Alternative method of groundwater sparging for petroleum hydrocarbon remediation

An alternative method of in-situ groundwater sparging, termed density-driven convection (patent pending), is presented. This method has been successfully used to remediate eight underground storage tank releases involving a wide distillation range of petroleum hydrocarbons (gasoline to waste oil) and in a variety of site soils (clay to sandy gravel). Application of the density-driven convection method is detailed in a case study. The system, installed to remediate a gasoline and diesel release from an underground storage tank, was operated and monitored for a period of one year. Monitoring data indicate reductions in total petroleum hydrocarbon concentrations in groundwater and in soil. Concentrations of aromatic hydrocarbons (benzene, toluene, ethylbenzene, xylenes, and naphthalene) also decreased in both media. Stimulation of natural biodegradation, the primary mechanism of removal, occurred rapidly. Natural biological activity gradually declined over the subsequent 150 days. After one year of operation, the sparging system has achieved or is rapidly approaching the regulatory cleanup goals for both soil and groundwater, including reduction of dissolved concentrations below maximum contaminant levels established under the Safe Drinking Water Act.     

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.     

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.     

Petroleum biodegradation in soil: The effect of direct application of surfactants

The direct application of surfactants to petroleum-contaminated soil has been proposed as a mechanism to increase the bioavailability of insoluble compounds. Solubilization of hydrophobic compounds into the aqueous phase appears to be a significant rate limiting factor in petroleum biodegradation in soil. Nonionic surfactants have been developed to solubilize a variety of compounds, thus increasing the desorption of contaminants from the soil. In this study, laboratory scale land treatment scenarios were used to monitor the bioremediation of petroleum contaminated soils. In efforts to achieve the lowest levels of residual petroleum hydrocarbons in the soil following biotreatment, 0.5 and 1.0% (volume/weight) surfactant was blended into soils under treatment. Two soil types were studied, a high clay content soil and a sandy, silty soil. In both cases, the addition of surfactant (Adsee 799®, a blend of ethoxylated fatty acids, Witco Corporation) stimulated biological activity as indicated by increased heterotropbic colony forming units per gram of soil. However, the increased activity was not correlated with removal of petroleum hydrocarbons. The results suggest that the application of surfactants directly to the soil for the purpose of solubilizing hydropbobic compounds was not successful in achieving greater levels of petroleum hydrocarbon removal.     

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.     

Enhanced land treatment of petroleum-contaminated soils using solid peroxygen materials

A pilot field study evaluated whether adding solid peroxygen materials during land treatment could cost effectively accelerate cleanup at a site contaminated with petroleum-related compounds. Five test cells were constructed containing approximately five cubic yards of soil contaminated with 300–400 mg/kg of total petroleum hydrocarbons (TPH). Three cells received treatment with solid peroxygen materials (either MgO₂ or CaO₂), while the other two cells served as controls (no peroxygen amendment). Adding solid peroxygen compounds effectively reduced the hydrocarbon contamination in the soils and decreased the treatment time. During this time, the concentration of TPH in soil in the three treatment cells decreased. In contrast, there was little loss of TPH from the two control cells simulating traditional land treatment. Adding the solid peroxygen materials reduced the total site remediation time, thereby reducing the overall costs.     

Alternatives to incineration in remediation of soil and sediments assessed

Contamination of soil and sediment by pollutants represents a major environmental challenge. Remediation of soil during the original Superfund years consisted primarily of dig and haul, capping, or containment. The 1986 amendments to CERCLA—SARA—provided the incentive for treatment and permanent remedies during site remediation. Thermal treatment, which routinely achieves the low cleanup criteria required by RCRA land-ban regulations, became one of the major technologies used for cleanup under the concept of ARAR. As the remediation industry matured and recognized specific market niches in soil remediation, a number of new technologies emerged. Thermal desorption, bioremediation, soil vapor extraction, soil washing, and soil extraction are being used on sites at which the technology offers advantages over incineration. In addition, a continuing stream of emerging technologies is being presented that requires careful evaluation relative to existing cleanup methods. Each of these technologies offers a range of options for achieving appropriate cleanup criteria, application to different soil matrices, cost, time of remediation, and public acceptability. Balancing cleanup criteria defined by regulation or risk assessment with technology cost and capability affords the opportunity to solve these problems with appropriate balance of cost and protection of human health and the environment.     

Case study: Using soil washing/leaching for the removal of heavy metal at the twin cities army ammunition plant

COGNIS TERRAMET® soil leaching and Bescorp soil washing systems have been successfully combined to remediate an ammunition test burn area at the Twin Cities Army Ammunition Plant (TCAAP), New Brighton, Minnesota. This cleanup is the first in the country to successfully combine these two technologies, and it offers a permanent solution to heavy metal remediation. Over 20,000 tons of soil were treated in the project. The cleaned soil remained on-site, and the heavy metal contaminants were removed, recovered, and recycled. Eight heavy metals were removed from the contaminated soil achieving the very stringent cleanup criteria of <175 ppm for residual lead and achieving background concentrations for seven other project metals (antimony, cadmium, chromium, copper, mercury, nickel, and silver). Initial contaminant levels were measured as high as 86,000 ppm lead and 100,000 ppm copper, with average concentrations over 1,600 ppm each. In addition, both live and spent ordnance were removed in the soil treatment plant to meet the cleanup criteria. By combining soil washing and leaching, COGNIS and Bescorp were able to assemble a process which effectively treats all the soil fractions so that all soil material can be returned on-site, no wastewater is generated, and the heavy metals are recovered and recycled. No hazardous waste requiring landfill disposal was generated during the entire remedial operation.     

