For sites contaminated with chloroethene non-aqueousphase liquids, designing a remediation system that couples in situ chemical oxidation (ISCO) with potassium permanganate (KMnO4) and microbial dechlorination may be complicated because of the potentially adverse effects of ISCO on anaerobic bioremediation processes. Therefore, one-dimensional column studies were conducted to understand the effect of permanganate oxidation on tetrachloroethene (PCE) dechlorination by the anaerobic mixed culture KB-1. Following the confirmation of PCE dechlorination, KMnO4 was applied to all columns at a range of concentrations and application velocities to simulate varied distances from oxidant injection. Immediately following oxidation, reductive dechlorination was inhibited; however, after passing several pore volumes of sterile growth medium through the columns after oxidation, a rebound of PCE dechlorination activity was observed in every inoculated column without the need to reinoculate. The volume of medium required for a rebound of dechlorination activity differed from 1.1 to 8.1 pore volumes (at a groundwater velocity of 4 cm/d), depending on the specific condition of oxidant application.

The presence of coal tars in the subsurface associated with former manufactured gas plants (MGPs) offers a remediation challenge due to their complex chemical composition, dissolution behaviour and recalcitrant characteristics. A former MGP site in Clearwater Beach, Florida was characterized and bench-scale analyses were conducted to assess the potential for in situ chemical oxidation (ISCO) using persulfate to treat MGP residuals. Completion of a conceptual site model identified a homogeneous, silty sand aquifer, with an average hydraulic conductivity of approximately 2.3x10-3 cm/s and a groundwater flow rate of 2 cm/day in the direction of S20°E. Six source zones, three near the water table and three in the deep aquifer were estimated to have a total volume of 108 m3. A multi-level well transect was installed to monitor concentrations of dissolved compounds and to estimate mass discharge downgradient of the source zones over time. On average, the morphology of the aqueous concentrations remained consistent with time. A total mass discharge across the transect of 94 mg/day was estimated for site-specific compounds. Bench-scale tests were conducted on aquifer sediments and groundwater samples. The aquifer was determined to have a low buffering capacity, low chemical oxygen demand, and low natural oxidant interaction (NOI) with persulfate. Aqueous batch experiments identified the potential for iron (II) activated persulfate to reduce concentrations of BTEX and PAHs below method detection limits (MDLs). Unactivated persulfate was able to reduce BTEX concentrations to below MDLs after 14 days; however, the concentration of PAH compounds remained above MDLs after 14 days. Higher iron doses within the system were shown to be more effective in reducing BTEX and PAH compounds. Column experiments designed to mimic site conditions were used to evaluate the feasibility of persulfate treatment on impacted sediments from the Clearwater site. Two sets of column experiments were conducted: one using unactivated persulfate followed by alkaline activated persulfate; and one using iron (II) activated persulfate. On average, unactivated persulfate was able to reduce BTEX and PAH aqueous effluent concentrations by > 75% and 40%, respectively, after a total dose of 60 g/g soil. Two additional doses of alkaline activated persulfate (total persulfate dose of ~80g/g soil) in these columns were able to further reduce effluent BTEX and PAH concentrations by > 90% and > 75%, respectively. Iron (II) activated persulfate reduced effluent BTEX concentrations by > 70% and PAHs by > 65% after a total dose of 35 g/g soil. Average reductions in mass for BTEX and PAH compounds were approximately of 48% and 26% respectively in the iron (II) activated persulfate columns, and 24% and 10%, respectively in the alkaline activated persulfate columns. The potential for the ability to use in situ chemical oxidation using persulfate for the remediation of MGP residuals in the subsurface is evaluated using field measurements and bench-scale experimentation. The reductions observed in aqueous phase compounds in MGP groundwater as observed in the laboratory indicate the potential for reductions in groundwater concentrations at this and other contaminated former MGP sites. However, column experiments, indicating the inability for activated persulfate to reduce all identified compounds in the MGP NAPL suggest source treatment with activated persulfate would not reduce concentrations to below Florida Department of Environmental Protection natural attenuation concentrations.

