In situ thermal remediation of DNAPL and LNAPL using electrical resistance heating

Electrical resistance heating (ERH) is an in situ treatment for soil and groundwater remediation that can reduce the time to clean up volatile organic compounds (VOCs) from years to months. The technology is now mature enough to provide site owners with both performance and financial certainty in their site‐closure process. The ability of the technology to remediate soil and groundwater impacted by chlorinated solvents and petroleum hydrocarbons regardless of lithology proves to be beneficial over conventional in situ technologies that are dependent on advective flow. These conventional technologies include: soil vapor recovery, air sparging, and pumpand‐treat, or the delivery of fluids to the subsurface such as chemical oxidization and bioremediation. The technology is very tolerant of subsurface heterogeneities and actually performs as well in low‐permeability silts and clay as in higher‐ permeability sands and gravels. ERH is often implemented around and under buildings and public access areas without upsetting normal business operations. ERH may also be combined with other treatment technologies to optimize and enhance their performance. This article describes how the technology was developed, how it works, and provides two case studies where ERH was used to remediate complex lithologies. © 2005 Wiley Periodicals, Inc.     

Successful solid-phase bioremediation of petroleum-contaminated soil

Biological processes have been used to remediate petroleum hydrocarbons, pesticides, chlorinated solvents, and halogenated aromatic hydrocarbons. Biological treatment of contaminated soils may involve solid-phase, slurry-phase, or in situ treatment techniques. This article will review the general principle of solid-phase bioremediation and discuss the application of this technique for the cleanup of total petroleum hydrocarbons on two sites. These remedial programs will reduce total petroleum hydrocarbon contamination from the mean concentration of 2,660 ppm to under the 200-ppm cleanup criteria for soil and under the 15-ppm cleanup criteria for groundwater. Over 32,000 yards of soil have been treated by solid-phase treatment to date. The in situ system operation is effectively producing biodegradation in the subsurface. The project is approximately one-third complete.     

In-situ sparging: Mass transfer mechanisms

In-situ sparging has been accepted as a method to rapidly remediate groundwater at considerably lower costs compared to remedies based on groundwater recovery alone. The success of in-situ sparging depends on effective mass transfer between air and contaminated media in the subsurface. Factors affecting mass transfer include advective airflow, diffusive transport, interphase chemical partitioning, and chemical and biological reaction rates between sparged gases and subsurface contaminants, minerals, and naturally occurring organic compounds. Understanding these factors can increase the design efficiency of in-situ sparging and assist in developing sparging systems that use gases other than air (i.e., oxygen, ozone, and methane).     

Remedial Process Optimization and Ozone Sparging for Petroleum Hydrocarbon‐Impacted Groundwater

A former natural gas processing station is impacted with total petroleum hydrocarbons (TPH) and benzene. Remedial process optimization (RPO) was conducted to evaluate the effectiveness of the historical air sparging/soil vapor extraction (AS/SVE) system and the current groundwater extraction and treatment system. The RPO indicated that both remedial activities offered no further benefit in meeting remediation goals. Instead, an in situ chemical oxidation (ISCO) system was recommended. Ozone was selected, and the results of a bench test indicated that the ozone demand was 8 to 12 mg ozone/mg TPH and that secondary by‐products would include hexavalent chromium and bromate. A capture zone analysis was conducted through groundwater flow modeling (MODFLOW) to ensure containment of the injected oxidant using the existing groundwater extraction system. Results of a pilot study indicated that the optimum frequency of ozone sparging is 60 minutes in order to reach a maximum radius of influence of 20 feet. TPH concentrations within the treatment zone decreased by 97 percent over two months of ozone sparging. Concentrations of hexavalent chromium and bromate increased from nondetect to 44 and 110 mg/L, respectively, during the ozone sparging but attenuated to nondetectable concentrations within three months of system shut down. ©2016 Wiley Periodicals, Inc.     

Case study: On-site remediation of soil and groundwater for a michigan town's water supply

In 1993 environmental consultants, working in concert with the State of Michigan, discovered groundwater contamination that threatened the drinking water supply of the town of Big Rapids. The contamination originated from leaking underground storage tanks and gasoline lines, which were removed. A pilot study indicated the contaminated area extended to 240′ x 180′ and affected soil as well as groundwater. A remediation plan was designed by and implemented by Continental Remediation Systems, Inc., a Natick, Massachusetts, firm. The remediation plan is ongoing and includes an interceptor trench to stop gasoline from flowing into the creek, as well as air sparging to vent and treat the contaminated soil. It is anticipated that the remediation project will take six months to complete. The chief advantage of on-site remediation is that it avoids the costs and liabilities associated with landfill disposal and no materials need leave the site.     

