Lessons learned from classroom training on natural attenuation of chlorinated solvents

Technology and information transfer are critical functions within the remediation industry. Researchers in the private sector, academia, and government all struggle to have their findings accepted and put to good use by the remediation industry at large but must work even harder to have their findings accepted and put into practice by state and federal regulators in the environmental agencies overseeing cleanups. Unfortunately, many technology and information transfer efforts fail to reach state and federal regulators, and even fewer achieve regulatory acceptance. A two‐year‐long campaign to deliver a training class on the natural attenuation of chlorinated solvents in groundwater is one prominent example of very effective technology and information transfer. Several of the elements and aspects of that successful training class are presented and discussed in order to provide others with a proven and workable template. © 2010 Wiley Periodicals, Inc.     

Enhanced anaerobic bioremediation of chlorinated solvents utilizing vegetable oil emulsions

The use of vegetable oil as an electron donor to enhance the reductive dechlorination of chlori‐nated solvents as an in situ remediation technology is gaining significant traction. Vegetable oil is a cost‐effective slow‐release electron donor with greater hydrogen‐release efficiency than other electron‐donor products. However, neat vegetable oil can inhibit distribution in aquifers due to the oil droplets blocking the flow of groundwater through the smaller pore spaces in the aquifer materials. This issue has been partially overcome by applying the vegetable oil as an oil‐water emulsion, which typically is created in the field. However, the field preparation results in a mixture of droplet sizes, including larger droplets that can make the emulsions unstable and reduce the soil permeability by blocking soil‐pore throats with oil. RNAS, Inc., has developed a kinetically sta‐ble soybean oil emulsion (“Newman Zone”) consisting of submicron droplets with less droplet‐size variation than field‐prepared emulsions. This product is composed of a blend of fast‐release (sodium lactate) and slow‐release (soybean oil) electron donors. The emulsion is produced in a stable factory environment in which it is pasteurized and packaged in sterile packaging. This ma‐terial can be utilized as an electron donor without further treatments or amendments in the field. This article discusses factors associated with selecting electron donors and the development of vegetable oil–based products. A case study of an application of Newman Zone at a former adhe‐sives manufacturing facility is then presented. The case study demonstrates the effect of Newman Zone in reducing chlorinated solvent concentrations in groundwater by both rapidly stimulating initial microbial activity and supporting long‐term reductive dechlorination with a slow‐release electron donor. © 2006 Wiley Periodicals, Inc.     

A deterministic approach to evaluate and implement monitored natural attenuation for chlorinated solvents

A US EPA directive and related technical protocol outline the information needed to determine if monitored natural attenuation (MNA) for chlorinated solvents is a suitable remedy for a site. For some sites, conditions such as complex hydrology or perturbation of the contaminant plume caused by an existing remediation technology (e.g., pump‐and‐treat) make evaluation of MNA using only field data difficult. In these cases, a deterministic approach using reactive transport modeling can provide a technical basis to estimate how the plume will change and whether it can be expected to stabilize in the future and meet remediation goals. This type of approach was applied at the Petro‐Processors Inc. Brooklawn site near Baton Rouge, Louisiana, to evaluate and implement MNA. This site consists of a multicomponent nonaqueous‐phase source area creating a dissolved groundwater contamination plume in alluvial material near the Mississippi River. The hydraulic gradient of the groundwater varies seasonally with changes in the river stage. Due to the transient nature of the hydraulic gradient and the impact of a hydraulic containment system operated at the site for six years, direct field measurements could not be used to estimate natural attenuation processes. Reactive transport of contaminants were modeled using the RT3D code to estimate whether MNA has the potential to meet the site‐specific remediation goals and the requirements of the US EPA Office of Solid Waste and Emergency Response Directive 9200.4‐17P. Modeling results were incorporated into the long‐term monitoring plan as a basis for evaluating the effectiveness of the MNA remedy. As part of the long‐term monitoring plan, monitoring data will be compared to predictive simulation results to evaluate whether the plume is changing over time as predicted and can be expected to stabilize and meet remediation goals. This deterministic approach was used to support acceptance of MNA as a remedy. © 2007 Wiley Periodicals, Inc.     

