistically significant quadratic models, which were adequate to predict responses and to carry out optimization under the conditions studied. It was demonstrated that the interaction between initial pH and [H₂O₂]/[Fe²⁺] ratio has a significant effect on the COD removal, while the interaction between [H₂O₂]/[Fe²⁺] ratio and reaction time shows a large impact on color removal. The optimal conditions were found to be initial pH 5.9, [Fe²⁺] = 9.60 mmol/L, [H₂O₂]/[Fe²⁺] ratio = 2.38, reaction time = 5.52 h. Under this optimal scheme, the COD and color in the effluent were reduced to 159 mg/L and 25°, respectively, with an increase of BOD₅/COD ratio from 0.05 to 0.21.     

Mathematical model analysis of Fenton oxidation of landfill leachate

The treatment of concentrated landfill leachate rejected from reverse osmosis (RO) with Fenton process was studied, and the system model was developed through the examination of reaction kinetics. The leachate is typically non-biodegradable with low BOD₅/COD ratio 0.01. The oxidation reactions of Fenton process was found to be a two-stage process, where a fast initial reaction (H₂O₂/Fe²⁺) was followed by a much slower one (H₂O₂/Fe³⁺). A simple and more accurate mathematics model based on COD and TOC removals has been derived successfully to describe the two-stage reaction kinetics. The two corresponding parameters involved in this model have been identified as the initial reaction rate and the maximum oxidation removal efficiency, respectively. It was found to be very useful for evaluating the performance of Fenton system and/or for process design using the two parameters under different experimental conditions.     

Photochemical Degradation of Aqueous Polyvinyl Alcohol in a Continuous UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> Process: Experimental and Statistical Analysis

Polyvinyl alcohol (PVA), being a dominant contributor of total organic carbon (TOC) in textile wastewater, is not easily degradable by conventional methods of wastewater treatment. This study investigates the degradation of aqueous PVA in a continuous UV/H₂O₂ photoreactor since the feeding strategy of hydrogen peroxide proves to have considerable effects on the process performance. Response surface methodology involving the Box–Behnken method is adopted for the experimental design to study the effects of operating parameters on the process performance. Experimental analysis shows that the TOC removal varies from 16.11 to 42.70 % along with a reduction of the PVA molecular weights from 56.7 to 95.3 %. The TOC removal is significantly lower than the molecular weight reduction due to the generation of the intermediate products during oxidation. Operating the UV/H₂O₂ process in a continuous mode facilitates the degradation of highly concentrated polymeric solutions using a relatively small hydrogen peroxide concentration in the feed with a small residence time ranges from 6.13 to 18.4 min.     

Treatment of MTBE‐Contaminated Waters with Fenton's Reagent

Methyl tertiary‐butyl ether (MTBE) is commonly used as a fuel additive because of its many favorable properties that allow it to improve fuel combustion and reduce resulting concentrations of carbon monoxide and unburnt hydrocarbons. Unfortunately, increased production and use have led to its introduction into the environment. Of particular concern is its introduction into drinking water supplies. Accordingly, research studies have been initiated to investigate the treatment of MTBE‐contaminated soil and groundwater. The summer 2000 issue of Remediation reported the results of an initial study conducted by the authors to evaluate the treatment of MTBE using Fenton's reagent. In this follow‐up study, experiments were conducted to further demonstrate the effectiveness of using Fenton's reagent (H₂O₂:Fe⁺²) to treat MTBE‐contaminated groundwater. The concentration of MTBE was reduced from an initial concentration of 1,300 μg/l (14.77 μ moles) to the regulatory level of 20 μg/l (0.23 μ moles) at a H₂O₂:Fe⁺² molar ratio of 1:1, with ten minutes of contact time and an optimum pH of 5. The by‐products, acetone and tertiary butyl alcohol, which are always present in MTBE in trace amounts, were not removed even after 60 minutes of reaction time. © 2002 Wiley Periodicals, Inc. *     

Pilot study on the advanced treatment of landfill leachate using a combined coagulation,fenton oxidation and biological aerated filter process

