Optimal Field Approaches for Electrokinetic In Situ Oxidation Remediation

Numerical simulations were used to identify and evaluate optimum electrode configurations and approaches for electrokinetic in situ chemical oxidation (EK‐ISCO) remediation of low‐permeability sediments. A newly developed groundwater and EK flow and reactive transport numerical model was used to conduct two‐dimensional scenario simulations of the coverage of an injected oxidant, permanganate, and the oxidation of a typical organic contaminant (tetrachloroethene, PCE). For linear configurations of vertical electrodes, the spacing of same‐polarity electrodes is recommended to be about one‐third to one‐quarter of the anode–cathode spacing. Greater coverage could also be achieved by locating additional oxidant injection wells at the divergence of the electric field in linear electrode configurations. Horizontal electrodes allowed greater contact between the injected permanganate and PCE and resulted in faster degradation of PCE compared to vertical electrodes. Pulsed oxidant injection, closer electrode spacing, and electric field reversal also resulted in faster EK‐ISCO remediation.     

In Situ Biorestoration as a Ground Water Remediation Technique

In situ biorestoration, where applicable, is indicated as a potentially very cost-effective and environmentally acceptable remediation technology. Many contaminants in solution in ground water as well as vapors in the unsaturated zone can be completely degraded or transformed into new compounds by naturally occurring indigenous microbial populations. Undoubtedly, thousands of contamination events are remediated naturally before the contamination reaches a point of detection. The need is for methodology to determine when natural biorestoration is occurring, the stage the restoration process is in, whether enhancement of the process is possible or desirable, and what will happen if natural processes are allowed to run their course.
In addition to the nature of the contaminant, several environmental factors are known to influence the capacity of indigenous microbial populations to degrade contaminants. These factors include dissolved oxygen, pH, temperature, oxidation-reduction potential, availability of mineral nutrients, salinity, soil moisture, the concentration of specific pollutants, and the nutritional quality of dissolved organic carbon in the ground water.
Most enhanced in situ bioreclamation techniques available today are variations of hydrocarbon degradation procedures pioneered and patented by Raymond and coworkers at Suntech during the period 1974 to 1978. Nutrients and oxygen are introduced through injection wells and circulated through the contaminated zone by pumping one or more producing wells.
The limiting factor in remediation technology is getting the contaminated subsurface material to the treatment unit or units, or in the case of in situ processes, getting the treatment process to the contaminated material. The key to successful remediation is a thorough understanding of the hydrogeologic and geochemical characteristics of the contaminated area.     

Comparison of Delivery Methods for Enhanced In Situ Remediation in Clay Till

Three methods for enhanced delivery of in situ remediation amendments in low-permeability deposits have been tested at a site in Denmark: pneumatic fracturing, direct-push delivery, and hydraulic fracturing. The testing was carried out at an uncontaminated part of a farm site, previously used for storage of chlorinated solvents, underlain by basal clay till with hydraulic conductivity ranging from 7.1× 10^–11 to 3.5 × 10^–7 m/s at testing depths 2.5 to 9.5 m b.s. Fluorescent tracers fluorescein and rhodamine WT were delivered. Tests of all three delivery methods have not been carried out at a single site before, and thus, this study provides unique data for comparison of enhanced delivery methods in both the vadose and saturated zone. Results show that pneumatic fracturing with nitrogen gas and propagation pressures of 1 to 9 bar had a distribution radius of less than 2 m, and produced dense networks of tracer-filled natural fractures above the redox boundary (0 to 3 m b.s.) and widely spaced, discrete, induced, tracer-filled subhorizontal fractures at depth (>3 m b.s.). Direct-push delivery at pressures of 8 to 30 bar had a distribution radius of approximately 1 m, distributed tracer primarily in natural fractures above the redox boundary and in discrete, closely spaced (but not merging) induced fractures below the redox boundary. Hydraulic fracturing with a sand-guar mixture at pressures of 0 to 6 bar produced an elliptical, asymmetrical, bowl-shaped fracture with a physical radius of approximately 3.5 m at 3 m b.s. The geometry of hydraulic fractures attempted emplaced at 6.5 and 9.5 m b.s. is uncertain, but clearly not horizontal as desired. The direct-push delivery method is robust and efficient for enhanced delivery at the clay till site in question, which based on thorough geological characterization is deemed a geologically representative basal clay till site.     