Interactions between biological and abiotic pathways in the reduction of chlorinated solvents

While biologically mediated reductive dechlorination continues to be a significant focus of chlorinated solvent remediation, there has been an increased interest in abiotic reductive processes for the remediation of chlorinated solvents. In situ chemical reduction (ISCR) uses zero‐valent iron (ZVI)–based technologies, such as nanoscale iron and bimetallic ZVI, as well as naturally occurring reduced minerals incorporating dual‐valent iron (DVI), such as magnetite, green rust, and iron sulfides that are capable of dechlorinating solvents. A more recent area of development in ISCR has been in combining biological and abiotic processes. There are several ways in which biological and abiotic processes can be combined. First, the interaction between the two may be “causative.” For example, the Air Force Center for Engineering and the Environment's biogeochemical reductive dechlorination (BiRD) technology combines a mulch barrier with hematite and gypsum to create an iron‐sulfide‐based reducing zone. Biodegradation under sulfate‐reducing conditions produces sulfide that combines with the hematite to form iron sulfides. As such, the BiRD technology is “causative”; the biological processes create reducing minerals. The biological generation of other reducing minerals such as magnetite, siderite, and green rust is feasible and is, with magnetite, observed in nature at some petroleum sites. A second type of interaction between abiotic and biotic processes is “synergistic.” For example, biological processes can enhance the activity of reduced metals/minerals. This is the basis of the EHC® ISCR technologies, which combine ZVI with a (slowly) degradable carbon substrate. This combination rapidly creates buffered, strongly reducing conditions, which result in more complete solvent degradation (i.e., direct mineralization). The extent and level of reducing activity commonly observed are much greater when both the carbon substrate and the ZVI are present. When the carbon substrate is expended, the reducing activity due to ZVI alone is much less. The understanding of biogeochemical processes and their impact on abiotic processes is still developing. As that understanding develops, new and improved methods will be created to enhance volatile organic compound destruction. © 2009 Wiley Periodicals, Inc.     

Closing the mass balance at chlorinated solvent sites: Sources and attenuation processes

Using detailed mass balance and simple analytical models, a spreadsheet‐based application (BioBalance) was developed to equip decision makers with a predictive tool that can provide a semiquantitative projection of source‐zone concentrations and provide insight into the long‐term behavior of the associated chlorinated solvent plume. The various models were linked in a toolkit in order to predict the composite impacts of alternative source‐zone remediation technologies and downgradient attenuation processes. Key outputs of BioBalance include estimates of maximum plume size, the time frame for plume stabilization, and an assessment of the sustainability of anaerobic natural attenuation processes. The toolkit also provides spatial and temporal projections of integrated contaminant flux and plume centerline concentrations. Results from model runs of the toolkit indicate that, for sites trying to meet traditional, “final” remedial objectives (e.g., two to three orders of magnitude reduction in concentration with restoration to potable limits), “dispersive” mechanisms (e.g., heterogeneous flow and matrix diffusion) can extend remedial time frames and limit the benefits of source remediation in reducing plume sizes. In these cases, the removal of source mass does not result in a corresponding reduction in the time frame for source remediation or plume stabilization. However, this should not discourage practitioners from implementing source‐depletion technologies, since results from the toolkit demonstrate a variety of measurable benefits of source remediation. Model runs suggest that alternative, “intermediate” performance metrics can improve and clarify source remediation objectives and better monitor and evaluate effectiveness. Suggested intermediate performance metrics include reduction in overall concentrations or mass within the plume, reduction of flux moving within a plume, and reduction in the potential for risk to a receptor or migration of a target concentration of contaminant beyond a site boundary. This article describes the development of two key modules of the toolkit as well as illustrates the value of using intermediate performance metrics to evaluate the performance of a source‐remediation technology. © 2010 Wiley Periodicals, Inc.     

Natural attenuation of chlorinated solvent plumes at Texas dry cleaners

Dry cleaners are the largest users of perchloroethene (PCE) solvents in the United States. Releases from dry cleaners to soil and groundwater, however, remain largely unstudied. This article presents a database of 137 chlorinated solvent plumes at dry cleaners in Texas. The data indicate that PCE plumes are generally shorter in extent than those from industrial sites. Degradation products were observed at more than 80 percent of the sites with groundwater contamination. Calculated attenuation rates are on the order of one‐to‐three‐year half‐lives for PCE and its degradation products. The estimated cleanup timeframe for calculated attenuation rates is < 50 years. More research is needed to understand the presence of organic carbon sources at dry cleaners and its implications for natural attenuation. © 2004 Wiley Periodicals, Inc.     