Mature landfill leachate is typically non-biodegradable. A combination process was developed that includes coagulation, Fenton oxidation, and biological aerated filtering to treat biologically-produced effluent. In this process, coagulation and Fenton oxidation were applied in order to reduce chemical oxygen demand (COD) organic load, and enhance biodegradability. Poly-ferric sulfate (PFS) at 600 mg l^?1 was found to be a suitable dosage for coagulation. For Fenton oxidation, an initial pH of 5, a total reaction time of 3 h, and an H₂O₂ dosage of 5.4 mmol l^?1, with a (H₂O₂)/n(Fe²⁺) ratio of 1.2 and two-step dosing were selected to achieve optimal oxidation. Under these optimal coagulation and Fenton oxidation conditions, the COD removal ratios were found to be 66.67% and 56%, respectively. Following pretreatment with coagulation and Fenton oxidation, the landfill leachate was further treated using a biological aerated filter (BAF). Our results show that COD was reduced to 75 mg l^?1, and the color was less than 10 degrees.     

Reductive decomposition of waste gypsum with SiO<Subscript>2</Subscript>, Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> additives

From the point of view of a sustainable and environment-friendly society based on the recycling of material resources, it is preferable to utilize waste gypsum as a substitute for lime, which is currently produced by the calcination of limestone. In the present work, the reductive decomposition of CaSO₄ was investigated under an atmosphere of CO: 2 vol%, CO₂: 30 vol%, with N₂ as a carrier gas without and with the addition of SiO₂, Al₂O₃, or Fe₂O₃. It was found that the decomposition temperature of CaSO₄ was significantly reduced from 1673 K to 1223 K when only 5 wt% Fe₂O₃ was added to CaSO₄. In the case of the addition of SiO₂ or Al₂O₃ to CaSO₄, the decomposition temperature was reduced from 1673 K to 1623 K. This was due to the formation of composite oxides (calcium ferrite, calcium silicate, or calcium aluminate) during the reaction of CaSO₄ with the additives at a lower temperature. In addition, the formation of unfavorable product CaS was inhibited in the presence of 5 wt% Fe₂O₃, and this inhibition effect further increased as the addition of Fe₂O₃ was increased. In contrast, no significant effect on the inhibition of CaS formation was observed on the addition of SiO₂ or Al₂O₃.     

Sonophotocatalytic Degradation of Chitosan in the Presence of Fe(III)/H2O2 System

The degradation of chitosan by means of ultrasound irradiation and its combination with homogeneous photocatalysis (photo-Fenton) was investigated. Emphasis was given on the effect of additive on degradation rate constants. 24 kHz of ultrasound irradiation was provided by a sonicator, while an ultraviolet source of 16 W was used for UV irradiation. To increase the efficiency of degradation process, degradation system was combined with Fe(III) (2.5 × 10⁻⁴mol/L) and H₂O₂ (0.020–0.118 mol/L) in the presence of UV irradiation and the rate of degradation process change from 1.873 × 10⁻⁹−6.083 × 10⁻⁹ mol^1.7 L s⁻¹. Photo-Fenton process led to complete chitosan degradation in 60 min with the rate increasing with increasing catalyst loading. Sonophotocatalysis in the presence of Fe(III)/H₂O₂ was always faster than the respective individual processes. A synergistic effect between ultrasound and ultraviolet irradiation in the presence of Fenton reagent was calculated. The degraded chitosans were characterized by X-ray diffraction (XRD), gel permeation chromatography (GPC) and Fourier transform infrared (FT-IR) spectroscopy and average molecular weight of ultrasonicated chitosan was determined by measurements of intrinsic viscosity of samples. The results show that the total degree of deacetylation (DD) of chitosan change, partially after degradation and the decrease of molecular weight led to transformation of crystal structure. A negative order for the dependence of the reaction rate on total molar concentration of chitosan solution within the degradation process was suggested. Results of this study indicate that the presence of catalyst in the reaction medium can be utilized to reduce molecular weight of chitosan while maintaining the power of irradiated ultrasound and degree of deacetylation.     

Effect of Nanoscale SiO<Subscript>2</Subscript> and TiO<Subscript>2</Subscript> as the Fillers on the Mechanical Properties and Aging Behavior of Linear Low-Density Polyethylene/Low-Density Polyethylene Blends

