Technical and economic analyses in the development of bioremediation processes

The very large extent of subsurface and groundwater contamination with toxic organic compounds has prompted research on a number of bioremedial processes. The justification of this research has been to achieve lower overall remedial costs than are incurred by currently existing technologies. Laboratory studies are often undertaken with the notion that a new set of process conditions can reduce reagent consumption or the time for treatment by a significant factor with an attendant reduction in overall remediation costs. Research programs are initiated on the basis of these simple premises. Our work has shown that many research projects have been undertaken for the wrong reasons and that experimental effort has often not been directed toward large-scale implementation. A preliminary process analysis has been shown to be a very valuable component of any research and development program on bioremedial and other innovative technologies. As described in this article, the analysis (1) identifies the critical engineering and cost parameters and (2) provides guidance to the research program in the design of experiments and the collection of data. The methodology is also useful in the review of proposed new technologies and treatment equipment. The article includes an example of a process analysis for an actual development project directed toward the remediation of solids contaminated with chlorinated hydrocarbons to illustrate the benefits and the power of the technique.     

An evaluation of permeable reactive barrier projects in California

Permeable reactive barriers made of zero‐valent iron (ZVI PRBs) have become a prominent remediation technology in addressing groundwater contamination by chlorinated solvents. Many ZVI PRBs have been installed across the United States, some as research projects, some at the pilot scale, and many at full scale. As a passive and in situ remediation technology, ZVI PRBs have many attractive features and advantages over other approaches to groundwater remediation. Ten ZVI PRBs installed in California were evaluated for their performance. Of those ten, three are discussed in greater detail to illustrate the complexities that arise when quantifying the performance of ZVI PRBs, and to provide comment on the national debate concerning the downgradient effects of source‐zone removal or treatment on plumes of contaminated groundwater. © 2009 Wiley Periodicals, Inc.     

Groundwater and Nutrient Discharge into Jiaozhou Bay,North China

The health of near shore marine ecosystems has long been a concern because of its importance to coastal areas. Jiaozhou Bay (JZB) is one such marine ecosystem experiencing rapid water quality degradation in the last several decades. From the area surrounding the bay, the nutrients discharged into the bay through surface water and groundwater has been greatly changed. The thickness of the aquifers and the permeability is relatively high, the concentrations of nutrients in the groundwater are generally high, and so the groundwater discharged into JZB is very significant. However, no attempt has ever been made to evaluate the amount of nutrients discharged into the bay area via groundwater. In this study, the cross-section method and water balance method were used to estimate the amount of groundwater and nutrients discharged into JZB via the subsurface. Groundwater was monitored and sampled at aquifers surrounding the bay area, and some previously available data was also analyzed. The results indicated that groundwater from the Baisha Aquifer east of JZB now is the major source of nutrients (nitrate, dissolved SiO₂) being discharged into the bay. The concentrations of nutrients in the groundwater have been increasing with intensive agricultural land use. However, Dagu Aquifer, the largest aquifer north of JZB, only provides limited nutrients to the bay area because of the construction of a low permeability subsurface dam. Historically, during the 1970s to the 1990s, the Baisha Aquifer experienced seawater intrusion due to excessive groundwater withdrawal. The same was true for the Dagu Aquifer from the 1980s to the 1990s. Because of this, no significant nutrients were discharged into the bay.     

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.     

