Emerging technologies for in-situ groundwater remediation

There are numerous technologies currently being tested by EPA, universities throughout the world, and private research organizations. A few of the more promising innovative technologies as well as fully tested and proven remedies for treating contaminated groundwater are presented in this article. Although several of those technologies have been in existence for only four to five years, the results of full-scale testing are being produced. The method for each of these promising technologies is described, results from recent field-scale studies are summarized, and a discussion of cost is presented.     

Comparing groundwater remediation options

Although many conventional physical remediation methods are viewed as proven, they often only relocate wastes to other sites or into the air. How do the emerging biological and chemical in situ methods perform in the same applications? This article reviews their results (much of it in the laboratory) as well as their promise of more complete neutralization of hazardous wastes, lower capital costs, and longer-duration cleanup processes. The optimal method may be a combination of chemical and biological in situ techniques with physical pump-and-treat methods.     

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.     

Sustainable groundwater remediation and reuse case study

Sustainability is an important consideration when designing a remedy given the value that can be demonstrated to all stakeholders. A case study is presented that illustrates an example where sustainability was emphasized during the selection and implementation of a groundwater remedy. An extensive free and/or residual product investigation was completed to demonstrate that hydraulic control is a suitable remedy and active direct treatment was not required pursuant to the state regulations. A pump and treat system for onsite hydraulic containment was installed to control plume migration. The system allows for 100 percent reuse of treated groundwater in the manufacturing process. Both the groundwater reuse and investigation conclusions have resulted in significant cost savings and sustainability benefits, including the reduction in the annual load on the drinking water aquifer by up to 138 million gallons per year.     

Comparing PFAS to other groundwater contaminants: Implications for remediation

Established groundwater contaminants such as chlorinated solvents and hydrocarbons have impacted groundwater at hundreds of thousands of sites around the United States and have been responsible for multibillion dollar remediation expenditures. An important question is whether groundwater remediation for the emerging contaminant class comprised of per‐ and polyfluoroalkyl substances (PFAS) will be a smaller, similar, or a larger‐scale problem than the established groundwater contaminants. A two‐pronged approach was used to evaluate this question in this paper. First, nine quantitative scale‐of‐remediation metrics were used to compare PFAS to four established contaminants: chlorinated solvents, benzene, 1,4‐dioxane, and methyl tert‐butyl ether. These metrics reflected the prevalence of the contaminants in the U.S., attenuation potential, remediation difficulty, and research intensity. Second, several key challenges identified with PFAS remediation were evaluated to see similar situations (qualitative analogs) that have been addressed by the remediation field in the past. The results of the analysis show that four out of nine of the evaluated quantitative metrics (production, number of potential sites, detection frequency, required destruction/removal efficiency) indicate that the scale of PFAS groundwater remediation may be smaller compared to the current scale of remediation for conventional groundwater contaminants. One attenuation metric, median plume length, suggests that overall PFAS remediation could pose a greater challenge compared to hydrocarbon sites, but only slightly larger than chlorinated volatile organic compounds sites. The second attenuation metric, hydrophobic sorption, was not definitive regarding the potential scale of PFAS remediation. The final three metrics (regulatory criteria, in‐situ remediation capability, and research intensity) all indicate that PFAS remediation might end up being a larger scale problem than the established contaminants. An assessment of the evolution of groundwater remediation capabilities for established contaminants identified five qualitative analogs for key PFAS groundwater remediation issues: (a) low‐level detection analytical capabilities; (b) methods to assess the risk of complex chemical mixtures; (c) nonaqueous phase dissolution as an analog for partitioning, precursors, and back diffusion at PFAS sites; (d) predictions of long plume lengths for emerging contaminants; and (e) monitored natural attenuation protocols for other non‐degrading groundwater contaminants. Overall the evaluation of these five analogs provided some comfort that, while remediating the potential universe of PFAS sites will be extremely challenging, the groundwater community has relevant past experience that may prove useful. The quantitative metrics and the qualitative analogs suggest a different combination of remediation approaches may be needed to deal with PFAS sites and may include source control, natural attenuation, in‐situ sequestration, containment, and point‐of‐use treatment. However, as with many chlorinated solvent sites, while complete restoration of PFAS sites may be uncommon, it should be possible to prevent excessive exposure of PFAS to human and ecological receptors.     