Linear low-density polyethylene (LLDPE) was blended with low-density polyethylene (LDPE) at a fixed ratio (80 wt LLDPE and 20 wt %LDPE) and filled with nanoparticles of SiO₂ and TiO₂ at a ratio up to wt 5%, so as to develop the polymeric composites suitable to preparing the agricultural micro-irrigation pipes having good environmental adaptability. These compounds were blended using calcium stearate, polyethylene wax, and titanate coupling agent as the auxiliary dispersants, and ethylene-vinyl acetate copolymer (EVA) as the toughness improver. The LLDPE/LDPE composites filled with the nanoparticles were extruded and injected to prepare the composites specimens for the performance evaluations and micro-irrigation pipe field test. The mechanical properties, thermostability, and processibility of the injected composites were investigated. The effect of heating in an oven and irradiating by ultraviolet on the mechanical properties of the composites was explored. The environmental adaptability of the micro-irrigation pipes made of the filled LLDPE/LDPE composites was evaluated making use of long-term outdoor field test in northwest China where the arid and harsh natural conditions are of great concerns. It was found that the LLDPE/LDPE blend with the LLDPE mass fraction fixed as 80% showed balanced mechanical and thermal properties and flexibility, and was suitable to be used as the basic resin matrix. The incorporation of nano-TiO₂ contributed to effectively improving the resistance to heating and ultraviolet irradiation of the composites. The composite made from 91% basic resin matrix, 6% EVA, and 3% mixed nano-SiO₂ and TiO₂, showed balanced comprehensive properties. The micro-irrigation pipes made of this filled LLDPE/LDPE composite had good environmental adaptability and service behavior in a three-year field test and were suitable to be used in arid area.     

阴离子对Fenton氧化降解聚乙烯醇的影响

研究了亚铁盐中NO3-、SO42-、Cl-、Br-等阴离子对Fenton氧化降解高浓度聚乙烯醇(PVA)效果的影响。实验结果表明:酸性条件下具有氧化性的阴离子NO3-或能被氧化形成具有氧化性物质的离子Cl-、Br-对Fenton氧化降解PVA有协同促进作用,且氧化性越强越容易促使PVA大分子链断裂;含NO3-、Cl-、Br-和SO42-的Fenton氧化降解PVA,COD去除率分别为70.05%、70.60%、72.40%和87.90%。采用COD去除率相差不大、产物分子量较小的硝酸亚铁、氯化亚铁、溴化亚铁中的一种作为Fenton试剂催化降解PVA较适宜。     

Desulfurization of coke oven gas from the coking of coking coal blended with a sorbent and waste plastic

A new way to implement the simultaneous reutilization of solid waste, the desulfurization of coke oven gas (COG), and even the desulfurization of coke by the co-coking of coking coal (CC) and waste plastic (WP) blended with a sorbent is proposed; the evolution of H₂S and the removal efficiency of H₂S from COG during the co-coking process were investigated in a lab-scale cylindrical reactor. The experimental results indicated that for the coking of CC blended with ZnO, Fe₂O₃, or blast furnace dust (BFD) as a sorbent, the instantaneous concentration of H₂S in COG was lower than 500 mg/m³ (which meets the technical specification requirement of the Chinese Cleaner Production Standard–Coking Industry, HJ/T 126-2003) when the molar ratio between the key component of the sorbent and the volatile S in CC or the CC/WP blend, n _Zn+Fe/n _S, was about 1.2 for ZnO and Fe₂O₃, but not for BFD under the same conditions, suggesting that ZnO and Fe₂O₃ are promising sorbents, but that BFD must be treated chemical or thermally before being used as a sorbent because of the size and complicated nature of the influence of its phase/chemical composition on its desulfurization ability. However, for the co-coking of CC and WP blended with ZnO as a sorbent, n _Zn+Fe/n _S must increase to 1.4 and 1.7 for 100/2 and 100/5 blends of CC/WP, respectively, to ensure a satisfactory efficiency for H₂S removal from COG. Part of this paper was presented at the International Symposium on EcoTopia Science 2005 (ISET05), Aug 8–9, 2005, Chikusa-ku, Nagoya, Japan     

Enhanced bioleaching efficiency of copper from waste printed circuit boards (PCBs) by dissolved oxygen-shifted strategy in <Emphasis Type="Italic">Acidithiobacillus ferrooxidans</Emphasis>