In situ remediation of MTBE utilizing ozone

There has been a great deal of focus on methyl tertiary butyl ether (MTBE) over the past few years by local, state, and federal government, industry, public stakeholders, the environmental services market, and educational institutions. This focus is, in large part, the result of the widespread detection of MTBE in groundwater and surface waters across the United States. The presence of MTBE in groundwater has been attributed primarily to the release from underground storage tank (UST) systems at gasoline service stations. MTBE's physical and chemical properties are different than other constituents of gasoline that have traditionally been cause for concern [benzene, toluene, ethylbenzene, and xylenes (BTEX)]. This difference in properties is why MTBE migrates differently in the subsurface environment and exhibits different constraints relative to mitigation and remediation of MTBE once it has been released to subsurface soils and groundwater. Resource Control Corporation (RCC) has accomplished the remediation of MTBE from subsurface soil and groundwater at multiple sites using ozone. RCC has successfully applied ozone at several sites with different lithologies, geochemistry, and concentrations of constituents of concern. This article presents results from several projects utilizing in situ chemical oxidation with ozone. On these projects MTBE concentrations in groundwater were reduced to remedial objectives usually sooner than anticipated. © 2002 Wiley Periodicals, Inc.     

Evidence for biodegradation and volatilisation of dissolved petroleum hydrocarbons during in situ air sparging in large laboratory columns

Laboratory column experiments run for up to 13 days compared air sparging of groundwater contaminated by dissolved petroleum hydrocarbons in sterile and non-sterile aquifer sediments as well as uncontaminated sediments and groundwater. Loss of dissolved BTEX compounds in the contaminated columns was very rapid, occurring through volatilisation. The majority of the dissolved total organic carbon (TOC) persisted for much longer periods however. A direct comparison between losses from sterile and non-sterile columns suggested a negligible contribution of biodegradation to the removal of TOC. This was difficult to confirm through examination of O₂ utilisation because oxidation of a small amount of reduced sulphur in the aquifer materials was the dominant sink for O₂. Despite this, it was possible to conclude that less than 22% of the removal of TOC was through biodegradation during the first three days of air sparging.     

Operation of a 27‐m3 biopile for the treatment of petroleum‐contaminated soil

Soil and groundwater contamination due to petroleum hydrocarbon spills is a frequent problem worldwide. In Mexico, even when programs oriented to the diminution of these undesirable events exist, in 2000, a total of 1,518 petroleum spills were reported. Exploration zones, refineries, and oil distribution and storage stations frequently are contaminated with total petroleum hydrocarbons (TPH); diesel fraction; gasoline fraction; benzene, toluene, ethyl benzene, and xylenes (BTEX); and polycyclic aromatic hydrocarbons (PAHs). Among the many methodologies available for the treatment of this kind of contaminated soil, bioremediation is the most favorable, because it is an efficient/low‐cost option that is environmentally friendly. This article discusses the capability of using a biopile to treat soils contaminated with about 40,000 mg/kg of TPH. Design and operation of a 27‐m³ biopile is described in this work, including microbiological and respirometric aspects. Parameters such as TPH, diesel fraction, BTEX, and PAHs considered by the U.S. Environmental Protection Agency were measured in biopile samples at 0, 2, 4, 6, 8, 10, and 22 weeks. A final average TPH concentration of 7,300 mg/kg was achieved in 22 weeks, a removal efficiency of 80 percent. © 2007 Wiley Periodicals, Inc.     

