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.

The contamination of aquifer systems by petroleum hydrocarbons is a global problem. Underground storage tanks used for storing these hydrocarbons often leak, resulting in subsurface contamination. The hazards associated with petroleum hydrocarbon contamination are mainly attributable to the BTEX compounds, namely benzene, toluene, ethylbenzene and xylenes together with trimethylbenzenes (TMBs) and naphthalene due to their potential to impact human health and the ease with which they can enter the groundwater system. In situ chemical oxidation (ISCO) is the delivery of strong chemical oxidants to the subsurface for the purpose of treating organic contaminants. ISCO can be an effective way to remediate organic contaminants from the soil and groundwater. Sodium persulphate is one of the newer oxidants to gain widespread use in treating petroleum hydrocarbon contamination, though without being fully understood. This investigation tested the ability of unactivated sodium persulphate in treating dissolved phase and residual BTEX contamination through bench-scale laboratory tests and a pilot-scale field study.

- Chapter 1: An overview of chemical oxidation including its development and application for in situ treatment of contaminated sites. The oxidation chemistry of Fenton's reagent, permanganate, and ozone are highlighted along with optional methods of oxidant delivery for in situ application. The results of lab-and field-scale applications are summarized.- Chapter 2: A description of the principles and processes of chemical oxidation using potassium or sodium permanganate for organic chemical degradation, including reaction stoichiometry, equilibria, and kinetics, as well as the effects of environmental factors.- Chapter 3: Information provided on the effects of permanganate on the behavior of metals.- Chapter 4: A discussion of the potential for permeability loss and other secondary effects during in situ oxidation using permanganate.- Chapter 5: A description of optional methods of oxidant delivery for in situ remediation.- Chapter 6: A description of a process for evaluation, design, and implementation of permanganate systems.- Chapter 7: A detailed description of five different applications of an in situ chemical oxidation using potassium or sodium permanganate.- Chapter 8: Highlights of the current status and future directions of this remediation technology.

The contamination of groundwater and subsurface soil in the United States is a widespread and challenging problem. There are estimated to be in excess of 200,000 sites requiring some form of remediation, and many of these sites potentially threaten groundwater resources. In areas where the groundwater resources are not considered at risk, there are frequently impediments to the reuse of brownfield sites. In addition, for many subsurface geological settings, conventional treatment methods, such as pump-and-treat technology, can be costly and inefficient. Emerging in situ groundwater and subsurface soil treatment technologies may provide effective, lower-cost alternatives, and it is important to fully understand all aspects of any new and innovative technology. This guidance document was developed to outline the technical and regulatory requirements of in situ chemical oxidation (ISCO), a group of technologies involving various combinations of oxidants and delivery techniques. The primary oxidants addressed in this document are hydrogen peroxide, potassium and sodium permanganate, sodium persulfate, and ozone. The effectiveness of some of these oxidants can be enhanced through activation (Fenton's reagent, activated persulfate) and used in conjunction with other oxidants (perozone). Additionally, this document is intended to expedite movement to a consensus on regulatory requirements through the Interstate Technology & Regulatory Council concurrence process. It should prove useful to regulators, stakeholders, consultants, and technology implementers. The document is divided into sections consisting of technology overview and applicability, remedial investigations, safety concerns, regulatory concerns, injection design, monitoring, stakeholder concerns, and case studies. From a regulatory perspective, the most important sections of the document are identification of injection restrictions, implementation, and post-closure monitoring.

This volume provides comprehensive up-to-date descriptions of the principles and practices of in situ chemical oxidation (ISCO) for groundwater remediation based on a decade of intensive research, development, and demonstrations, and lessons learned from commercial field applications.

At hundreds of thousands of commercial, industrial, and military sites across the country, subsurface materials including groundwater are contaminated with chemical waste. The last decade has seen growing interest in using aggressive source remediation technologies to remove contaminants from the subsurface, but there is limited understanding of (1) the effectiveness of these technologies and (2) the overall effect of mass removal on groundwater quality. This report reviews the suite of technologies available for source remediation and their ability to reach a variety of cleanup goals, from meeting regulatory standards for groundwater to reducing costs. The report proposes elements of a protocol for accomplishing source remediation that should enable project managers to decide whether and how to pursue source remediation at their sites.