Acidithiobacillus ferrooxidans, as chemolithotrophic aerobic bacterium, can obtain energy by oxidation of ferrous ions (Fe²⁺) to ferric ions (Fe³⁺) and use molecular oxygen (O₂) as terminal electron acceptor. In this study, the effects of dissolved oxygen (DO) levels in culture medium on cell growth and copper extraction from waste printed circuit boards (PCBs) were investigated in A. ferrooxidans. The whole culture period was divided into two stages of cell growth and copper extraction. At the former stage, relatively lower DO level was adopted to satisfy bacterial growth while avoiding excessive Fe²⁺ oxidation. At the later stage, higher DO was used to promote copper extraction. Moreover, shift time of DO from lower to higher level was determined via simulating Gauss function. By controlling DO at 10 % for initial 64 h and switching to 20 % afterwards and with 18 g/l PCBs addition at 64 h, final copper recovery reached 94.1 %, increased by 37.6 and 48.3 % compared to constant DO of 10 and 20 % operations. More importantly, copper leaching periods were shortened from 108 to 60 h. It was suggested that application of DO-shifted strategy to enhancing copper extraction from PCBs with reduced leaching periods is being feasible.     

Evaluation of landfill leachate treatment by advanced oxidative process by Fenton’s reagent combined with membrane separation system

A high content of refractory organic matter, ammonia and toxic compounds is characteristic of landfill leachate. Advanced oxidative processes (AOPs) are an attractive alternative for landfill leachate treatment. However, when applied as a unique process treatment, they do not provide a complete solution for the effluent treatment. Combining AOP with a membrane separation process (MSP) presents a number of benefits and provides an adequate solution for this problem. With this in mind, the present work aims to evaluate, using a bench scale, leachate treatability through AOP by Fenton’s reagent (AOP/Fenton) combined with microfiltration (MF) and nanofiltration (NF). A high efficient removal of COD (63%), true color (76%) and humic substances (50%) was observed during AOP/Fenton under optimized conditions (1.7 g H₂O₂/g COD_{raw leachate}; FeSO₄·7H₂O:H₂O₂ = 1:5.3; pH = 3.8; reaction conditions = 115 rpm/28 min). According to the evaluated parameters, MSP presented an efficient complementary treatment, in which the integrity of the stages was sufficient for reaching regulatory levels in the effluent (Deliberação Normativa Conjunta COPAM/CERH-MG N^o. 1, May 5, 2008).     

Degradation Mechanism of CF/EP Composites in Supercritical <Emphasis Type="Italic">n</Emphasis>-Butanol with Alkali Additives

CF/EP (carbon fibre/epoxy resin) composites were degraded by supercritical n-butanol with alkali additive KOH in a batch reactor. The catalytic degradation mechanism of the composites was investigated based on the analysis of liquid phase products by GC–MS and solid phase products by FTIR. The results indicate that alkali additive (KOH) can promote Guerbet reaction and increase hydrogen donor capability of supercritical n-butanol. The H^· can combine promptly with the free radical formed by the scission of linear and crosslinked chains in epoxy resin to generate the liquid products, including phenol, 4-isopropylphenol, 4-(2-methylallyl)phenol and other derivatives of benzene and phenol. The combination of supercritical n-butanol with alkali additive is an effective way to degrade and recycle CF/EP composites.     

An advanced study on the hydrometallurgical processing of waste computer printed circuit boards to extract their valuable content of metals

This study refers to two chemical leaching systems for the base and precious metals extraction from waste printed circuit boards (WPCBs); sulfuric acid with hydrogen peroxide have been used for the first group of metals, meantime thiourea with the ferric ion in sulfuric acid medium were employed for the second one. The cementation process with zinc, copper and iron metal powders was attempted for solutions purification. The effects of hydrogen peroxide volume in rapport with sulfuric acid concentration and temperature were evaluated for oxidative leaching process. 2 M H₂SO₄ (98% w/v), 5% H₂O_2, 25 °C, 1/10 S/L ratio and 200 rpm were founded as optimal conditions for Cu extraction. Thiourea acid leaching process, performed on the solid filtrate obtained after three oxidative leaching steps, was carried out with 20 g/L of CS(NH₂)₂, 6 g/L of Fe³⁺, 0.5 M H₂SO₄, The cross-leaching method was applied by reusing of thiourea liquid suspension and immersing 5 g/L of this reagent for each other experiment material of leaching. This procedure has lead to the doubling and, respectively, tripling, of gold and silver concentrations into solution. These results reveal a very efficient, promising and environmental friendly method for WPCBs processing.     

