Chemical oxidation using stabilized hydrogen peroxide in high temperature,saline groundwater impacted with hydrocarbons and MTBE

In situ chemical oxidation (ISCO) of petroleum hydrocarbons (PHCs) within groundwater is considered a proven approach to addressing PHC‐impacted groundwater in nonsaline environments. One of the most common oxidants used for oxidation of PHCs in groundwater is hydrogen peroxide (H₂O₂). Due to its highly reactive nature, H₂O₂ is often stabilized to aid in increasing its reactivity lifespan. Limited research and application of ISCO has been completed in warm, saline groundwater environments. Furthermore, even fewer studies have been completed in these environments for ISCO using stabilized H₂O₂. In this research, stabilized H₂O₂ was examined to determine its effectiveness in the treatment of PHCs and the additive methyl tert‐butyl ether (MTBE). Three stabilizers (citrate, phytate, silica [SiO₂]) were tested to determine if the stabilizers could enhance and extend the treatment life of H₂O₂ within saline groundwater. To determine the effect of salinity on the three stabilizers, groundwater and aquifer samples were collected from two saline locations that had different salinity (total dissolved solids of about 7,000 mg/L and 18,000 mg/L). Specific target chemicals for treatment were water soluble, mobile components of gasoline including benzene, toluene, ethylbenzene, xylenes, (BTEX) and MTBE. Previous studies using unactivated persulfate indicated that the PHCs within the groundwater could be oxidized, however, only limited oxidation of the MTBE could be affected. The results of the laboratory tests indicated that greater than 95 percent of the target hydrocarbons were removed within 7 days of treatment. Microcosms with citrate‐stabilized H₂O₂ demonstrated a significantly faster and greater decline with most hydrocarbon concentrations reaching < 5 μg/L. The exceptions were ethylbenzene and m‐xylene, which were slightly decreased to about 30 and 20 μg/L, respectively. Initial mean concentrations of the BTEX compounds within the citrate‐stabilized microcosms were 10,554 μg/L, 9,318 μg/L, 6,859 μg/L, and 14,435 μg/L, respectively. The silicate‐stabilized H₂O₂ microcosms showed no significant benefit over the unstabilized control microcosms. The better performance of citrate‐stabilized microcosms was confirmed by increasing δ13C values of remaining hydrocarbons. MTBE declined from > 400 mg/L to < 100 mg/L in all microcosms, again with the best removal (> 90 percent) being measured in the citrate‐stabilized microcosms. Unfortunately, H₂O₂ oxidation in the microcosms also resulted in production of up to 40 mg/L TBA or approximately 10 percent of the MTBE oxidized.     

Removal of Cinnamic Acid Derivatives from Aqueous Effluents by Fenton and Fenton-like Processes as an Alternative to Direct Biological Treatment

The removal of various phenolic acids (p-coumaric, caffeic and ferulic acids), typically found in wastewaters of agricultural origin, from model effluents by chemical and biological means has been investigated. Chemical oxidation processes comprising hydrogen peroxide and a homogeneous or heterogeneous copper or iron catalyst were employed over a wide range of experimental conditions. Chemical oxidation is capable of removing most of the total organic carbon initially present in the effluent at relatively mild treatment conditions (i.e. reaction times up to 120 min and temperatures up to 80°C), while removal rates generally increase with increasing temperature, H₂O₂ and catalyst concentrations. The anaerobic degradability and toxicity of p-coumaric acid has been assessed using the biochemical methane potential and anaerobic toxicity assay respectively. p-Coumaric acid, at concentrations below about 1 g/L, is not toxic against methanogens and slowly degrades over a period of about 35 days at 35°C. In light of this, chemical oxidation may provide a promising alternative to direct biological treatment for either the partial or complete removal of phenolic acids at reasonable treatment times; the implications for wastewater treatment are discussed.     