Innovative applications of subgrade biogeochemical reactors: Three case studies

Subgrade biogeochemical reactors (SBGRs) are an in situ remediation technology shown to be effective in treating contaminant source areas and groundwater hot spots, while being sustainable and economical. This technology has been applied for over a decade to treat chlorinated volatile organic compound source areas where groundwater is shallow (e.g., less than approximately 30 feet below ground surface [ft bgs]). However, this article provides three case studies describing innovative SBGR configurations recently developed and tested that are outside of this norm, which enable use of this technology under more challenging site conditions or for treatment of alternative contaminant classes. The first SBGR case study addresses a site with groundwater deeper than 30 ft bgs and limited space for construction, where an SBGR column configuration reduced the maximum trichloroethene (TCE) groundwater concentration from 9,900 micrograms per liter (μg/L) to <1 μg/L (nondetect) within approximately 15 months. The second SBGR is a recirculating trench configuration that is supporting remediation of a 5.7‐acre TCE plume, which has significant surface footprint constraints due to the presence of endangered species habitat. The third SBGR was constructed with a new amendment mixture and reduced groundwater contaminant concentrations in a petroleum hydrocarbon source area by over 97% within approximately 1 year. Additionally, a summary is provided for new SBGR configurations that are planned for treatment of additional classes of contaminants (e.g., hexavalent chromium, 1,4‐dioxane, dissolved explosives constituents, etc.). A discussion is also provided describing research being conducted to further understand and optimize treatment mechanisms within SBGRs, including a recently developed sampling approach called the aquifer matrix probe.     

In‐Situ and Ex‐Situ Bioremediation Options for Treating Perchlorate in Groundwater

Perchlorate has been identified as a water contaminant in 14 states, including California, Nevada, New Mexico, Arizona, Utah, and Texas, and current estimates suggest that the compound may affect the drinking water of as many as 15 million people. Biological treatment represents the most‐favorable technology for the effective and economical removal of perchlorate from water. Biological fluidized bed reactors (FBRs) have been tested successfully at the pilot scale for perchlorate treatment at several sites, and two full‐scale FBR systems are currently treating perchlorate‐contaminated groundwater in California and Texas. A third full‐scale treatment system is scheduled for start‐up in early 2002. The in‐situ treatment of perchlorate through addition of specific electron donors to groundwater also appears to hold promise as a bioremediation technology. Recent studies suggest that perchlorate‐reducing bacteria are widely occurring in nature, including in groundwater aquifers, and that these organisms can be stimulated to degrade perchlorate to below the current analytical reporting limit (< 4 μg/l) in many instances. In this article, in‐situ and ex‐situ options for biological treatment of perchlorate‐contaminated groundwater are discussed and results from laboratory and field experiments are presented. © 2002 Wiley Periodicals, Inc.     

Occurrence and behavior of per‐ and polyfluoroalkyl substances from aqueous film‐forming foam in groundwater systems

Per‐ and polyfluoroalkyl substances (PFAS) are fluorinated compounds and the active ingredient in aqueous film‐forming foam (AFFF). AFFF has been identified as a significant source of PFAS contamination in groundwater. PFAS are also present in many other industrial and consumer products and their manufacture and use has led to numerous contaminated sites. Human health risks have been identified with studies linking firefighter cancers to training facilities where AFFF was used. Given the widespread release of these compounds to the environment and their potential health risks, understanding their mobility characteristics is important. This article details the occurrence and behavior of these substances in groundwater systems to help guide the emerging fields of PFAS investigation and remediation. Background is presented on AFFF and PFAS source characteristics, including common industrial and consumer PFAS sources. In addition, chemical properties, sorption and retention parameters, and observed transformation properties of PFAS and related compounds are discussed. Finally, knowledge gaps are identified for future laboratory and field studies.     

Successfully applying sparging technologies

Air sparging is an innovative methodology for remediating organic compounds present in contaminated, saturated soil zones. In the application of the technology, sparging (injection) wells are used to inject a hydrocarbon-free gaseous medium (typically air) into the saturated zone below or within the areas of contamination. Two major mechanisms of remediation are engaged/enhanced due to the sparging process. First, volatile organic compounds are dissolved in the groundwater and sorbed on the soil partition into the advective air phase, effectively simulating an in-situ air stripping system. The stripped contaminants are transported in the air phase to the vadose zone, generally within the radius of influence of a standard vapor extraction and vapor treatment system. Second, with optimal environmental conditions, volatile and semivolatile organic compounds may be biodegraded by utilizing the sparging process to oxygenate the groundwater, thereby enhancing the growth and activity of the indigenous bacterial community. Air sparging is a complex multifluid phase process which has been applied successfully in Europe since the mid-1980s. Major design considerations include site geology, contaminant type, gas injection pressures and flow rates, injection interval (areal and vertical), and site-specific biofeasibility parameters. Site-specific geology and biofeasibility are the dominant design parameters. Pilot testing and full-scale design considerations should also be addressed. Mathematical models have been developed to simulate the air flow field during the sparging process and to examine the limitations imposed by site geology. Correct design and operation of this technology have been demonstrated to achieve groundwater cleanup to low part-per-billion contaminant levels. Incorrect design and operation can introduce significant pollution liability through undesirable contaminant migration in both the dissolved and vapor phases.     