The purpose of this study was to use controlled release technology combining with in situ chemical oxidation (ISCO) and permeable reactive barrier (PRB) to remediate TCE-contaminated groundwater. In this study, potassium permanganate (KMnO4) releasing material was designed for potassium permanganate release in groundwater. The components of potassium permanganate releasing material included poly (£`-caprolactone) (PCL), potassium permanganate, and starch with a weight ratio of 2:1:0.5. Approximately 63.8% (w/w) of potassium permanganate was released from the material after 76 days of operation. The released was able to oxidize contaminant in groundwater. Results from the solid oxidation demand (SOD) experiment show that the consumption rate increased with increased contaminant concentration. TCE removal efficiency increased with the increased TCE concentration. The second-order rate law can be used to simulate the TCE degradation trend. In the column experiment, results show that the released MnO4- could oxidize TCE and TCE degradation byproducts when 95.6 pore volume (PV) of contaminated groundwater was treated. More than 95% of TCE removal can be observed in the column study. Although the concentration of manganese dioxide (MnO2) began to rise after 8.8 PV of operation, TCE removal was not affected. Results also show that low level of hexavalent chromium was detected (< 0.05 mg/L). Results from the scanning electron microscope (SEM) and energy-dispersive spectroscope (EDX) analyses show that the amounts of manganese and potassium in the materials decreased after the releasing experiment. Results indicate that the concentration of TCE and SOD need to be analyzed before the releasing materials are applied in situ. In the practical application, the releasing materials will not become solid wastes because they are decomposed after use. If this slow-releasing technology can be combined with a permeable reactive barrier system, this technology will become a more economic and environmentally-friendly green remedial system.

Soil and groundwater at many existing and former industrial areas and disposal sites is contaminated by organic solvent compounds that were released into the environment. Organic solvent compounds are heavier than water. When they are released into the subsurface, they tend to adsorb onto the soils and cause the appearance of LNAPL (light nonaqueous phase liquid) and DNAPL (dense nonaqueous phase liquid) pool. The industrial petroleum hydrocarbons (e.g., methyl tertiary-butyl ether, MTBE and benzene) and chlorinated solvent (e.g., trichloroethylene, TCE) are among the most ubiquitous organic compounds found in subsurface contaminated environment. One cost-effective approach for the remediation of the chlorinated solvent and petroleum products contaminated aquifers is the installation of permeable reactive zones or barriers within aquifers. As contaminated groundwater moves through the emplaced reactive zones, the contaminants are removed, and uncontaminated groundwater emerges from the downgradient side of the reactive zones. The objectives of this study were developed to evaluate the feasibility of applying in-situ chemical oxidation (ISCO) barrier and in-situ slow polycolloid-releasing substrate (SPRS) biobarrier system on the control of petroleum hydrocarbons and chlorinated solvent plume in aquifer. In the ISCO barrier system, it contained oxidant-releasing materials, to release oxidants (e.g., persulfate) contacting with water for oxidating contaminants existed in groundwater. In this study, laboratory-scale fill-and-draw experiments were conducted to determine the compositions ratios of the oxidant-releasing materials and evaluate the persulfate release rates. Results indicate that the average persulfate-releasing rate of 7.26 mg S2O82-/d/g was obtained when the mass ratio of sodium persulfate/cement/sand/water was 1/1.4/0.24/0.7. The column study was conducted to evaluate the efficiency of in situ application of the developed ISCO barrier system on MTBE and benzene oxidation. Results from the column study indicate that approximately 86-92% of MTBE and 95-99% of benzene could be removed during the early persulfate-releasing stage (before 48 pore volumes of groundwater pumping). The removal efficiencies for MTBE and benzene dropped to approximately 40-56% and 85-93%, respectively, during the latter part of the releasing period due to the decreased persulfate-releasing rate. Results reveal that acetone, byproduct of MTBE, was observed and then further oxidized completely. Results suggest that the addition of ferrous ion would activate the persulfate oxidation. However, excess ferrous ion would compete with organic contaminants for persulfate, causing the decrease in contaminant oxidation rates. In the SPRS biobarrier system, the food preparation industry has tremendous experiences in producing stable oil-in-water (W/O, 50/50) emulsions with a uniformly small droplet size. Surfactant mixture (71 mg/L of SL and 72 /L of SG) blending with water could yield a stable and the optimal emulsion was considered the best. The small absolute value of the emulsion zeta potential reduces inter-particle repulsion, causing the emulsion droplets to stick to each other when they collided. Overtime, large masses of flocculated droplets can form which then clog the sediment pores. The results can be used to predict abiotic interactions and distribution of contaminant mass expected after SPRS injection, and thus provides a more accurate estimate of the mass of TCE removed due to enhanced biodegradation. The effect of TCE partitioning to the vegetable oil on contaminant migration rates can be approximated using a retardation factor approach, where 0.28 years through a 3 m barrier. In anaerobic microcosm experiments, result show that SPRS can be fermented to hydrogen and acetate could be used as a substrate to simulate reductive dehalorination. The apparent complete removal of nitrate and sulfate by SPRS addition was likely a major factor that promoted the complete reduction of TCE at later stages of this study. Results from the column experiment indicate that occurrence of anaerobic reductive dechlorination in the biobarrier system can be verified by: (1) the oil: water partition coefficients of dissolved TCE into vegetable oil were be used to predict abiotic interactions and distribution of contaminant mass expected after SPRS injection. (2) The SPRS can ferment to hydrogen and acetate could be used as a substrate to simulate reductive dechlorination. The proposed treatment scheme would be expected to provide a more cost-effective alternative to remediate other petroleum hydrocarbons and chlorinated solvents-contaminated aquifers. Experiments and operational parameters obtained from this study provide an example to design a passive barriers system for in-site remediation.