石油烃污染土壤微生物修复促进技术

采用原位修复法处理石油烃污染土壤,考察了土壤中石油烃的自然降解情况,研究了土壤改良剂和生物营养剂对石油烃降解的促进作用。实验结果表明:将总石油烃含量约为5 g/kg的实验土样降解30 d,自然降解时总石油烃降解率为7.8%;当单独加入1.0%(w)的土壤改良剂时,总石油烃降解率达36.0%;当单独加入1.0 g/kg的生物营养剂时,总石油烃降解率为51.6%;最佳促进剂配方为土壤改良剂加入量1.0%(w),生物营养剂加入量1.0 g/kg,此条件下总石油烃降解率为80.1%。     

Practical Perspectives of 1,4‐Dioxane Investigation and Remediation

1,4‐Dioxane (dioxane) is a contaminant of emerging concern that is classified by the U.S. Environmental Protection Agency as a likely human carcinogen. Dioxane has been used as a minor or major ingredient in many applications, and is also generated as an unwanted by‐product of industrial processes associated with the manufacturing of polyethylene, nonionic surfactants, and many consumer products (cosmetics, laundry detergents, shampoos, etc.). Dioxane is also a known stabilizer of chlorinated solvents, particularly 1,1,1‐trichloroethane, and has been commonly found comingled with chlorinated solvent plumes. Dioxane plumes at chlorinated solvent sites can complicate site closure strategies, which to date have not typically focused on dioxane. Aggressive treatment technologies have greatly advanced and are clearly capable of achieving lower parts per billion cleanup criteria using ex situ advanced oxidation processes and sorption media. In situ chemical oxidation has also been demonstrated to effectively remediate dioxane and chlorinated solvents. Other in situ remedies, such as enhanced bioremediation, phytoremediation, and monitored natural attenuation, have been studied; however, their ability to achieve cleanup levels is still somewhat questionable and is limited by co‐occurring contaminants. This article summarizes and provides practical perspectives on dioxane analysis, plume stability relative to other contaminants, and the development of investigation tools and treatment technologies.     

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.     

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.     

Assessing cleanup levels for industrial sites under state risk reduction programs

Many states are promoting the cleanup and reuse of industrial sites. The reasons stem from the need to implement cost-effective risk reduction programs that show reasonable progress in the cleanup of contaminated sites and from the need to make effective use of industrial sites instead of abandoning them and making use of greenfield sites for new industrial facilities. The industrial land-use cleanup criteria developed by states are primarily risk-based. Several EPA regional offices also have developed similar risk-based cleanup criteria. This article addresses methodologies employed for assessing and evaluating the level of cleanup at several industrial sites in Texas, Michigan, and Ohio. This includes defining the regulatory framework, estimating the level and extent of contamination of soil and groundwater, assessing migration pathways, performing health risk assessments, and estimating cleanup requirements and associated costs. The implications associated with the various types of risk reduction options available for these states also are addressed.     

Bioremediation of Dissolved and Free Phase Oil in Wastewater from Equipment Maintenance Activities

Land treatment facilities can provide effective treatment of secondary oily wastewater from maintenance operations, particularly in arid climates. Soil and underlying groundwater from a land treatment facility, which has been operating for eight years, were analyzed to determine the effectiveness of using bioremediation for the treatment of dissolved and free‐phase oil in maintenance wastewater. The study was conducted at a mining site in Western Australia. The facility was capable of treating 140 kiloliters (kL) of oily wastewater per day. The average petroleum hydrocarbon content of the wastewater was 2 percent weight per volume (w/v) based on data available for the first five years. The soil data indicate that the land treatment process has been operating efficiently even at high wastewater loadings with maximum degradation rates of 10–242 mg/kg per day. Based on the soil data, there is no evidence of accumulation of any metal or polycyclic aromatic hydrocarbon (PAH) compounds. The land treatment facility has led to only low levels of TPH (total petroleum hydrocarbons) contamination (<4 ppm) in the underlying groundwater. However, nitrate concentrations in the groundwater were shown to increase over the first five years of the facility's operation. This article reports and discusses the operational data from the land treatment process, illustrating its effectiveness in treating oily wastewater. © 2001 John Wiley & Sons, Inc.     

Impact: A Model for calculation of soil cleanup levels

The establishment of soil cleanup levels is a primary concern in site remediation projects. Soil cleanup levels provide targets that drive the remediation process from technology selection through closure. Several state regulatory agencies are currently in the process of developing scientifically based soil cleanup standards. The underlying premise in the derivation of such standards is to ensure that the site will not pose a threat to human health and the environment after remediation has been completed. To accomplish this, remediation project managers must consider several contaminant transport pathways. This article presents the salient features of a model named IMPACT, which was developed to assist in the derivation of soil cleanup levels. IMPACT considers the soil-to-groundwater pathway and predicts the cleanup levels in a contaminated soil layer in the vadose zone such that groundwater quality standards are met at any point in the aquifer.     