Application of source removal and natural attenuation remediation strategies at MGP sites in Wisconsin

This article presents site closure strategies of source material removal and dissolved‐phase groundwater natural attenuation that were applied at two manufactured gas plant (MGP) sites in Wisconsin. The source removal actions were implemented in 1999 and 2000 with groundwater monitoring activities preceding and following those actions. Both of these sites have unique geological and hydrogeological conditions. The article briefly presents site background information and source removal activities at both of these sites and focuses on groundwater analytical testing data that demonstrate remediation of dissolved‐phase MGP‐related groundwater impacts by natural attenuation. A statistical evaluation of the data supports a stable or declining MGP parameter concentration trend at each of the sites. A comparison of the site natural attenuation evaluation is made to compare with the requirements for site closure under the Wisconsin Department of Natural Resources regulations and guidance. © 2003 Wiley Periodicals, Inc.     

Natural attenuation of a low mobility chlorinated insecticide in low-level and high-level contaminated soil: A feasibility study

Endosulfan is an economically important insecticide and widespread environmental pollutant, originating from a wide range of agricultural activities. The major implication from the feasibility study described was that endosulfan I can be remediated by natural attenuation processes in cotton-farming soil, in which concentrations were relatively low, as well as heavily contaminated soil, from an agricultural chemical waste (evaporation) pit. Endosulfan I, the major isomer of endosulfan, was present in agricultural soils with low (2.2 mg/kg) and high (417 mg/kg) concentrations of technical-grade endosulfan. The half-lives of the major isomer of endosulfan were 94 and greater than 350 days in the low-level (cotton farming soil) and high-level (contaminated soil), respectively. Even under conditions of minimal intervention, as in the current study, endosulfan concentrations in contaminated soils can be substantially reduced. The nonbiological process of soil binding was predominantly responsible for the natural attenuation of endosulfan I in both soils. Low levels of mineralization of the chlorinated ring ¹⁴C-labelled carbons were also reported, but mineralization did not play an important role in natural attenuation of endosulfan I in either soil studied.     

Performance evaluation of an in situ source area combined remedy for the remediation of commingled chlorinated ethanes and ethenes

The chlorinated volatile organic compounds (CVOCs), tetrachloroethene (PCE), trichloroethene (TCE), and 1,1,1‐trichloroethane (1,1,1‐TCA), often found as commingled contaminants of concern (COCs) in groundwater, can degrade via a variety of biotic and abiotic reductive pathways. In situ remediation of a groundwater contaminant source area containing commingled 1,1,1‐TCA, PCE, and TCE was conducted using a combined remedy/treatment train approach. The first step was to create geochemically reducing conditions in the source area to degrade the CVOCs to lesser chlorinated CVOCs (i.e., 1,1‐dichloroethane [1,1‐DCA], 1,1‐dichlorethene [1,1‐DCE], cis‐1,2‐dichoroethene [cis‐1,2‐DCE], and vinyl chloride [VC]) via enhanced reductive dechlorination (ERD). Carbon substrates were injected to create microbial‐induced geochemically reducing conditions. An abiotic reductant (zero‐valent iron [ZVI]) was also used to further degrade the CVOCs, minimizing the generation of 1,1‐DCE and VC, and co‐precipitate temporarily mobilized metals. An in situ aerobic zone was created downgradient of the treatment zone through the injection of oxygen. Remaining CVOC degradation products and temporarily mobilized metals (e.g., iron and manganese) resulting from the geochemically reducing conditions were then allowed to migrate through the aerobic zone. Within the aerobic zone, the lesser chlorinated CVOCs were oxidized and the solubilized metals were precipitated out of solution. The injection of a combination of carbon substrates and ZVI into the groundwater system at the site studied herein resulted in the generation of a geochemically reducing subsurface treatment zone that has lasted for more than 4.5 years. Mass concentrations of total CVOCs were degraded within the treatment zone, with near complete transformation of chlorinated ethenes and a more than 90 percent reduction of CVOC mass concentrations. Production of VC and 1,1‐DCE has been minimized through the combined effects of abiotic and biological processes. CVOC concentrations have declined over time and temporarily mobilized metals are precipitating out of the dissolved phase. Precipitation of the dissolved metals was mitigated using the in situ oxygenation system, also resulting in a return to aerobic conditions in downgradient groundwater. Chloroethane (CA) is the dominant CVOC degradation product within the treatment zone and downgradient of the treatment zone, and it is expected to continue to aerobically degrade over time. CA did not accumulate within and near the aerobic oxygenation zone. The expectations for the remediation system are: (1) the concentrations of CVOCs (primarily in the form of CA) will continue to degrade; (2) total organic carbon concentrations will continue to decline to pre‐remediation levels; and, (3) the groundwater geochemistry will experience an overall trend of transitioning from reducing back to pre‐remediation mildly oxidizing conditions within and downgradient of the treatment zone.     