This study focuses on the Kaohsiung industrial pier sediment survey, assessment and feasibility study of the approach. In this study, field monitoring operations, including the close Salt Water River mouth area of the industrial port (area A), the far Salt Water River mouth area of the industrial port (area B) and for the factories and shipyards at the junction of the terminal area (area C), The sampling of sediments of three core and three surface sediments of area A that used as treating test at laboratory. The survey results show that the industrial pier some heavy metals in the sediment concentration is higher than the quality indicators in the sediment above the limit (ULV), especially copper and zinc. In addition, the concentration of heavy metals of industrial pier area A, B and C of the sediment at least one of them is than current soil control standard. Among them, the frequency of exceeding control standards of copper concentration is the highest, the surface sediments of area A, B and C were about 75%, 42% and 0% respectively, while the core sediments were about 20%, 90% and 15%. These results indicate that the industrial pier sediment required to carry out appropriate pre-treatment to reclamation land to recycling. After investigation, simulation and estimation, the required appropriate treatment sediment in order to landfill volume of industrial pier area A and B (Salt Water River mouth) were approximately 40,000 and 36,400 cubic meters, the total approximately 76,400 cubic meters. Industrial pier is located in the Salt Water River mouth, and therefore withstand the effects of pollutants of the upstream sources flowed in, and than the sediment quality was poor. Sediments were accumulated in the bottom should be removed and sediments at the upstream Salt Water River should be treated too, the remediation and pollution source control for the future to improve the sediment quality is the most important work in Taiwan. In this study, chemical washing and chemical oxidation of the two treatment technology for industrial pier sediment organic pollutants (total petroleum hydrocarbons (TPH) as the target pollutants) to deal with the feasibility test. Sediment to be processed was collected neart the industrial pier, the pH value of approximately 7.1, the moisture content was 43.9%, 20.1% organic matter content, while the particle size composition of mainly fine particles (silt + clay) to about 84.3% handling may be more difficult. The sediments of the TPH concentration of 8,691 mg / kg. Three surfactants Simple Green (SG), Triton X-100 (TX-100) and Tween 80 (TW80) were used at sediment washing test,washing with 60 pv and 5% (v / v) SG could remove 97.3% TPH at the end of the mud; 0.5% (v / v) TX-100 could remove 96.8% TPH; washing with 30 pv, 1% (v / v) TX-100 could remove 94.6% the TPH; washing with 10 pv, 5% (v / v) TX-100 could remove 96.7% TPH; but TW80 leaching ineffective. Oxidation processing, applied 6% H2O2 reaction 180 min, 58.2% of TPH could be removed. Connection of washing and oxidation treatment process, could be removed total of 86% of TPH. The sediment surface morphology before and after treatment were observed by SEM were not significantly different, no surfactant emulsion was left at sediment after treated, this result revealed the connection of washing and oxidation treatment process could remove most of TPH and less harmful to the environment was an available technique.