Removal of Reactive Blue 19 dye from synthetic wastewater using UV/H2O2 and UV/Cl advanced oxidation processes

The textile and dyeing industries are among the largest water-consuming and polluting industries in the world. The most important feature of the textile dyeing industry wastewater is its color, due to the use of colored materials. Most of these dye compounds are resistant to conventional purification methods and their biodegradation is very low through secondary purification processes, resulting in incomplete removal. Therefore, selecting the optimal method to remove these color compounds is essential. In this study, we studied the removal of an organic dye contaminant (Reactive Blue dye 19 [RB19]) using advanced oxidation processes (AOPs). For this purpose, ultraviolet (UV) mercury lamps with a wavelength of 254 nm and a voltage of W16 inside a reactor were used as an energy source. The experiments were performed in a collimated beam reactor inside a dark chamber. Two oxidizers, sodium hypochlorite (NaOCl) and hydrogen peroxide (H₂O₂), were used to remove RB19 from the artificial sewage stream. Removal of RB19 with a concentration of 20 mg/L with variable pH (5, 7, and 9), oxidant concentrations (5, 10, and 20 mg/L), and time (5, 10, 15, and 30 min) were investigated during the processes of photolysis, chemical oxidation (by H₂O₂ and NaOCl), and UV/NaOCl and UV/H₂O₂ AOPs. The photolysis process did not remove the RB19. The highest removal efficiencies of RB19 by chemical oxidation processes with NaOCl and H₂O₂, UV/NaOCl, and UV/H₂O₂ at optimal conditions (pH = 5, [oxidant] = 20 mg/L, RB19 = 20 mg/L, and radiation intensity of 1005 mJ/cm²) were 64.49%, 0.88%, 99.7%, and 13.31%, respectively. These results indicate that the hydroxyl radical was produced, under optimum conditions, more in the acidic medium; thus, the RB19 removal efficiency was higher in the acidic medium. The combination of UV rays with oxidants resulted in the production of more hydroxyl radicals and increased removal efficiency.     

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.     

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.     

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).     

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. *     

In-situ bioremediation of an aquifer contaminated with 1,2-dichloroethane

This article describes the application of in-situ bioremediation for the treatment of an aquifer contaminated with 1,2-dichloroethane (DCA). The first step in the process was to properly delineate the contamination and to contain the contaminated groundwater using a pumping well. The second step was to isolate in the groundwater microorganisms able to degrade DCA and to demonstrate the possibility of increasing their efficiency by injecting in-situ nutrients and hydrogen peroxide (H₂O₂) solution. In the third step, after the characterization of the hydrogeology of the aquifer with tracing experiments, the in-situ bioremediation of the groundwater was conducted. The analyses show that 95 percent of DCA was destroyed by this treatment, leading to a DCA concentration around the pumping well of about 0.2 mg/l.     

Six pilot‐scale studies evaluating the in situ treatment of PFAS in groundwater

Per‐ and polyfluoroalkyl substances (PFAS) have been identified by many regulatory agencies as emerging contaminants of concern in a variety of media including groundwater. Currently, there are limited technologies available to treat PFAS in groundwater with the most frequently applied approach being extraction (i.e., pump and treat). While this approach can be effective in containing PFAS plumes, previous studies of pump and treat programs have met with limited remedial success. In situ treatment studies of PFAS have been limited to laboratory and a few field studies. Six pilot‐scale field studies were conducted in an unconfined sand aquifer coimpacted by petroleum hydrocarbon along with PFAS to determine if a variety of reagents could be used to attenuate dissolved phase PFAS in the presence of petroleum hydrocarbons. The six reagents consisted of two chemical oxidants, hydrogen peroxide (H₂O₂) and sodium persulfate (Na₂S₂O₈), and four adsorbents, powdered activated carbon (PAC), colloidal activated carbon (CAC), ion‐exchange resin (IER), and biochar. The reagents were injected using direct push technology in six permeable reactive zone (PRZ) configurations. Groundwater concentrations of various PFAS entering the PRZs ranged up to 24,000 µg/L perfluoropentanoic acid, up to 6,200 µg/L pentafluorobenzoic acid, up to 16,100 µg/L perfluorohexanoic acid, up to 6,080 µg/L perfluoroheptanoic acid, up to 450 µg/L perfluorooctanoic acid, and up to 140 µg/L perfluorononanoic acid. Performance groundwater sampling within and downgradient of the PRZs occurred for up to 18 months using single and multilevel monitoring wells. Results of groundwater sampling indicated that the PFAS were not treated by either the persulfate nor the peroxide and, in some cases, the PFAS increased in concentration immediately following the injection of peroxide and persulfate. Concentrations of PFAS in groundwater sampled within the PAC, CAC, IER, and biochar PRZs immediately after the injection were determined to be less than the method detection limits. Analyses of groundwater samples over the 18‐month monitoring period, indicated that all the PRZs exhibited partial or complete breakthrough of the PFAS over the 18‐month monitoring period, except for the CAC PRZ which showed no PFAS breakthrough. Analysis of cores for the CAC, PAC, and biochar PRZs suggested that the CAC was uniformly distributed within the target injection zone, whereas the PAC and biochar showed preferential injection into a thin coarse‐sand seam. Similarly, analysis of the sand packs of monitoring wells installed before the injection of the CAC, PAC, and biochar indicated that the sand packs of the PAC and biochar preferentially accumulated the reagents compared with the reagent concentrations within the surrounding aquifer by up to 18 times.     