Historical analysis of monitored natural attenuation: A survey of 191 chlorinated solvent sites and 45 solvent plumes

A survey of experts in the application of natural attenuation was conducted to better understand how monitored natural attenuation (MNA) is being applied at chlorinated solvent sites. Thirty‐four remediation professionals provided general information for 191 sites where MNA was evaluated, and site‐specific data for 45 chlorinated solvent plumes being remediated by MNA. Respondents indicated that MNA was precluded as a remedy at only 23 percent of all sites where evaluated as a remedial option. Leading factors excluding MNA as a remedial approach were the presence of an expanding plume and an unreasonably long estimated remediation time frame. MNA is being used as the sole remedy at about 30 percent of the sites, and 33 percent are implementing MNA in conjunction with source zone remediation. The remaining sites are implementing MNA with plume remediation (13 percent), source containment (9 percent), or some other strategy (16 percent). © 2004 Wiley Periodicals, Inc.     

Use of a low‐cost substrate in a continuous recirculation process to stimulate plumewide anaerobic dechlorination of chlorinated solvents

Over the past 20 years, significant time and money have been spent on better understanding and successfully applying bioremediation in the field. The results of these efforts provide a deeper un‐derstanding of aerobic and anaerobic microbial processes, the microbial species and environ‐mental conditions that are desirable for specific degradation pathways, and the limitations that may prevent full‐scale bioremediation from being successfully applied in heterogeneous subsur‐face environments. Numerous substrates have been identified as effective electron donors to stimulate anaerobic dechlorination of chlorinated ethenes, but methods of delivering these sub‐strates for in situ bioremediation (direct‐push injections, slug injections, high‐pressure injections, fracture wells, etc.) have yet to overcome the main limitation of achieving contact between these substrates and the contaminants. Therefore, although it is important (from a full‐scale remedia‐tion standpoint) to select an appropriate, low‐cost substrate that can be supplied in sufficient quantity to promote remediation of a large source area and its associated plume, it is equally im‐portant to ensure that the substrate can be delivered throughout the impacted plume zone. Failure to achieve substrate delivery and contact within the chlorinated solvent plume usually re‐sults in wasted money and limited remediation benefit. Bioremediation is a contact technology that cannot be effectively implemented on a large scale unless a method for rapidly delivering the low‐cost substrate across the entire source and plume areas is utilized. Unfortunately, many cur‐rent substrate delivery methods are not achieving sitewide distribution or treatment of the sorbed contaminant mass that exists in the organic fraction of a soil matrix. The following discussion sum‐marizes substrate delivery using an aggressive groundwater recirculation approach that can achieve plumewide contact between the contaminants and substrate, thus accelerating dechlori‐nation rates and shortening the overall remediation time frame. © 2006 Wiley Periodicals, Inc.     

Environmental assessment and remediation: Estimating the costs of uncertainty

Current cost estimates for the assessment and remediation of environmental contamination at facilities operated by the U.S. Department of Energy (DOE) are based largely on assumptions, with a resulting high level of uncertainty. Therefore, consistent and reliable methods for estimating the uncertainty inherent in the estimates are of vital importance. This article presents an approach and format for estimating contingency in DOE's Environmental Restoration Program. The method involves an analysis of risk factors having a potential to affect the cost of the major elements in the estimate. Application of the contingency analysis to a project site is included in the discussion.