Arrays of Unpumped Wells for Plume Migration Control by Semi-Passive In Situ Remediation

Arrays of unpumped wells can be used as discontinuous permeable walls in which each well serves both as a means to focus ground water flow into the well for treatment and as a container either for permeable reactive media which directly destroy dissolved ground water contaminants or for devices or materials which release amendments that support in situ degradation of contaminants within the aquifer downgradient of the wells. This paper addresses the use of wells for amendment delivery, recognizing the potential utility of amendments such as electron acceptors (e.g., oxygen nitrate), electron donors (primary substrates), and microbial nutrients for stimulating bioremediation, and the potential utility of oxidizers, reducers, etc., for controlled abiotic degradation. Depending on its rate and constraints, the remedial reaction may occur within the well and/or downgradient. For complete remediation of ground water passing through the well array, the total flux of amendment released must meet or exceed the total flux demand imposed by the plume. When there are constraints on the released concentration of amendment (relative to the demand), close spacing of the wells may be required. If the flux balance allows wider spacing, it is likely that limited downgradient spreading of the released amendment will then be the primary constraint on interwell spacing. Divergent flow from the wells, roughly two times the well diameter, provides the bulk of downgradient spreading and constrains maximum well spacing in the absence of significant lateral dispersion. Stronger lateral dispersion enhances the spreading of amendment, thereby increasing the lateral impact of each well, which allows for wider well spacing.     

Optimizing the Environmental Performance of In Situ Thermal Remediation Technologies Using Life Cycle Assessment

In situ thermal remediation technologies provide efficient and reliable cleanup of contaminated soil and groundwater, but at a high cost of environmental impacts and resource depletion due to the large amounts of energy and materials consumed. This study provides a detailed investigation of four in situ thermal remediation technologies (steam enhanced extraction, thermal conduction heating, electrical resistance heating, and radio frequency heating) in order to (1) compare the life‐cycle environmental impacts and resource consumption associated with each thermal technology, and (2) identify options to reduce these adverse effects. The study identifies a number of options for environmental optimization of in situ thermal remediation. In general, environmental optimization can be achieved by increasing the percentage of heating supplied in off peak electricity demand periods as this reduces the pressure on coal‐based electricity and thereby reduces the environmental impacts due to electricity production by up to 10%. Furthermore, reducing the amount of concrete in the vapor cap by using a concrete sandwich construction can potentially reduce the environmental impacts due to the vapor cap by up to 75%. Moreover, a number of technology‐specific improvements were identified, for instance by the substitution of stainless steel types in wells, heaters, and liners used in thermal conduction heating, thus reducing the nickel consumption by 45%. The combined effect of introducing all the suggested improvements is a 10 to 21% decrease in environmental impacts and an 8 to 20% decrease in resource depletion depending on the thermal remediation technology considered. The energy consumption was found to be the main contributor to most types of environmental impacts; this will, however, depend on the electricity production mix in the studied region. The combined improvement potential is therefore to a large extent controlled by the reduction/improvement of energy consumption.     

In Situ Remediation of Jet A in Soil and Ground Water by High Vacuum, Dual Phase Extraction

This report summarizes the initial results of subsurface remediation at Terminal 1, Kenneth International Airport, to remediate soil and ground water contaminated with Jet A fuel. The project was driven and constrained In the const ruction schedule of a major new terminal at the facility. The remediation system used a combination of ground water pumping, air injection, and soil vapor extraction. In the first five months of operation, the combined processes of dewatering, volatilization, and biodegradation removed a total of 36,689 pounds of total volatile and semivolatile organic jet fuel hydrocarbons from subsurface soil and ground water. The. results of this case study have shown that 62 percent of the removal resulted from biodegradation, 21 percent occurred as a result of liquid removal, and 11 percent resulted from the extraction of volatile organic compounds (VOC's).     

Evaluation of Extensive Secondary Maximum Contaminant Level Exceedances Following Remediation by In Situ Chemical Oxidation

In situ chemical oxidation (ISCO) with activated persulfate is commonly used for the remediation of petroleum impacted soil and groundwater because of its proven efficiency and the perception that reaction end products are completely innocuous. While the reaction products are less hazardous compared to the contaminants being treated, they may inadvertently prolong site closure in areas that have adopted the U.S. Environmental Protection Agency (EPA) Secondary Maximum Contaminant Levels (SMCLs) as enforceable standards. This study examines the occurrence and persistence of iron, manganese, sulfate, sodium, and total dissolved solids (TDS) in groundwater following persulfate ISCO. The concentrations of these chemicals were observed remaining above their respective regulatory criteria almost 3 years following the chemical application. Background concentrations and mobilization due to the petroleum contamination and ISCO application are also evaluated. Baseline sampling revealed substantially higher iron and manganese concentrations inside the plume area compared to the upgradient and downgradient wells suggesting mobilization due to redox reactions occurring inside of the plume. Iron was not a component in the applied chemical formula, yet the iron concentration spiked by 366% in the key monitoring well during the first post-remediation monitoring event. Ionic interactions between the ISCO amendment and native soils are believed to be responsible for displacing significant quantities of iron from the soil. Sulfate, sodium, and TDS exceedances are primarily associated with decomposition products of the ISCO amendments. The iron, manganese, sulfate, sodium, and TDS concentrations are trending downward over time, but still exceed regulatory criteria or pre-ISCO concentrations.     