Managing the negative impacts of groundwater flow on electrothermal remediation

Rapid groundwater fluxes often influence subsurface temperature distributions during in situ thermal remediation using electrothermal or conduction heating technologies. This study used a numerical approach to evaluate the impact of groundwater flow on electrothermal heating, as well as the effectiveness of several upgradient heat loss management strategies, in a hypothetical treatment volume. Design alternatives using upgradient (i) hydraulic barriers, (ii) physical barriers, and (iii) increased energy input are evaluated. Results indicate that target temperatures can be achieved, despite the presence of local groundwater flow velocities greater than 0.3 m/day, through the careful design and implementation of the alternatives evaluated. However, physical barriers need to be designed to prevent groundwater flow through the heated volume to be effective. Field data from an electrothermal application are also presented, where boiling temperatures were achieved after steam injection and upgradient pumping wells were implemented.     

地下水原位修复渗透性反应墙反应介质的改良与展望

渗透性反应墙(PRBs)是倍受关注的地下水原位修复技术之一,具有高效廉价、安装简便、维护简单等优点。详细总结了零价铁、活性炭、无机矿物材料和生物质材料等PRBs反应介质的结构、性能、适用范围、改良方法及增强吸附机制,介绍了PRBs技术在国内外地下水原位修复领域的工程应用实例,指出研发可再生型反应介质、深入研究复杂体系的污染物去除主导机制以及开展多介质混合、多种原位修复技术集成应用研究将是今后PRBs的主要研究方向。     

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.     

Nanotechnology and groundwater remediation: A step forward in technology understanding

Nanotechnology application to contaminated site remediation, and especially the use of nanoscale zero‐valent iron particles to treat volatile organic compound (VOC)‐impacted groundwater, is now recognized as a promising solution for cost‐effective in situ treatment. Results obtained during numerous pilot tests undertaken by Golder Associates between 2003 and 2005 in North America (United States and Canada) and Europe have been used to present a synthetic cross‐comparison of technology dynamics. The importance of a comprehensive understanding of the site‐specific geological, hydrogeological, and geochemical conditions, the selection of appropriate nanoscale particles, the importance of monitoring geochemical parameters during technology application, and the potential of nanoparticle impact on microbial activity are discussed in this article. The variable technology dynamics obtained during six pilot tests (selected among numerous other tests) are then presented and discussed. © 2006 Wiley Periodicals, Inc.     

A European approach to increase innovative soil and groundwater remediation technology applications

The European Commission (EC) has recognized a need for strengthening innovation of environmental technologies in order to increase competitiveness of European technologies on a global market and to achieve a more sustainable development in Europe. In the area of soil and groundwater remediation, innovative technologies are principally available and have proven applicability and performance on demonstration scales, but market uptake is disappointing. Consequently, initiatives have been launched in order to promote application of these technologies and to investigate on the harmonization of applications. The European Co‐ordination Action for Demonstration of Efficient Soil and Groundwater Remediation (EURODEMO), an EC‐funded project, is one strategic initiative for supporting these goals. This article summarizes results obtained so far regarding the investigation of the European situation and some undertaken and envisaged measures to achieve better market uptake. The results of this research project may serve as prerequisites for a European Environmental Technologies Verification (ETV) process. © 2006 Wiley Periodicals, Inc.     

Insufficient source area remediation results in the rebound of TCE breakdown products in groundwater