石油烃污染地下水原位修复技术研究进展

概述了石油烃污染地下水原位修复技术的进展，包括原位化学氧化、原位电动修复、渗透反应格栅、冲洗、土壤气抽出、地下水曝气、生物修复，并对今后的研究发展趋势进行了展望。     

Developing Life‐Cycle Environmental Response Costs for Leaking Underground Storage Systems at Service Station Sites

Leaking underground storage tank systems at service stations have resulted in tens of thousands of petroleum releases and associated groundwater chemical plumes often extending hundreds of feet off‐site. Technical and engineering approaches to assess and clean up releases from underground tanks, product lines, and dispensers using technologies such as soil vapor extraction, air sparging, biostimulation, and monitored natural attenuation are well understood and widely published throughout the literature. This article summarizes life‐cycle environmental response costs typically encountered using site‐specific cost estimation or metric‐based cost categories considering the overall complexity of site conditions: (1) simple sites where response actions require smaller scale assessments and/or remediation and have limited or no off‐site impacts; (2) average sites where response actions require larger scale assessments and/or remediation typical of petroleum releases; (3) complex sites where response actions require greater on‐site and/or off‐site remediation efforts; and (4) mega sites where petroleum plumes have impacted public or private water supplies or where petroleum vapors have migrated into occupied buildings. Associated cleanup cost estimates rely upon appropriate combinations of individual work elements and the duration of operation, maintenance, and monitoring activities. These cost estimates can be offset by state reimbursement funds, coverage in purchase agreements, and insurance policies. A case study involving a large service station site portfolio illustrates the range of site complexity and life‐cycle environmental response costs. © 2014 Wiley Periodicals, Inc.     

Defining contamination limits with pneumatic hammer soil probes

There have been more than 100,000 confirmed releases of petroleum from underground storage tanks (USTs) in the United States and its territories. The 10,000-gallon spill and cleanup of unleaded gasoline, detailed in this article, that occurred from 1988 to 1990 on Cape Cod, Massachusetts, illustrates the author's argument that electric pneumatic-hammer soil probes are the fastest, most convenient, and least costly way of performing the soil-gas surveys needed to locate spilled petroleum product, evaluate vapor intrusion into basements, and determine the extent of groundwater contamination for remediation purposes. Current state soil-gas requirements are also included.     

In Situ flushing of contaminated soils from a refinery: Organic compounds and metal removals

This article demonstrates the applicability of in situ flushing for the remediation of soil contaminated with petroleum hydrocarbons at a Mexican refinery. The initial average total petroleum hydrocarbon (TPH) concentration for the demonstration field test was 55,156 g/kg. After six weeks of in situ flushing with alternate periods of water and water/surfactant, an average concentration of 1,407 mg/kg was reached, achieving a total removal efficiency of 98 percent. At the end of the process, no hydrocarbons such as diesel; gasoline; benzene, toluene, ethyl benzene, and xylene (BTEX); or petroleum aromatic hydrocarbons (PAHs) were found. Iron washing achieved a removal efficiency of 70 percent, and for vanadium, the removal efficiency was 94.4 percent. The volume of soil treated was 41.6 m³ (38 m²), equivalent to 69.5 tons of soil. A rough calculation of the process costs estimated a total cost of $104.20/m³ ($114.00/m²). Our research indicates that there are a few studies demonstrating in situ flushing experiences under field conditions where both organic (TPH, diesel, gasoline, PAHs, BTEX) and metal (iron and vanadium) removals are reported. © 2004 Wiley Periodicals, Inc.     

Let biodegradation promote in-situ soil venting

Although vapor extraction systems (VES) certainly help remediate volatile hydrocarbons (e.g., gasoline in unsaturated soils), recent studies have found that much of the related hydrocarbon removal is due to aerobic biodegradation, not simple volatilization. In many cases, more than 50 percent of the hydrocarbon removal by these systems is due to biodegradation. By emphasizing biodegradation and minimizing volatilization, the costs of system operation can be reduced, especially for off-gas treatment. Maximizing biodegradation also supports more efficient site remediation because not only are the volatile hydrocarbons cleaned up, but the less volatile contaminants are also cleaned up—by biodegradation. More complete site cleanups are possible through bioventing, especially when cleanup criteria are related to total petroleum hydrocarbons. This article explores the major environmental conditions that influence biodegradation, analyzes several bioventing case histories, and calculates biodegradation's remedial costs.     

Using ultraviolet light to investigate petroleum-contaminated soil

Ultraviolet (UV) light can aid in the investigation of petroleum-contaminated soil and sediment. The visible fluorescence of many petroleum products under UV illumination often results in a striking contrast when compared with surrounding, uncontaminated media. This contrast can be used in a variety of applications, including delineating the extent of petroleum in excavations, locating seeps along shorelines, and selecting sample intervals in sediment cores. In another application, a field screening test using UV light combined with solvent extraction was developed to detect low levels of petroleum in soil. The test rapidly screens soil samples for the presence and relative concentration of petroleum hydrocarbons. The test was used to screen samples for laboratory analysis and identify residual petroleum product in boring samples.     