Kinetic and Mechanistic Studies of NO X Selective Catalytic Reduction Over In/Al2O3 and N2O Decomposition Over Ru/Al2O3

Detailed kinetic studies are presented for two reactions: the nitric oxide (NO) selective catalytic reduction (SCR) by propene over indium/alumina (In/Al₂O₃) and the nitrous oxide (N₂O) reduction over ruthenium/alumina (Ru/Al₂O₃). Both reactions were studied in the presence of excess oxygen (O₂) to simulate the composition of flue gases. Apparent activation energies and apparent orders of reaction were calculated in experiments performed under differential reaction conditions. We used our experimental results to propose the reaction mechanism that leads to nitrogen formation over the two catalysts. The NO reduction proceeds through the initial formation of C _X H _Y O _Z N, a reaction intermediate that reacts with activated nitrogen oxides (NO _X ). Nitrous oxide is catalytically decomposed to nitrogen (N₂) over Ru/Al₂O₃.     

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     

Photo-Stabilisation and UV Blocking Efficacy of Coated Macro and Nano-Rutile Titanium Dioxide Particles in Paints and Coatings

Surface treated macro and nanoparticle TiO₂ samples have been prepared, characterised and their efficiency as UV blockers evaluated in clear coatings and paints. The particle size of the ‘base’ TiO₂ has been optimised to block UV radiation and the surface treatment developed to deactivate the photocatalytic activity of the surface of the TiO₂ particles. The resultant UV blockers have been evaluated in both solvent and water-based clear coatings. Nanoparticle TiO₂ has been prepared from ‘seed’ and the particle size was controlled by calcination. It was found that the choice of particle size is a compromise between UVA absorption, UVB absorption, visible transmission and photoactivity. It has been demonstrated that TiO₂ with a crystallite size of 25 nm yields a product with the optimum properties. A range of dispersants was successfully used to disperse and mill the TiO₂. Both organic and inorganic dispersants were used; 2-amino-2-methyl-1-propanol and 1-amino-2-propanol (MIPA) and P₂O₅ and Na₂SiO₃ respectively. The surface of the nano-TiO₂ was coated with mixed oxides of silicon, aluminium, zirconium and phosphorous. Addition of the resultant coated nano-rutiles to an Isocyanate Acrylic clear coating prolonged the lifetime of that coating compared to the blank. Generally, a surface treatment based on SiO₂, Al₂O₃ and P₂O₅ was more successful than one based on ZrO₂, Al₂O₃ and P₂O₅. Higher addition levels of the surface treatment were beneficial for protecting the polymeric coating. The UV blocker products were also evaluated in a water-based acrylic, first a water-based dispersion of the UV blocker was prepared before addition to the acrylic. The dispersions and resultant acrylic thin films were evaluated using UV/Vis spectroscopy and durability assessed. The ratio of absorbance at 300:500 nm for the water-based dispersion was shown to be a good predictor of both the transparency of the resultant acrylic thin film and the durability of that film, in terms of weight loss. Macro grade titanium dioxide pigments were also prepared and coated with treatments of silica, alumina and siloxane and their photo-stabilising activity in alkyd paint film assessed and found to be directly related to the electron–hole pair mobility and trapping as determined by micro-wave spectroscopy.     

Selective catalytic reduction of NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> using RDF char and municipal solid waste char based catalyst

Experiments were performed in order to investigate the possibility for the development of catalysts for low-temperature selective catalytic reduction (SCR) using municipal waste char and RDF byproduct. Physical and chemical activations, using water, and HCl and KOH, were employed to increase the catalytic activities. The characteristics of the activated catalysts were investigated using N₂ adsorption–desorption and FT-IR. The catalysts activated chemically using basic treatment showed higher NO _x removal efficiencies than those activated physically or chemically using acidic treatment. The de-NO _x performance of the activated catalysts was dependent on the chemical properties, such as oxygen functional groups as well as physical properties, such as specific surface area and pore volume. In order to investigate the effect of MnO _x , which has been reported to be efficient for the removal of NO _x in low-temperature SCR processes, the chemically activated catalyst was impregnated with manganese. The Mn-impregnated catalyst had the highest NO _x conversion at all of the temperatures tested in this study.     