The presence of coal tars in the subsurface associated with former manufactured gas plants (MGPs) offers a remediation challenge due to their complex chemical composition, dissolution behaviour and recalcitrant characteristics. A former MGP site in Clearwater Beach, Florida was characterized and bench-scale analyses were conducted to assess the potential for in situ chemical oxidation (ISCO) using persulfate to treat MGP residuals. Completion of a conceptual site model identified a homogeneous, silty sand aquifer, with an average hydraulic conductivity of approximately 2.3x10-3 cm/s and a groundwater flow rate of 2 cm/day in the direction of S20°E. Six source zones, three near the water table and three in the deep aquifer were estimated to have a total volume of 108 m3. A multi-level well transect was installed to monitor concentrations of dissolved compounds and to estimate mass discharge downgradient of the source zones over time. On average, the morphology of the aqueous concentrations remained consistent with time. A total mass discharge across the transect of 94 mg/day was estimated for site-specific compounds. Bench-scale tests were conducted on aquifer sediments and groundwater samples. The aquifer was determined to have a low buffering capacity, low chemical oxygen demand, and low natural oxidant interaction (NOI) with persulfate. Aqueous batch experiments identified the potential for iron (II) activated persulfate to reduce concentrations of BTEX and PAHs below method detection limits (MDLs). Unactivated persulfate was able to reduce BTEX concentrations to below MDLs after 14 days; however, the concentration of PAH compounds remained above MDLs after 14 days. Higher iron doses within the system were shown to be more effective in reducing BTEX and PAH compounds. Column experiments designed to mimic site conditions were used to evaluate the feasibility of persulfate treatment on impacted sediments from the Clearwater site. Two sets of column experiments were conducted: one using unactivated persulfate followed by alkaline activated persulfate; and one using iron (II) activated persulfate. On average, unactivated persulfate was able to reduce BTEX and PAH aqueous effluent concentrations by > 75% and 40%, respectively, after a total dose of 60 g/g soil. Two additional doses of alkaline activated persulfate (total persulfate dose of ~80g/g soil) in these columns were able to further reduce effluent BTEX and PAH concentrations by > 90% and > 75%, respectively. Iron (II) activated persulfate reduced effluent BTEX concentrations by > 70% and PAHs by > 65% after a total dose of 35 g/g soil. Average reductions in mass for BTEX and PAH compounds were approximately of 48% and 26% respectively in the iron (II) activated persulfate columns, and 24% and 10%, respectively in the alkaline activated persulfate columns. The potential for the ability to use in situ chemical oxidation using persulfate for the remediation of MGP residuals in the subsurface is evaluated using field measurements and bench-scale experimentation. The reductions observed in aqueous phase compounds in MGP groundwater as observed in the laboratory indicate the potential for reductions in groundwater concentrations at this and other contaminated former MGP sites. However, column experiments, indicating the inability for activated persulfate to reduce all identified compounds in the MGP NAPL suggest source treatment with activated persulfate would not reduce concentrations to below Florida Department of Environmental Protection natural attenuation concentrations.

No description available.

No description available.