In the early 1990s, a soil removal action was completed at a former disposal pit site located in southern Michigan. This action removed waste oil, cutting oil, and chlorinated solvents from the unsaturated zone. To contain groundwater contaminant migration at the site, a groundwater pump‐and‐treat system comprised of two extraction wells operating at a combined flow of 50 gallons per minute, carbon treatment, and a permitted effluent discharge was designed, installed, and operated for over 10 years. Groundwater monitoring for natural attenuation parameters and contaminant attenuation modeling demonstrated natural attenuation of the contaminant plume was adequate to attain site closure. As a result of incomplete contaminant source removal, a rebound of contaminants above the levels established in the remedial action plan (RAP) has occurred in the years following system shutdown and site closure. Groundwater concentrations have raised concerns regarding potential indoor air quality at adjacent residential properties constructed in the past 9 to 10 years. The only remedial option available in the original RAP is to resume groundwater pump‐and‐treat. To remediate the source area, an alternate remediation strategy using an ozone sparge system was developed. The ozone sparge remediation strategy addresses the residual saturated zone contaminants beneath the former disposal pit and reestablishes site closure requirements without resumption of the pump‐and‐treat system. A pilot study was completed successfully; and the final system design was subsequently approved by the Michigan Department of Environmental Quality. The system was installed and began operations in July 2010. As of the January 2011 monitoring event, the system has shown dramatic improvement in site contaminant concentrations. The system will continue to operate until monitoring results indicate that complete treatment has been obtained. The site will have achieved the RAP objectives when the system has been shut down and meets groundwater residential criteria for four consecutive quarters. © 2011 Wiley Periodicals, Inc.     

铁活化过硫酸盐修复石油烃污染土壤的研究进展

分析了Fe~0、Fe~(2+)和Fe~(3+)活化过硫酸盐氧化石油烃的机理,介绍了土壤中石油烃污染物降解的影响因素以及总结了铁活化过硫酸盐修复石油烃污染土壤技术的不足。指出应以铁活化过硫酸盐原位修复作为土壤中高浓度有机污染物的前处置方法,再结合微生物或植物修复等技术,以减少对土壤理化性质的影响;另外,检测仪器的发展有利于土壤修复技术的应用。     

Designing funnel‐and‐gate groundwater remediation systems near property corners

Numerical models were used to simulate alternative funnel‐and‐gate groundwater remediation structures near property corners in hypothetical homogeneous and heterogeneous unconfined aquifers. Each structure comprised a highly permeable central gate (hydraulic conductivity = 25 m/d) and soil‐bentonite slurry walls (hydraulic conductivity = 0.00009 m/d). Gates were perpendicular to regional groundwater flow and approximately 5 m from a contaminant plume's leading tip. Funnel segments collinear to the central gate reached property boundaries; additional funnel segments followed property boundaries in the most hydraulically upgradient direction. Structures were 1 m thick and anchored into the base of the aquifer. Two structures were simulated for each aquifer: one with a 3.0‐m‐long central gate and funnels on either side; and a second with a 1.5‐m‐long central gate, funnels on either side, and 0.75‐m‐long end gates. Funnels were lengthened in successive simulations, until a structure contained a contaminant plume. Results suggest that, for the same total gate length, one‐gate structures may facilitate more rapid remediation, up to 44 percent less time in trials conducted in this study, than multiple‐gate structures constructed near property corners. However, in order to effectively contain a plume, one‐gate structures were up to 46 percent larger than multiple‐gate structures. © 2011 Wiley Periodicals, Inc.     

Cyclodextrin‐enhanced remediation of organic and metal contaminants in porous media and groundwater

Heavy metals and toxic organic contaminants are found at numerous industrial and military sites. The generally poor performance of conventional pump‐and‐treat schemes has made the development of improved methods for contaminated site remediation a significant environmental priority. One such innovative method is cyclodextrin‐enhanced flushing of the contaminated porous media and groundwater. Cyclodextrin is a glucose‐based molecule that is produced on industrial scales by microorganisms. Over the last years, several cyclodextrin derivatives have received extensive research interest. It was shown that cyclodextrins can significantly enhance the solubility of toxic organics, and in some cases, heavy metals and radioactive isotopes. As a sugar, cyclodextrin is considered relatively non‐toxic to humans, plants, and soil microbes. Thus, there are minimal health‐related concerns associated with the injection of cyclodextrin into the subsurface, which is an inherent advantage for use of cyclodextrins as a remediation agent. This paper provides a review of the available literature concerning use of cyclodextrin for remediation of groundwater and soil.     

Field application of reactive iron walls for in-situ degradation of volatile organic compounds in groundwater

Reactive walls containing metallic iron have been installed at several commercial sites in the United States to degrade chlorinated organic compounds in groundwater. Although the results of laboratory studies conducted to determine reaction mechanisms have been widely disseminated, little information has been published on the full-scale application of this technology. This article describes the construction, implementation, and cost of in-situ reactive walls at three commercial sites.     