Chemical Oxidation Performance in High Temperature,Saline Groundwater Impacted With Hydrocarbons

A series of laboratory microcosm experiments and a field pilot test were performed to evaluate the potential for in situ chemical oxidation (ISCO) of aromatic hydrocarbons and methyl tertiary butyl ether (MTBE), a common oxygenate additive in gasoline, in saline, high temperature (more than 30 °C) groundwater. Groundwater samples from a site in Saudi Arabia were amended in the laboratory portion of the study with the chemical oxidants, sodium persulfate (Na₂S₂O₈) and sodium percarbonate (Na₂(CO₃)₂), to evaluate the changes in select hydrocarbon and MTBE concentrations with time. Almost complete degradation of the aromatic hydrocarbons, naphthalene and trimethylbenzenes (TMBs), was found in the groundwater sample amended with persulfate, whereas the percarbonate‐amended sample showed little to no degradation of the target hydrocarbon compounds in the laboratory. Isotopic analyses of the persulfate‐amended samples suggested that C‐isotope fractionation for xylenes occurred after approximately 30 percent reduction in concentration with a decline of about 1 percent in the δ¹³C values of xylenes. Based on the laboratory results, pilot‐scale testing at the Saudi Arabian field site was carried out to evaluate the effectiveness of chemical oxidation using nonactivated persulfate on a high temperature, saline petroleum hydrocarbon plume. Approximately 1,750 kg of Na₂S₂O₈ was delivered to the subsurface using a series of injection wells over three injection events. Results obtained from the pilot test indicated that all the target compounds decreased with removal percentages varying between 86 percent for naphthalene and more than 99 percent for the MTBE and TMBs. The benzene, toluene, ethylbenzene, and xylene compounds decreased to 98 percent on average. Examination of the microbial population upgradient and downgradient of the ISCO reactive zone suggested that a bacteria population was present following the ISCO injections with sulfate‐reducing bacteria (SRB) being the dominant bacteria present. Measurements of inorganic parameters during injection and postinjection indicated that the pH of the groundwater remained neutral following injections, whereas the oxidation–reduction potential remained anaerobic throughout the injection zone with time. Nitrate concentrations decreased within the injection zone, suggesting that the nitrate may have been consumed by denitrification reactions, whereas sulfate concentrations increased as expected within the reactive zone, suggesting that the persulfate produced sulfate. Overall, the injection of the oxidant persulfate was shown to be an effective approach to treat dissolved aromatic and associated hydrocarbons within the groundwater. In addition, the generation of sulfate as a byproduct was an added benefit, as the sulfate could be utilized by SRBs present within the subsurface to further biodegrade any remaining hydrocarbons. ©2015 Wiley Periodicals, Inc.     

Efficiency of physicochemical and biological treatments of vinasse and their influence on indigenous microbiota for disposal into the environment

Molasses-based distilleries are one of the most polluting industries generating large volumes of high strength wastewater called vinasse. Different processes covering anaerobic, aerobic as well as physicochemical methods have been employed to treat this effluent. This study evaluated the microbial communities present in the vinasse during different stages of its treatment by traditional and molecular methods. The analysis of the efficiency of each treatment was performed by physicochemical parameters and toxicity analysis. The treatment of vinasse was performed in the following steps: high flow fermentation; filtration; chemical flakes; low-flow fermentation; filtration; and neutralization. The physicochemical analysis in different stages of the vinasse treatment demonstrated that phases of treatment influenced the performance of the evaluated parameters. Among the 37 parameters, 9 were within the limits established by the Commission for Environmental Policy of Minas Gerais, Brazil (COPAM), especially BOD (96.7% of pollution reduction), suspended solids (99.9%), pH, copper (88%), iron (92.9%), and manganese (88%). Some parameters, even after treatment, did not fit the maximum allowed by legislation. The microbial population decreased reaching 3 log CFU/ml present in the steps of the flakes chemical and disinfection treatment of vinasse. Lactobacillus brevis and Pichia kudriavzevii were present in all stages of the treatments, showing that these microorganisms were resistant and demonstrated that they might be important in the treatment of vinasse. The vinasse showed a significant reduction of pollution load after the disinfection treatment however still should not be discarded into water bodies because the high values of tannins and sediment solids, but suggest the use of the effluent in the cooling coil during the distillation process of the beverage.     