The use of waste basic oxygen furnace slag and hydrogen peroxide to degrade 4-chlorophenol

A new treatment method is developed to degrade 4-chlorophenol (4-cp) and its oxidation intermediates. The experimental results of this research demonstrate that 4-cp and its oxidation intermediates can be decomposed completely by basic oxygen furnace slag (BOF slag) with hydrogen peroxide (H₂O₂) in an acid solution. The factors that effect the treatment efficiency were studied including initial concentration of 4-cp, pH of the solution, concentration of H₂O₂ and amount of BOF slag. The BOF slags are final waste materials in the steel making process. The major components of BOF slag are CaO, SiO₂, Fe₂O₃, FeO, MgO and MnO. As the BOF slag in an acid solution, FeO and Fe₂O₃ can be dissociated to produce ferrous ion and ferric ion. Ferrous ion reacts with hydrogen peroxide to form “Fenton's reagent” which can produce hydroxyl radicals (OH^.). Hydroxyl radical possession of high oxidation ability can oxidize organic chemicals effectively. Results show that 100 mg/l of 4-cp is decomposed completely within 30 min by 438.7 g/l BOF slag with 8.2 mM hydrogen peroxide in pH=2.8±0.2 solution. The COD value of the solution is reduced from 290 to 90 mg/l. The factors studied which affect the 4-cp decomposition efficiency were the hydrogen peroxide concentration, BOF slag concentration, pH of the solution and initial concentration of 4-cp. Because large amounts of Fe₂O₃ and FeO are present in the BOF slag, the BOF slag not only has a high treatment efficiency, but also can be used repeatedly.     

Remedial options for chlorinated volatile organics in a partially anaerobic aquifer

A laboratory study was conducted for the selection of appropriate remedial technologies for a partially anaerobic aquifer contaminated with chlorinated volatile organics (VOCs). Evaluation of in situ bioremediation demonstrated that the addition of electron donors to anaerobic microcosms enhanced biological reductive dechlorination of tetrachloroethene (PCE), trichloroethene (TCE), and 1,1,1‐trichloroethane (1,1,1‐TCA) with half‐lives of 20, 22, and 41 days, respectively. Nearly complete reductions of PCE, TCE, 1,1,1‐TCA, and the derivative cis‐dichloroethene were accompanied by a corresponding increase in chloride concentrations. Accumulation of vinyl chloride, ethene, and ethane was not observed; however, elevated levels of ¹⁴CO₂ (from ¹⁴C‐TCE spiked) were recovered, indicating the occurrence of anaerobic oxidation. In contrast, very little degradation of 1,2‐dichloropropane (1,2‐DCP) and 1,1‐dichlorethane (1,1‐DCA) was observed in the anaerobic microcosms, but nutrient addition enhanced their degradation in the aerobic biotic microcosms. The aerobic degradation half‐lives for 1,2‐DCP and 1,1‐DCA were 63 and 56 days, respectively. Evaluation of in situ chemical oxidation (ISCO) demonstrated that chelate‐modified Fenton's reagent was effective in degrading aqueous‐phase PCE, TCE, 1,1,1‐TCA, 1,2‐DCP, etc.; however, this approach had minimal effects on solid‐phase contaminants. The observed oxidant demand was 16 g‐H₂O₂/L‐groundwater. The oxidation reaction rates were not highly sensitive to the molar ratio of H₂O₂:Fe²⁺:citrate. A ratio of 60:1:1 resulted in slightly faster removal of chemicals of concern (COCs) than those of 12:1:1 and 300:1:1. This treatment resulted in increases in dissolved metals (Ca, Cr, Mg, K, and Mn) and a minor increase of vinyl chloride. Treatment with zero‐valent iron (ZVI) resulted in complete dechlorination of PCE, and TCE to ethene and ethane. ZVI treatment reduced 1,1,1‐TCA only to 1,1‐DCA and chloroethane (CA) but had little effect on reducing the levels of 1,2‐DCP, 1,1‐DCA, and CA. The longevity test showed that one gram of 325‐mesh iron powder was exhausted in reaction with > 22 mL of groundwater. The short life of ZVI may be a barrier to implementation. The ZVI surface reaction rates (k_sa) were 1.2 × 10^?2 Lm^?2h^?1, 2 × 10^?3 Lm^?2h^?1, and 1.2 × 10^?3 Lm^?2h^?1 for 1,1,1‐TCA, TCE, and PCE, respectively. Based upon the results of this study, in situ bioremediation appeared to be more suitable than ISCO and ZVI for effectively treating the groundwater contamination at the site. © 2004 Wiley Periodicals, Inc.