In the past few decades, several aqueous oxidants have been employed (e.g., permanganate, persulfate) to remediate petroleum hydrocarbons. However, the majority of the research in this field has been focused primarily on the use of oxidants in treating fresh water at low groundwater temperature. In this study, bench experiments were carried out to investigate the effectiveness of persulfate (PS) as an oxidant to remediate petroleum hydrocarbons in alternative settings (saline environments at high groundwater temperature). Benzene, Toluene, Ethylbenzene, Xylenes (BTEX), Trimethylbenzenes (TMBs), and Naphthalene were the target organic compounds investigated. Three important aspects were examined during this laboratory study: 1) the evaluation of (alkaline activated and non-activated) persulfate as a chemical oxidation agent; 2) the investigation of the effect of different temperatures (10°C versus 30°C); and 3) the examination of the effect of different persulfate concentration (20 versus 100 g/L) on the reactivity of persulfate. The results showed the high potential of persulfate to remediate the target contaminants under certain conditions. In general, alkaline-activated persulfate showed a higher potential than the non-activated persulfate. However, precipitations of calcium hydroxide were observed due to the reaction between sodium hydroxide and the high concentration of calcium which will limit the use of alkaline-activated persulfate in this particular groundwater setting The results also showed that the initial concentration of persulfate and the system temperature can play important roles in enhancing the effectiveness of PS to oxidize the target contaminants. For instance, the oxidation rate of the target contaminants was seen to be dramatically increased by increasing the persulfate addition from 20 to 100 g/L as well as with increasing the system temperature from 10°C to 30°C. However, increasing both factors (temperature and concentration) accelerated the decomposition rate of PS. Lowering the system pH was tremendously successful in order to enhance the oxidation rate of all compounds. Moreover, the expected effect of the radicals scavenging at acidic pH by Cl- and Br – ,which was reported in the literatures (e.g., Pignatello et al., 2006; Grebel et al., 2010; Suri et al., 2010), was not observed in this study which might be attributed to the contribution of the produced halogen radicals to the contaminant oxidation.

In the past few decades, several aqueous oxidants have been employed (e.g., permanganate, persulfate) to remediate petroleum hydrocarbons. However, the majority of the research in this field has been focused primarily on the use of oxidants in treating fresh water at low groundwater temperature. In this study, bench experiments were carried out to investigate the effectiveness of persulfate (PS) as an oxidant to remediate petroleum hydrocarbons in alternative settings (saline environments at high groundwater temperature). Benzene, Toluene, Ethylbenzene, Xylenes (BTEX), Trimethylbenzenes (TMBs), and Naphthalene were the target organic compounds investigated. Three important aspects were examined during this laboratory study: 1) the evaluation of (alkaline activated and non-activated) persulfate as a chemical oxidation agent; 2) the investigation of the effect of different temperatures (10°C versus 30°C); and 3) the examination of the effect of different persulfate concentration (20 versus 100 g/L) on the reactivity of persulfate. The results showed the high potential of persulfate to remediate the target contaminants under certain conditions. In general, alkaline-activated persulfate showed a higher potential than the non-activated persulfate. However, precipitations of calcium hydroxide were observed due to the reaction between sodium hydroxide and the high concentration of calcium which will limit the use of alkaline-activated persulfate in this particular groundwater setting The results also showed that the initial concentration of persulfate and the system temperature can play important roles in enhancing the effectiveness of PS to oxidize the target contaminants. For instance, the oxidation rate of the target contaminants was seen to be dramatically increased by increasing the persulfate addition from 20 to 100 g/L as well as with increasing the system temperature from 10°C to 30°C. However, increasing both factors (temperature and concentration) accelerated the decomposition rate of PS. Lowering the system pH was tremendously successful in order to enhance the oxidation rate of all compounds. Moreover, the expected effect of the radicals scavenging at acidic pH by Cl- and Br – ,which was reported in the literatures (e.g., Pignatello et al., 2006; Grebel et al., 2010; Suri et al., 2010), was not observed in this study which might be attributed to the contribution of the produced halogen radicals to the contaminant oxidation.