Effect of Ozonation and Sonication on Biochemical Methane Potential of Biosludge from Textile Mill Effluent

The aim of this study was to justify the method to determine biochemical methane potential (BMP) of biosludges and investigate the effect of ozonation and sonication on the biosludge from textile mill effluent to its biodegradability and toxicity. This study revealed that the exented anaerobic toxicity assay at a chemical oxygen demand (COD) concentration in the assay of about 1,500 mg/L was the appropiate technique to determine BMP of the biosludge. Moreover, it was found that the biodegradability of biosludge was satisfactorily increased by both of ozonation and sonication. The use of ozone dose of 0.005 g O₃/g COD and 0.01 O₃/g COD increased the biodegradability from 62% to 69% and 76%, respectively. While for sonication on frequency 51 kHz ±6%, 120 W for 30 and 60 min increased the biodegradability from 62% to 68% and 73%, respectively.     

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.     

Coal fly ash based carbons for SO2 removal from flue gases

Two different coal fly ashes coming from the burning of two coals of different rank have been used as a precursor for the preparation of steam activated carbons. The performance of these activated carbons in the SO₂ removal was evaluated at flue gas conditions (100 °C, 1000 ppmv SO₂, 5% O₂, 6% H₂O). Different techniques were used to determine the physical and chemical characteristics of the samples in order to explain the differences found in their behaviour. A superior SO₂ removal capacity was shown by the activated carbon obtained using the fly ash coming from a subbituminous–lignite blend. Experimental results indicated that the presence of higher amount of certain metallic oxides (Ca, Fe) in the carbon-rich fraction of this fly ash probably has promoted a deeper gasification in the activation with steam. A more suitable surface chemistry and textural properties have been obtained in this case which explains the higher efficiency shown by this sample in the SO₂ removal.     

H2O2/VisUV photo-oxidation process for treatment of waterborne hazardous substances—Reaction mechanism, rate model, and data for tubular flow and flow stirred tank reactors

This paper presents the chemical reaction engineering development of the H₂O₂/VisUV photo-oxidation process for treatment of hazardous waterborne substances, that occur in groundwater, leachates, and industrial wastewater. Reaction results, on benzene (BNZ), dichlorobenzene (DCB), trichloroethene (TCE), trichloroethane (TCA), and carbon tetrachloride (CTC), have been obtained, providing engineering data and models that can be used to size full-scale equipment. A photochemical flow stirred tank reactor (pcfSTR) and a photo-chemical tubular flow reactor (pcTFR) were used in the experimental work. Two experimental discoveries were made in the course of the work: (1) conventional thermal kinetics do not apply, the rate controlling variable is the photon flux, and (2) for the photo-chemical reactors used, the pcfSTR was more effective than the pcTFR. The following sub-topics are discussed: reaction mechanism, reactor hydrodynamics, photon flux effects, typical reaction data (on benzene and trichloroethane), and rate constants.     

Effect of MgO and CaO/SiO2 on the immobilization of chromium in synthetic slags

This work investigated the chemical and mineralogical properties of CaO–SiO₂–Cr₂O₃–CaF₂–MgO slags. Synthetic slags were prepared and the effect of the slag basicity (mass ratio CaO/SiO₂) and MgO contents on the stability of the mineralogical species formed was analyzed. The morphology and composition of the slags were analyzed by X-ray powder diffraction (XRD) and scanning electron microscope-energy dispersive spectroscopy (SEM–EDS), whilst their chemical stability was evaluated by leaching with an aqueous acetic acid solution. It was found that in slags with CaO/SiO₂?=?1, the main Cr-compound was MgCr₂O₄ spinel, which forms octahedron crystals. Small amounts of CaCr₂O₄ and CaCrO₄ were also observed. It was found that with increasing the slag basicity from 1 to 2 the compounds MgCr₂O₄ and CaCr₂O₄ were formed together with the Cr(V)-containing compound complex Ca₅(CrO₄)₃F which forms hexagonal crystals. The results showed that the highest Cr concentration levels in the leaching liquors corresponded to slags with CaO/SiO₂?=?2, probably owing to the formation of CaCrO₄ and Ca₅(CrO₄)₃F, whilst the lowest chromium concentration levels corresponded to MgO-based slags owing to the stable binding of chromium in spinel with MgO. Additionally, potential–pH diagrams for the Ca–Cr–H₂O and Mg–Cr–H₂O systems at 25?°C were calculated.