Temperature‐Activated Auto‐Decomposition Reactions: An Under‐Utilized In Situ Remediation Solution

The remediation industry has witnessed multiple innovations arising from a greater understanding of the physical, chemical, and biological processes that control the fate and transport of chemicals in the subsurface environment. In addition, increasing emphasis is being placed on remediation solutions that are greener, simpler, and more resource efficient. The positive impacts that can be derived from this emphasis include reduced energy consumption, reduced waste emissions, and lower costs. Temperature‐activated auto‐decomposition reactions represent a potentially underutilized option for the in situ remediation of certain organic contaminants, and an option that can be both highly effective and greener than other available technologies.     

Considerations for the Design of In Situ Vapor Extraction Systems: Radius of Influence vs. Zone of Remediation

When designing in situ soil vapor extraction systems, the number and placement of vapor extraction wells arc typically based on the radius of influence determined from some combination of pilot test data, theoretical considerations, and experience. In this report, we examine common methods used to determine the radius of influence, and through examples we illustrate how effective this remedial design approach is. Significant conclusions arc the following: (a) systems designed by radius of influence-based approaches may never achieve desired remedial goals: (b) systems designed by radius of influence-based approaches may result in longer operation times and higher total costs than a system that incorporates remedial goals and some level of fundamentally based predictive modeling: and (c) at best, the radius of influence-based approach ensures containment of contaminant vapors.     

The Application of In Situ Air Sparging as an Innovative Soils and Ground Water Remediation Technology

Vapor extraction (soil venting) has been demonstrated to be a successful and cost-effective remediation technology for removing VOCs from the vadose (unsaturated) zone. However, in many cases, seasonal water table fluctuations, drawdown associated with pump-and-treat remediation techniques, and spills involving dense, non-aqueous phase liquids (DNAPLS) create contaminated soil below the water table. Vapor extraction alone is not considered to be an optimal remediation technology to address this type of contamination.
An innovative approach to saturated zone remediation is the use of sparging (injection) wells to inject a hydrocarbon-free gaseous medium (typically air) into the saturated zone below the areas of contamination. The contaminants dissolved in the ground water and sorbed onto soil particles partition into the advective air phase, effectively simulating an in situ air-stripping system. The stripped contaminants are transported in the gas phase to the vadose zone, within the radius of influence of a vapor extraction and vapor treatment system.
In situ air sparging is a complex multifluid phase process, which has been applied successfully in Europe since the mid-1980s. To date, site-specific pilot tests have been used to design air-sparging systems. Research is currently underway to develop better engineering design methodologies for the process. Major design parameters to be considered include contaminant type, gas injection pressures and flow rates, site geology, bubble size, injection interval (areal and vertical) and the equipment specifications. Correct design and operation of this technology has been demonstrated to achieve ground water cleanup of VOC contamination to low part-per-billion levels.     

Diffusive Oxygen Emitters for Enhancement of Aerobic In Situ Treatment

Aerobic biodegradation can be enhanced within contaminant plumes by elevating typically low dissolved oxygen (D.O.) levels using materials or devices that passively release oxygen. We have developed passive devices that provide a uniform, steady, long-term source of oxygen by diffusion from pressurized polymeric tubing and report test results under lab and field conditions. Lab flow-through reactor tests were conducted to determine the diffusion coefficient (D) of oxygen through four readily available tubing materials. Oxygen diffusion was greatest through Tygon® 3350 platinum-cured silicone (D = 6.67 ± 10^-7 cm²/sec), followed by 2075 Ultra Chemical Resistant Tygon (1.59 ± 10^-7 cm²/sec), 2275 High Purity Tygon (5.11 ± 10^-8 cm²/sec), and low-density polyethylene (LDPE; 1.73 ± 10^-8 cm²/sec). Variable-pressure release tests with LDPE resulted in very close estimates of D, which confirmed that mass transfer is controlled by diffusion and that the concentration gradient is a valid approximation of the chemical potential driving diffusion. LDPE emitter devices were designed and installed in seven 8-inch-diameter well screens across a portion of a gasoline plume at a former service station. With the devices pressurized to 620.5 kPag (kilopascals gauge) late in the test, steady-state D.O. concentrations reached as high as 25 mg/L, comparing favorably to the value predicted using the mass-transfer coefficient estimated from the lab test (26.3 mg/L). The method can also be used to release other gases for other reasons: gaseous tracers (i.e., sulphur hexafluoride, helium, and argon), hydrogen (for reductive dechlorination), or light alkanes (for cometabolic biodegradation of methyl tertiary butyl ether [MTBE] or chlorinated solvents).