Abstract The purpose of this study was to evaluate the efficiency of biosparging for in situ remediation of groundwater at a site contaminated by petrochemicals. To this end, laboratory-scale (lab-scale for short) and pilot-scale tests were carried out. In the lab-scale study, three possible ways (i.e., by injecting air, by adding hydrogen peroxide, and by adding magnesium peroxide) of increasing the dissolved oxygen content in the groundwater were evaluated in terms of the resulting total bacterial count. Under the conditions used in this work, air injection was found to the most effective one. By injecting compressed air into the mixture of petrochemicals-contaminated soil and groundwater at a flow rate of 175mL/min for five minutes, the total bacterial count of the aerobic bacteria was increased greatly from 102CFU/mL to 107CFU/mL. The concentrations of benzene, toluene, ethyl benzene, and xylenes (BTEX) also were reduced to lower than 0.5£gg/L. Based on the findings obtained from the lab-scale study, air injection was adopted for the enhancement of pilot-scale in situ bioremediation of petrochemicals-contaminated groundwater at a selected site in a petrochemical plant. To evaluate the treatment efficiency of biosparging for the removal of BTEX and naphthalene, in addition to an upstream groundwater well, six one-meter-apart monitoring wells were installed in at the test site the flow direction of groundwater. In the center of the test site, one air injection well and ten soil gas monitoring points also were installed to determining the radius of influence of the air injection well. It was found that an air injection rate of 40L/min was capable of providing sufficient air to all of the monitoring wells of groundwater and increasing the total bacterial count of aerobic bacteria from the order of 102CFU/mL to 106CFU/mL. For a test period of 99 days, the concentrations of all target contaminants in each groundwater monitoring well were decreased markedly. More specifically, the total organic carbon was reduced from 12.7-43.4 mg/L to 3.5-14.9 mg/L; biochemical oxygen demand, from 124-526 mg/L to 43-153 mg/L; benzene; toluene, from 29.88-62.34 mg/L to 11.72-12.82 mg/L ; ethyl benzene, from 0.92-5.30 mg/L to 0.86 mg/L-< 0.5£gg/L; xylenes, from 9.31-47.58 mg/L to 4.07 mg/L -< 0.5£gg/L; and naphthalene, from15.31-0.92 mg/L to < 0.5 £gg/L. Additionally, pH, temperature, and concentrations of various cations determined for the groundwater as well. During the 99-day test period, the following were found: pH varied in the range of 6.75-7.45; temperature, 30-32¢J; Ca2+, 45-65 mg/L; Mg 2+, 16-24 mg/L; Na+, 35-60 mg/L; K+, 8-14 mg/L; and total iron, 2.0-4.0 mg/L. Thus, under the conditions used in this work, the biosparging technology employed was found to have an overall treatment efficiency of over 60% for BTEX and 100% for naphthalene. To increase the overall treatment efficiency, a prolonged air injection is needed at this test site. Keywords: biosparging, groundwater, contaminated site, petrochemicals

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This study examined the effect of in-situ biosparging on pentachlorophenol (PCP) degradation and bacterial communities in PCP contaminated groundwater. Bacteria were identified by sequencing the 16s rDNA fragment from DNA extracted from groundwater cultures and comparing those sequences to a database using a basic local alignment search tool, BLAST. The PCP-degraders Burkholderia cepacia and Flavobacterium (Sphingobium) chlorophenolicum were identified in multiple wells, as were the 4-chlorophenol degrader Herbaspirillum sp., and the common soil bacteria Pseudomonas sp., Aquaspirillum sp., and Rhodocista sp., among others. Numerous bacterial samples also appeared in the results as “uncultured”. Bacterial community changes were observed using terminal restriction fragment length polymorphism (TRFLP) analysis to identify operational taxonomic units of bacteria at various locations inside and outside the biosparging zone of treatment over time. Diversity measures including species richness, Simpson’s and Shannon’s indices, and species evenness were calculated from operational taxonomic unit results for each well at each sampling point in order to better understand changes in the bacterial community. Species richness tended to be higher at wells further away from the biosparging line, while diversity and evenness varied throughout the area. Correlations between PCP concentration, operational taxonomic units, and distance from biosparging wells were determined by Pearson’s product-moment correlation and Spearman’s rank correlation. Positive correlations were found between distance from biosparging wells and PCP concentration, species richness and distance, and to a smaller degree, diversity and distance. Biosparging remediation has a significant impact on the types of PCP-degrading bacteria within the groundwater matrix, and installations of this type of treatment should be applied to maximize the use of the native bacteria to assist in degradation of the contaminant.