Petroleum hydrocarbon (PHC) contamination poses a serious threat to aquifer systems worldwide. Accidental releases of PHCs due to gasoline spills and leakage from underground storage tanks can often result in PHC subsurface contamination. The main compounds of concern associated with gasoline spills are benzene, toluene, ethylbenzene and xylenes (BTEX), trimethylbenzenes (TMBs) and naphthalene, due to their high mobility and potential human health risks. Sodium persulphate is one of the newest oxidants to gain widespread use for in situ chemical oxidation (ISCO), however its effectiveness in treating PHCs is not fully understood. In this study, the ability to use unactivated sodium persulphate as a remediation tool in treating dissolved and residual BTEX contamination was tested during a bench-scale laboratory study and within a pilot-scale field investigation. In both cases unactivated sodium persulphate was used at a concentration of 100 g/L. A laboratory-scale degradation potential batch test was conducted to assess the efficacy of unactivated sodium persulphate to oxidize petroleum hydrocarbon contaminated groundwater in conjunction with aquifer material from a field site. Data from the control reactions indicated that persulphate was stable for the entire 35-day experimental period and that the decrease in PHC concentrations for most of the samples followed a first-order degradation. The behaviour and ability for sodium persulphate to oxidize dissolved and residual BTEX contamination was further evaluated in a controlled pilot scale field study. 200 kg of sodium persulphate was dissolved in 2000 L of water and injected into the subsurface. Electrical conductivity (EC), pH, sodium, persulphate, sulphate and BTEX concentrations were all monitored throughout the 158-day study period. Field research showed that there was a strong correlation between EC and sodium concentrations. Hence, this relationship allowed for real-time EC measurements to be used to effectively predict the extent of the injectate. Based on the calculated aqueous density of sodium persulphate at a concentration of 100g/L, predicted simulation model results and observed tracer field results, density effects were present and played a very important role in the transport of the injectate. The heterogeneous geology of the site also greatly influenced the transport of the injectate. The majority of the injectate appeared to have flowed out of the layers with higher hydraulic conductivity that intersected the upper and lower portion of the injection well’s screen length. The extent of the injected slug in the layers with lower hydraulic conductivity located in the centre portion of the injection well’s screen length was less in comparison. In general, areas with elevated tracer, persulphate and sulphate concentrations, also showed a decrease in BTEX concentration. Four main responses were observed. Group 1 consists of sampling points where tracer levels were elevated along with a corresponding short-term decrease in dissolved BTEX. Group 2 consists of sampling points where elevated tracer levels was observed along with a long-term apparent decrease in dissolved BTEX. Group 3 consists of sampling points where the tracer was elevated however dissolved BTEX levels remained essentially at background levels. And finally, group 4 consists of sampling points where the tracer was not observed to be elevated hence no decrease in dissolved BTEX was observed. Laboratory studies showed that the oxidation of BTEX compounds by unactivated sodium persulphate could be very successful. However, field study results showed that complexities such as heterogeneity of the field site and injectate density effects play a key role in the success of the remediation system.

Optical-electrical, rendering, paper-making, and sewage treatment plants emit odorous waste gases containing dimethyl sulfide (DMS) as one of the major odorous compounds. For the protection of ambient air quality and prevention of odor complaints, DMS should be eliminated from the gases before venting them into the atmosphere. This study aimed to develop a process for eliminating DMS in the waste gases by introducing an enough amount of chlorine gas to oxidize DMS therein to non-odorous dimethyl sulfone (DMSO2). The vented gas from the oxidation step is then contacted with a bed of granular activated carbon (GAC) to convert the residual chlorine to GAC-adsorbed hydrochloric acid and get a nearly odor-free gas. Both lab-scale and field tests were performed in this study. Results from the lab test indicate that the GAC had only an equilibrium DMS adsorption capacity of 4.30 mg/g GAC with 15-30 ppm DMS and no chlorine in the test gas. With an empty-bed gas-GAC contact time (EBCT) of around 0.49 s and no DMS in the test gas, 42 ppm gaseous chlorine could completely be reduced to HCl and the reduction product adsorbed to the GAC. The GAC had a minimum chlorine elimination capacity of around 110 mg/g GAC. Lab tests also indicate that with a molar Cl2/DMS ratio (R) of around 0.9 and a gas-phase reaction time of 5 s, and an EBCT of 0.58 s, the influent 22 ppm DMS could be removed to below detectable limits. Results from field tests in an optical-electrical wastewater plant show that by the developed process, < 1 ppm DMS in the plant¡¦s waste gas could be treated to an odor-free degree with a chlorine dose of 4-10 ppm.