Contributions of common sources of polycyclic aromatic hydrocarbons to soil contamination

Asphalt products, particularly sealants, are prepared using petroleum products that contain a com‐plex mixture of aliphatic and aromatic hydrocarbons, including polycyclic aromatic hydrocarbons (PAHs). Clearly, these products are ubiquitous in urban environments, which raises an issue regard‐ing the potential for PAHs to be transported from parking lots to underlying or adjacent soil, surface‐water bodies, or groundwater. Based on a literature review, there are limited studies focus‐ing on this issue; however, the studies that have been published have fascinating conclusions. The literature shows, as expected, that asphalt‐based products contain PAHs. The highest PAH concen‐trations are present in asphalt sealants, particularly those manufactured using coal tar. Furthermore, due to the low solubility and high partition coefficients of PAHs, the potential for PAHs to leach from asphalt surfaces is negligible, which has been confirmed by leachability studies. Thus, there is little risk that PAHs will be present in stormwater runoff or leach into groundwater from asphalt‐paved areas in a dissolved form. However, asphalt pavement and sealants produce particulate matter that can contain concentrations of PAHs in the sub‐percent range (100s to 1,000s mg/kg total PAHs) that is transported in stormwater runoff. Some studies show that this can cause soil and sediment con‐tamination with total PAH concentrations in the range of 1 to 10 mg/kg. From a remediation per‐spective, many site cleanups are conducted to remediate the presence of PAHs to cleanup goals below 1 mg/kg or, in some cases, 0.1 mg/kg or lower. From a total risk perspective, remediating sites to low PAH cleanup goals may be unwarranted in light of the risk of transportable PAHs produced from paved parking surfaces. In other words, is it reasonable to conduct a cleanup to remediate low PAH concentrations and then redevelop the area with asphalt pavement and sealant, which may pose a greater PAH‐related risk? © 2006 Wiley Periodicals, Inc.     

Carbon isotope forensics for methane source identification

Methane (CH₄) in ecosystems originates from ancient petroleum formed deep within the earth and/or via microbial fermentation of organic carbon and subsequent reduction of carbon dioxide (CO₂). Given the complexity of different ecosystems, origins of CH₄ present can be difficult to determine. This issue was realized in a situation where an antimethanogenic in situ chemical reduction (ISCR) remedial amendment containing organic carbon plus zero‐valent iron was applied to treat chlorinated solvents in groundwater at a former dry cleaner facility. The technology rapidly and effectively reduced the concentration of tetrachloroethene in groundwater thus meeting project goals without the stoichiometric accumulation of catabolites such as trichloroethene (TCE), cis‐1,2‐dichloroethene, or vinyl chloride and without excessive methanogenesis (e.g., <2 mg/L) in the treated area. However, approximately 9 months after treatment, increased levels of CH₄ (from 5 to 10 mg/L) were observed downgradient from the treated area. The applied remedial amendment contained approximately 60% (weight basis) fermentation organic carbon and was therefore a potential source of this CH₄. However, there was <500 mg/L total organic carbon in groundwater emanating from the upgradient treatment area which was unlikely sufficient to produce that much CH₄. Moreover, the soil gas also contained benzene, toluene, ethylbenzene, and xylenes and other gasoline constituents. These data suggested that the presence of three gasoline/diesel underground storage tanks that were previously closed in place with no active remediation performed could be the source of elevated CH₄. Thirdly, there were sewer lines, utilities, multiple gasoline stations, and industrial activities in the immediate area. With an initial assumption that CH₄ source(s) could include the ISCR amendment over stimulation of production, gasoline sourced CH₄ from nearby leaking lines, or sewage from local fractured pipes, carbon isotope analyses—radiocarbon (Δ¹⁴C) and stable carbon (δ¹³C)—were coupled with CH₄ and CO₂ concentration data from groundwater samples to determine the origin of respired carbon. The δ¹³C range for carbon sources respired in the process would be approximately ?26.5‰ to ?33.0‰ for the ISCR amendment and total petroleum hydrocarbons (TPH) residuals, respectively. Δ¹⁴C is approximately 0‰ and ?999‰ for the ISCR amendment (young carbon) and TPH (old carbon), respectively. The isotopic signature of respired gasses confirmed that elevated CH₄ downgradient of the treated area originated primarily from sewer gasses (or fermentation of liquids released from sewer lines). This study provides an overview of the capability to apply carbon isotope geochemistry to confirmation of remedial protocols and sources of anthropogenic carbon pools that conclusively identify the origin of CH₄ in a complex ecosystem undergoing a remedial action.     