Best Available Treatment Technologies Applied to Groundwater Circulation Wells

Groundwater circulation wells (GCWs) are a quasi‐in‐situ method for remediating groundwater in areas where remediation techniques that limit the water available for municipal, domestic, industrial, or agricultural purposes are inappropriate. The inherently resource‐conservative nature of groundwater circulation wells is also philosophically appealing in today's culture, which is supportive of green technologies. Groundwater circulation wells involve the circulation of groundwater through a dual‐screen well, with treatment occurring between the screens. The wells are specifically designed so that one well screen draws in groundwater and the second returns the groundwater after it has been treated within the well. Historically, the treatment has been performed with specialized equipment proprietary to GCW vendors. Two full‐scale pilot systems at a formerly used Defense Superfund site in Nebraska used best available technologies for treatment components. A multiple‐tray, low‐profile air stripper typically used for pump‐and‐treat remediation systems was successfully adapted for the GCW pilot system located in a trichloroethylene (TCE) hot spot. An ultraviolet water disinfection system was successfully adapted for the GCW pilot system located in a hot spot contaminated with the explosive compound hexhydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX). The pilot systems showed that GCW technology is competitive with a previously considered pump‐and‐treat alternative for focused extraction, and the regulatory community was supportive of additional GCW applications. A remedial design for the site includes 12 more GCW systems to complete focused remediation requirements. © 2002 Wiley Periodicals, Inc.     

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.     

Recent Developments in Cleanup Technologies

Although the reaction mechanics are somewhat mysterious, the use of iron for in situ groundwater treatment has recently gained considerable attention and respect in the remediation industry. The basic scientific principles of both applications of iron have been known for over a century; however, both were nearly unheard of as remediation technologies five years ago. Both technologies have a strong potential for widespread use. They are commercially available, have been proven in field studies, are less expensive than traditional pump and treat technologies, and, in many types of groundwater systems, may be able to meet difficult-to-achieve groundwater treatment standards. As these technologies continue to undergo development, there could be considerably more aggressive applications used to treat ground-water containing high concentrations of chlorinated organics and DNAPLs.     

Status of nanoremediation and its potential for future deployment: Risk‐benefit and benchmarking appraisals

NanoRem (Taking Nanotechnological Remediation Processes from Lab Scale to End User Applications for the Restoration of a Clean Environment) was a research project, funded through the European Commission's Seventh Framework Programme, which focuses on facilitating practical, safe, economic, and exploitable nanotechnology for in situ remediation of polluted soil and groundwater, which closed in January 2017. This article describes the status of the nanoremediation implementation and future opportunities for deployment based on risk‐benefit appraisal and benchmarking undertaken in the NanoRem Project. As of November 2016, NanoRem identified 100 deployments of nanoremediation in the field. While the majority of these are pilot‐scale deployments, there are a number of large scale deployments over the last five to 10 years. Most applications have been for plume control (i.e., pathway management in groundwater), but a number of source control measures appear to have taken place. Nanoremediation has been most frequently applied to problems of chlorinated solvents and metals (such as chromium VI). The perception of risk‐benefit balance for nanoremediation has shifted as the NanoRem Project has proceeded. Niche benefits are now more strongly recognized, and some (if not most) of the concerns, for example, relating to environmental risks of nanoremediation deployment, prevalent when the project was proposed and initiated, have been addressed. Indeed, these now appear overstated. However, it appears to remain the case that in some jurisdictions the use of nanoparticles remains less attractive owing to regulatory concerns and/or a lack of awareness, meaning that regulators may demand additional verification measures compared to technologies with which they have a greater level of comfort.     