Petroleum hydrocarbon (PHC) contamination poses a serious threat to aquifer systems worldwide. Accidental releases of PHCs due to gasoline spills and leakage from underground storage tanks can often result in PHC subsurface contamination. The main compounds of concern associated with gasoline spills are benzene, toluene, ethylbenzene and xylenes (BTEX), trimethylbenzenes (TMBs) and naphthalene, due to their high mobility and potential human health risks. Sodium persulphate is one of the newest oxidants to gain widespread use for in situ chemical oxidation (ISCO), however its effectiveness in treating PHCs is not fully understood. In this study, the ability to use unactivated sodium persulphate as a remediation tool in treating dissolved and residual BTEX contamination was tested during a bench-scale laboratory study and within a pilot-scale field investigation. In both cases unactivated sodium persulphate was used at a concentration of 100 g/L. A laboratory-scale degradation potential batch test was conducted to assess the efficacy of unactivated sodium persulphate to oxidize petroleum hydrocarbon contaminated groundwater in conjunction with aquifer material from a field site. Data from the control reactions indicated that persulphate was stable for the entire 35-day experimental period and that the decrease in PHC concentrations for most of the samples followed a first-order degradation. The behaviour and ability for sodium persulphate to oxidize dissolved and residual BTEX contamination was further evaluated in a controlled pilot scale field study. 200 kg of sodium persulphate was dissolved in 2000 L of water and injected into the subsurface. Electrical conductivity (EC), pH, sodium, persulphate, sulphate and BTEX concentrations were all monitored throughout the 158-day study period. Field research showed that there was a strong correlation between EC and sodium concentrations. Hence, this relationship allowed for real-time EC measurements to be used to effectively predict the extent of the injectate. Based on the calculated aqueous density of sodium persulphate at a concentration of 100g/L, predicted simulation model results and observed tracer field results, density effects were present and played a very important role in the transport of the injectate. The heterogeneous geology of the site also greatly influenced the transport of the injectate. The majority of the injectate appeared to have flowed out of the layers with higher hydraulic conductivity that intersected the upper and lower portion of the injection well’s screen length. The extent of the injected slug in the layers with lower hydraulic conductivity located in the centre portion of the injection well’s screen length was less in comparison. In general, areas with elevated tracer, persulphate and sulphate concentrations, also showed a decrease in BTEX concentration. Four main responses were observed. Group 1 consists of sampling points where tracer levels were elevated along with a corresponding short-term decrease in dissolved BTEX. Group 2 consists of sampling points where elevated tracer levels was observed along with a long-term apparent decrease in dissolved BTEX. Group 3 consists of sampling points where the tracer was elevated however dissolved BTEX levels remained essentially at background levels. And finally, group 4 consists of sampling points where the tracer was not observed to be elevated hence no decrease in dissolved BTEX was observed. Laboratory studies showed that the oxidation of BTEX compounds by unactivated sodium persulphate could be very successful. However, field study results showed that complexities such as heterogeneity of the field site and injectate density effects play a key role in the success of the remediation system.

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.

Many soil and aquifer systems in the United States have been subjected to chemical contamination from past industrial and military activities. While many remediation technologies are currently being applied, in situ chemical oxidation (ISCO) is one option that is often favored because of its potential for fast remediation times and high user control. This technology involves the direct injection of chemical oxidizers (e.g. hydrogen peroxide, ozone, or permanganate) into targeted contaminant zones within the subsurface, and it has been proven to be amenable to both BTEX compounds and other volatile organic compounds such as chlorinated solvents. This study had several key objectives. Firstly, multiple soil samples, each containing an elevated level of a targeted chemical constituent, were successfully collected in order to provide a wide range of soil types in order to make important comparisons and correlations related to ISCO?s impacts. Secondly, the impact of common soil constituents on process reagent transport was studied in order to determine which soil constituents would act as primary hindrances for the transport of hydrogen peroxide and ozone into the subsurface. Thirdly, experiments were performed to pinpoint certain personnel safety threats such as excess oxygen and heat generation that might arise during process application. Fourthly, the impact of ISCO process application on soil fabric properties was examined. Soil aerobic microbial populations, soil hydraulic conductivity, soil natural organic matter constituents, and soil adsorptive properties were all shown to be impacted following the application of chemical oxidizers.

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.