In-situ biological treatment of vinyl acetate-contaminated soil: An emergency response action

In-situ biological solid-phase (or land) treatment was cost-effectively used to remediate 1,500 cubic yards (1,100 m³) of contaminated soil within three months of field operation following spillage of an estimated 12,000 gallons (45,000 L) of vinyl acetate from a railroad tank car onto surface soil. The vinyl acetate rapidly hydrolyzed to acetate and acetaldehyde with concentrations ranging up to 22,000 and 3,000 mg/kg, respectively. Ethanol, a metabolic intermediate, was found to accumulate in soil to concentrations as high as 280 mg/kg. The estimate for excavation, transportation, and disposal of the contaminated soil as a special waste, and for backfilling of the excavated area, was $850,000. The cost for biological remediation of the contaminated soil was $400,000, which was less than half the cost of excavation. In-situ biological treatments have been used to readily remove contaminants, such as acrylonitrile, styrene, butylcellosolve, ethylacrylate, and n-butylacrylate, at other sites involving railroad incidents.     

Microbially Mediated In Situ Desorption Accelerates Remediation of Large Gasoline Product Plume

Remediation of a large separate‐phase hydrocarbon product and associated dissolved‐phase gasoline plume was accelerated by coupling multiphase extraction with in situ microbial stimulation. At the beginning of remediation activities, the separate‐phase hydrocarbon plume extended an estimated seven acres with product thickness measuring up to 2.1 feet thick. Within 18 months after beginning extraction, reduction of gasoline constituents in groundwater became asymptotic and measureable product disappeared from the upgradient source area. At that time, the remediation team initiated a program of limited in situ anaerobic bioremediation with the goal of stimulating production of natural surfactants from native microbes to release petroleum from the soil matrix. Groundwater concentrations of gasoline constituents increased gradually over the next three years, improving recovery without biofouling the pump‐and‐treat infrastructure. Using this approach, the groundwater component of the remedy was completed in less than five years, substantially less than the 10 years to 15 years predicted by modeling. This strategy demonstrated a more sustainable approach to remediation, reducing electrical usage by an estimated 800 megawatt hours, reducing infrastructure requirements, and preserving an estimated 150 million gallons of groundwater for this arid agricultural area. © 2014 Wiley Periodicals, Inc.     

Examining the economics of remediation by fluid injection with vacuum extraction

Enhanced methods of in-situ remediation based on patented technology involving fluid injection with vacuum extraction have been used successfully at the Sand Creek Superfund Site in Commerce City, Colorado. Approximately 177,000 pounds of volatile organic compounds (VOCs) were removed from the subsurface in six months, two months ahead of schedule. Remediation goals were achieved on this thermally enhanced soil vapor extraction project by using vertical and horizontal wells interchangeably in vacuum or pressure service for vapor extraction, dual vacuum extraction, heated vapor reinjection, and air sparging. Although VOCs consisted of mixed chlorinated and petroleum hydrocarbons, the petroleum hydrocarbons, some in the form of nonaqueous phase liquids, had not been fully characterized. This article examines the evolution of the remedial design from that conceptualized in the Record of Decision (ROD) of the U.S. EPA, presents the rationale for the selection of alternative system components, and provides a cost analysis of the selected remedial technology, with comparisons to that of alternatives considered for use at Sand Creek.     

Vegetative remediation process offers advantages over traditional pump-and-treat technologies

The use of bioremediation technologies to clean up contaminated soil and groundwater is increasingly winning favor over more costly and often ineffective mechanical approaches. One new type of bioremediation process, known as TreeMediation^TM, uses trees and other vegetation to remediate soil by acting as a natural pump to extract and remediate contaminated groundwater in aquifers less than 30 feet deep. This article describes this innovative treatment method, shows its advantages over traditional pump and-treat techniques, and explains how TreeMediation is being used to extract nitrate and ammonium contamination from an aquifer in New Jersey.