Nanotechnology for site remediation

As a remediation tool, nanotechnology holds promise for cleaning up hazardous waste sites cost‐effectively and addressing challenging site conditions, such as the presence of dense nonaqueous phase liquids (DNAPLs). Some nanoparticles, such as nanoscale zero‐valent iron (nZVI) are already in use in full‐scale projects with encouraging success. Ongoing research at the bench and pilot scale is investigating particles such as self‐assembled monolayers on mesoporous supports (SAMMS™), dendrimers, carbon nanotubes, and metalloporphyrinogens to determine how to apply their unique chemical and physical properties for full‐scale remediation. There are many unanswered questions regarding nanotechnology. Further research is needed to understand the fate and transport of free nanoparticles in the environment, whether they are persistent, and whether they have toxicological effects on biological systems. In October 2008, the U.S. Environmental Protection Agency's Office of Superfund Remediation and Technology Innovation (OSRTI) prepared a fact sheet entitled “Nanotechnology for Site Remediation,” and an accompanying list of contaminated sites where nanotechnology has been tested. The fact sheet contains information that may assist site project managers in understanding the potential applications of this group of technologies. This article provides a synopsis of the US EPA fact sheet, available at http://clu‐in.org/542F08009 , and includes background information on nanotechnology; its use in site remediation; issues related to fate, transport, and toxicity; and a discussion of performance and cost data for field tests. The site list is available at http://clu‐in.org/products/nanozvi . © 2008 Wiley Periodicals, Inc.     

Operating windows to assess whether monitored natural attenuation is a technically feasible remediation option for BTEX‐contaminated groundwater

When used in combination with source management strategies, monitored natural attenuation (MNA) is likely to be a technically feasible remediation option if the contaminant persistence time along the flow path is less than (a) the transport time to the compliance point and (b) the time available for groundwater remediation objectives to be achieved. Biodegradation is often the most significant natural attenuation process for benzene, toluene, ethylbenzene, and xylenes (BTEX) in groundwater. While BTEX transport rates increase with groundwater velocity, examination of data obtained from the published literature for seven sites undergoing MNA revealed significant positive correlations between groundwater velocity and first‐order biodegradation rates for toluene (r = 0.83, P < 0.05), ethylbenzene (r = 0.93, P < 0.01), m‐ and p‐xylene (r = 0.96, P < 0.01), and o‐xylene (r = 0.78, P < 0.05). This is attributed to increased dispersion at higher velocities leading to more mixing of electron acceptors with the contaminant plume. There was no positive correlation between groundwater velocity and first‐order biodegradation rates for benzene due to noise in the relationship caused by variations in (a) the concentrations of electron acceptors in the uncontaminated groundwater and (b) the proportions of benzene in the total BTEX concentration in the source area. A regression model of the relationship between groundwater velocity and the first‐order biodegradation rate can be used to delineate operating windows for groundwater velocity within which the contaminant persistence time is less than the transport and remediation times for a given source concentration, target concentration, distance to compliance point, retardation factor, and remediation time. The operating windows can provide decision makers with a rapid indication of whether MNA is likely to be a technically feasible remediation option at a given site. © 2005 Wiley Periodicals, Inc.     

Geochemical evaluation of metals in groundwater at long‐term monitoring sites and active remediation sites

At many sites, long‐term monitoring (LTM) programs include metals as chemicals of concern, although they may not be site‐related contaminants and their detected concentrations may be natural. At other sites, active remediation of organic contaminants in groundwater results in changes to local geochemical conditions that affect metal concentrations. Metals should be carefully considered at both types of sites, even if they are not primary contaminants of concern. Geochemical evaluation can be performed at LTM sites to determine if the monitored metals reflect naturally high background and, hence, can be removed from the analytical program. Geochemical evaluation can also be performed pre‐ and post‐treatment at active remediation sites to document the effects of organics remediation on metals and identify the processes controlling metal concentrations. Examples from both types of sites are presented in this article. © 2008 Wiley Periodicals, Inc.