This study evaluated the effect of chemical oxidation on the bioremediation of polycyclic aromatic hydrocarbons (PAHs) contaminated sediments. Sediments were treated in sequential steps: biotreatment, chemical oxidation, and biotreatment. The first biotreatment step was initiated via addition of nutrients, microbial seeds, co-metabolites, and/or Tween 80 (surfactant). The chemical oxidation step was conducted using Fenton?s Reagent, ozonation, and peroxone (combination of ozone and hydrogen peroxide). The objective was to enhance the PAHs bioavailability via oxidation of natural organic matter and transformation of Heavy PAHs into more biodegradable compounds. Biotreatment was reestablished as a final polishing step to further degrade remaining PAHs and more biodegradable oxidation by-products. The proposed mechanism was proven successful for the less contaminated sediment (Scioto River) and not the highly contaminated and chemically more complex sediment (Lake Superior). Given this mechanism only worked for the Scioto River sediment, further research is required to determine the mechanisms limiting treatment.

Landfill fires are relatively common incidents that landfill operators encounter which have great impact on landfill structure and the environment. According to a U.S. Fire Administration report in 2001, an average of 8,300 landfill fires occurs each year in the United States, most of them in the spring and summer months. Subsurface spontaneous fires are considered the most dangerous and difficult to detect and extinguish among landfill fires. Few studies have been conducted on spontaneous fires in landfills. Information regarding the thermal behavior of solid waste is not available nor have measurements been made to evaluate spontaneous ignition of solid waste. The purpose of this research was to provide information concerning the initiation of spontaneous ignition incidents in landfills, and investigate the conditions favoring their occurrence. This study enabled better understanding of the self-heating process and spontaneous combustion in landfills. Effects of parameters critical to landfill operation on spontaneous combustion were determined. Spontaneous combustion occurs when materials are heated beyond the ignition temperature. Temperature rise occurs inside the landfill due to exothermic reactions which cause self-heating of the solid waste. Oxygen introduction leading to biological waste degradation and chemical oxidation is believed to be the main cause of rising solid waste temperatures to the point of ignition. A survey was distributed to landfill operators collecting information regarding spontaneous firs incidents in their landfills. Survey results raised new questions necessitating further study of subsurface fires incidents. Subsurface spontaneous fires were not restricted to any landfill geometry or type of waste (municipal, industrial, commercial, and construction and demolition). Results showed that landfill fires occur in landfills that do and do not recirculate leachate. Although new methods have been developed to detect subsurface fires, landfill operators depend primarily on visual observation of smoke or steam to detect the subsurface fires. Also, survey results indicated that excavating and covering with soil are the most widespread methods for extinguishing subsurface fires. Methane often has been suspected for initiating spontaneous subsurface firs in the landfill. However, combustible mixture of methane and oxygen requires very high temperature to ignite. In this study it was shown that spontaneous fires are initiated by solid materials with lower ignition points. Laboratory tests were conducted evaluating the effect of moisture content, oxygen concentration and leachate on spontaneous ignition of solid waste. A new procedure for testing spontaneous ignition is described based on the crossing-point method. The procedure was used to study the spontaneous combustion of solid waste and determine the auto-ignition temperature of the solid waste components and a synthesized solid waste. Correlations have been established between auto-ignition temperature, specific weight and energy content and between self-heating temperature and specific weight. Correlations indicated that compaction can help avoid spontaneous combustion in the landfill. Dense materials require higher energy to increase in temperature and limit the accessibility of oxygen. In the experimental work, moisture was found to promote both biological and chemical self-heating. Increasing moisture content lowers the solid waste permeability and absorbs more energy as it evaporates. Dissolved solids in leachate were found to promote self-heating and ignition more than distilled water. Varying oxygen concentrations indicated that heat generation occurs due to chemical oxidation even at oxygen concentration as low as 10% by volume. However, at 10% by volume oxygen, solid waste did not exhibit thermal runaway nor flammable combustion. At 0% by volume oxygen, tests results indicated occurrence of self-heating due to slow pyrolysis. A numerical one-dimensional energy model was created to simulate temperature rise in landfill for four different scenarios. Using the results from the laboratory experiment, the model estimated the heat generation in solid waste due to chemical reactions. Results from the scenario simulations indicated that moisture evaporation is the major heat sink in the landfill. The model showed that gas flow has a cooling effect due to increasing amount of evaporated water and can control the temperature inside the landfill. The model showed that a temperature higher than the biological limit can be maintained in the landfill without initiating spontaneous fire.