Full‐scale in‐situ biobarrier demonstration for containment and treatment of MTBE

The Naval Facilities Engineering Service Center (NFESC), Arizona State University, and Equilon Enterprises LLC are partners in an innovative Environmental Security Technology Certification Program cleanup technology demonstration designed to contain dissolved MTBE groundwater plumes. This full‐scale demonstration is being performed to test the use of an oxygenated biobarrier at Naval Base Ventura County, in Port Hueneme, California. Surprisingly, few cost‐effective in‐situ remedies are known for the cleanup of MTBE‐impacted aquifers, and remediation by engineered in‐situ biodegradation was thought to be an unlikely candidate just a few years ago. This project demonstrates that MTBE‐impacted groundwater can be remediated in‐situ through engineered aerobic biodegradation under natural‐flow conditions. With respect to economics, the installation and operation costs associated with this innovative biobarrier system are at least 50 percent lower than those of a conventional pump and treat system. Furthermore, although it has been suggested that aerobic MTBE biodegradation will not occur in mixed MTBE‐BTEX dissolved plumes, this project demonstrates otherwise. The biobarrier system discussed in this article is the largest of its kind ever implemented, spanning a dissolved MTBE plume that is over 500 feet wide. This biobarrier system has achieved an in‐situ treatment efficiency of greater than 99.9 percent for dissolved MTBE and BTEX concentrations. Perhaps of greater importance is the fact that extensive performance data has been collected, which is being used to generate best‐practice design and cost information for this biobarrier technology. © 2001 John Wiley & Sons, Inc.     

Low intervention soil remediation approaches

Traditional bioremediation approaches have been used to treat petroleum source contamination in readily accessible soils and sludges. Contamination under existing structures is a greater challenge. Options to deal with this problem have usually been in the extreme (i.e., to dismantle the facility and excavate to an acceptable regulated residual, or to pump and treat for an inordinately long period of time). The excavated material must be further remediated and cleanfill must be added to close the excavation. If site assessments were too conservative or incomplete, new contamination adulterating fill soils may result in additional excavation at some later date. Innovative, cost-efficient technologies must be developed to remove preexisting wastes under structures and to reduce future remediation episodes. An innovative soil bioremediation treatment method was developed and evaluated in petroleum hydrocarbon contaminated (PHC) soils at compressor stations of a natural gas pipeline running through Louisiana. The in-situ protocol was developed for remediating significant acreage subjected to contamination by petroleum-based lubricants and other PHC products resulting from a chronic leakage of lubricating oil used to maintain the pipeline itself. Initial total petroleum hydrocarbon (TPH) measurements revealed values of up to 12,000 mg/kg soil dry weight. The aim of the remediation project was to reduce TPH concentration in the contaminated soils to a level of <200 mg/kg soil dry weight, a level negotiated to be acceptable to state and federal regulators. After monitoring the system for 122 days, all sites showed greater than 99-percent reduction in TPH concentration.     

A comparison of mesophilic composting and unamended land treatment for the bioremediation of aged tar residues in soil

A field study was conducted to compare the effectiveness of land treatment and mesophilic composting in removing aged polycyclic aromatic hydrocarbons (PAH) from soil. The soil composting treatment, which had 20 percent (w/w) fresh organic matter incorporated into the soil, reached mesophilic temperatures of 45 to 50°C at week 3–4 and was effective in reducing PAH from 2240 mg/kg to 120 mg/kg after 224 days of treatment. Conventional land treatment with and without added cow manure (5 percent w/w) was less effective in removing the PAH from the soil than was the mesophilic soil composting treatment. In a parallel laboratory trial, PAH concentrations were reduced below 500 mg/kg (the target cleanup concentration for the site) when the contaminated soil was amended with 20 to 30 percent (w/w) fresh organic matter after 186 days of treatment. PAH degradation was lower in the laboratory trial compared with the field trial and no self-heating of soil was demonstrated in the laboratory. Based on the relatively high total heterotrophic and naphthalene-degrading microbial populations in the nonsterile treatments, it was apparent that the absence of microorganisms was unlikely to have limited the biodegradation of PAH in the current study. Fresh organic matter amendments of green tree waste and cow manure, regular mixing of the compost, and maintenance of moisture by regular watering were critical factors in achieving the target PAH concentrations.     

Hydrogen peroxide for physicochemically degrading petroleum-contaminated soils

Catalyzed hydrogen peroxide was applied to contaminated soil at an equipment storage yard in Reno, Nevada, that had also been used as a dump for motor oil and diesel fuel for twenty years. The site is only a quarter mile from the Truckee River—a principal source of Reno's drinking water. This article details hydrogen peroxide's advantages, disadvantages, costs, and treatment for reducing to below the 100 mg/kg Nevada action level the petroleum hydrocarbons in the yard's arid soil, which is characterized by low organic carbon content and low manganese oxide content.