Air sparging is a technique used to remediate gasoline contamination. In sparging, air is injected below the target zone and removes contamination via two separate mechanisms; volatilization and biodegradation. In volatilization, the air contacts the contamination as it moves upward. The contaminant will partition to the vapor phase based on its volatility and will be removed as the air reaches the atmosphere. For biodegradation, the oxygen in the airstream is used for microbial activity. Pulsed air sparging, otherwise known as pulsed biosparging, has been found to be more effective than continuous air sparging. Pulsed biosparging enhances treatment because it induces groundwater movement and mixing. The general mechanisms for treatment of gasoline sources using air sparging are relatively well characterized. However, air flow through the subsurface and the total hydrocarbon mass lost are difficult to predict and quantify. This project was intended to quantify the mass lost through volatilization and through biodegradation at the E10 gasoline source using pulsed biosparging, and to determine the effect of the source zone removal on downgradient dissolved BTEX concentrations. The remedial system consisted of two major components: the air sparging system, with three injection points; and a soil gas collection system. The soil gas collection system was comprised of an airtight box that covered the source area and the monitoring wells upgradient and downgradient of the source. Off-gas from the soil gas collection system was monitored continuously using a PID. The off-gas was also sampled frequently for BTEX, pentane, and hexane to determine the hydrocarbon mass removed; and for O2 and CO2 to determine biodegradation rates. The remedial system ran for approximately 280 hours over 33 days. Of the estimated 22.3 kg of gasoline residual in the source zone, 4.6 kg or 21% of the residual was removed via volatilization and 4.9 kg or 22% of the residual was removed via biodegradation. Leakage outside the system was estimated at less than 0.1% of the total mass. Groundwater samples were collected when the last sparged air was calculated to arrive at the row 2 downgradient fence. The average BTEX groundwater concentration after sparging was 40% of the pre-sparging concentration. The benzene mass discharge decreased 27%, the ethylbenzene mass discharge decreased 65%, the p/m-xylene mass discharge decreased 6%, and the o-xylene mass discharge decreased 5%. The mass discharge for naphthalene and TMB isomers increased 19%. However, these values fit in with long-term groundwater concentration trends. Additional sampling is recommended to determine if the sparging made a significant impact on mass discharge leaving the source.

Air sparging is a technique used to remediate gasoline contamination. In sparging, air is injected below the target zone and removes contamination via two separate mechanisms; volatilization and biodegradation. In volatilization, the air contacts the contamination as it moves upward. The contaminant will partition to the vapor phase based on its volatility and will be removed as the air reaches the atmosphere. For biodegradation, the oxygen in the airstream is used for microbial activity. Pulsed air sparging, otherwise known as pulsed biosparging, has been found to be more effective than continuous air sparging. Pulsed biosparging enhances treatment because it induces groundwater movement and mixing. The general mechanisms for treatment of gasoline sources using air sparging are relatively well characterized. However, air flow through the subsurface and the total hydrocarbon mass lost are difficult to predict and quantify. This project was intended to quantify the mass lost through volatilization and through biodegradation at the E10 gasoline source using pulsed biosparging, and to determine the effect of the source zone removal on downgradient dissolved BTEX concentrations. The remedial system consisted of two major components: the air sparging system, with three injection points; and a soil gas collection system. The soil gas collection system was comprised of an airtight box that covered the source area and the monitoring wells upgradient and downgradient of the source. Off-gas from the soil gas collection system was monitored continuously using a PID. The off-gas was also sampled frequently for BTEX, pentane, and hexane to determine the hydrocarbon mass removed; and for O2 and CO2 to determine biodegradation rates. The remedial system ran for approximately 280 hours over 33 days. Of the estimated 22.3 kg of gasoline residual in the source zone, 4.6 kg or 21% of the residual was removed via volatilization and 4.9 kg or 22% of the residual was removed via biodegradation. Leakage outside the system was estimated at less than 0.1% of the total mass. Groundwater samples were collected when the last sparged air was calculated to arrive at the row 2 downgradient fence. The average BTEX groundwater concentration after sparging was 40% of the pre-sparging concentration. The benzene mass discharge decreased 27%, the ethylbenzene mass discharge decreased 65%, the p/m-xylene mass discharge decreased 6%, and the o-xylene mass discharge decreased 5%. The mass discharge for naphthalene and TMB isomers increased 19%. However, these values fit in with long-term groundwater concentration trends. Additional sampling is recommended to determine if the sparging made a significant impact on mass discharge leaving the source.