Application of passive soil gas technology to determine the source and extent of a PCE groundwater plume in an urban environment

In situations where groundwater supplies have been impacted by volatile organic compounds (VOCs), such as tetrachloroethene (PCE), and the source has not been identified, the costs to identify the source and plume migration patterns may be extremely high. The costs for an investigation increase with the number and depth of borings and the number of samples that are collected and analyzed. An environmental investigator and the Arizona Department of Environmental Quality (ADEQ) have successfully utilized passive soil gas (PSG) surveys in Arizona to cost‐effectively investigate VOC impacts to groundwater and identify potential sources of impact. PSG surveys are minimally intrusive, and more samples can be collected for the same cost when compared to active soil gas surveys and conventional soil and groundwater sampling programs. The result is a surficial representation of the contaminant plume and the location of “hot spots,'' which are the potential sources. This provides a better understanding of the nature and extent of the impact and allows for a focused subsurface investigation, which subsequently reduces drilling and sampling costs. © 2008 Wiley Periodicals, Inc.     

How much heterogeneity? Flow versus area from a big data perspective

Over the past 10 years, there has been an increased recognition that matrix diffusion processes are a significant factor controlling the success of groundwater remediation. New field techniques and modeling tools have, consequently, been developed to understand how contaminants diffuse into and then out of low‐permeability (“low‐k”) zones and assess the resulting impact on groundwater quality. Matrix diffusion, in turn, is driven by one key factor: geologic heterogeneity. The importance of heterogeneity is being emphasized in the groundwater field by general rules of thumb such as “90% of the mass flux occurs in 10%‐20% of the cross‐sectional area” and conceptual models that show most of the groundwater flow occurs through the aquifer's “mobile porosity” which just a small fraction of commonly used effective porosity values (between 0.02 and 0.10 for mobile porosity vs. 0.25 for effective porosity). For this study, 141 boring logs from 43 groundwater remediation sites were evaluated to develop an empirically based estimate of the groundwater flow versus aquifer cross‐sectional area to confirm or reject the general flow versus area rules of thumb. This study indicated that at these 43 sites, an average of 30% of the cross‐sectional area carried 90% of the groundwater flow. Our flow‐only analysis does provide moderate (but not confirmatory) support for the “mobile porosity” concept with an estimated representative mobile porosity value of about 0.11 at the 43 sites.     

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.     

Successful application of monitored natural attenuation in a surficial aquifer

Groundwater investigations conducted since 1988 at a Tennessee Department of Environment and Conservation (TDEC) Voluntary Oversight and Assistance Program (VOAP) site located in Millington, Tennessee, have defined the lateral and vertical extent of site chemicals of concern (COCs) consisting of tetrachloroethene (PCE), trichloroethene (TCE), and associated degradation products. Results of a groundwater remedial investigation determined that aquifer conditions were favorable for anaerobic degradation of COCs through reductive dechlorination. A subsequent groundwater feasibility study determined that monitored natural attenuation (MNA) coupled with long‐term groundwater monitoring was the most effective and suitable remedial option for the site. A Record of Decision was issued by the TDEC VOAP approving MNA and long‐term groundwater monitoring as the remedial option for the site, a first for such a site in Tennessee involving chlorinated organics. A groundwater fate and transport model (the 1998 model) developed during the RI was used as the basis for the MNA remedy. Analytical data from 1998 to 2008 indicate COCs in former high‐concentration areas continue to degrade at rates consistent with or ahead of the 1998 model predictions. Evidence of reductive dechlorination is also supported by the continued presence of breakdown products—specifically, vinyl chloride and ethene (terminal endpoint of PCE breakdown through reductive dechlorination). The continued detection of breakdown products along the flow‐path wells also confirms the effectiveness of the MNA remedy at the site. Current analytical data indicate that COC plumes beneath the site are not migrating and are actually retracting. © 2010 Wiley Periodicals, Inc.     

Climate-influenced hydrobiogeochemistry and groundwater remedy design: A review

The process of designing a remedy for contaminated groundwater historically has not commonly included climate-future, hydrologic, and biogeochemical aquifer characteristics. From experience, the remedy design process also has not consistently nor directly integrated or projected future hydrologic and biogeochemical effects of the human-induced or developed environment—aka the anthropogenic influence—on potential remedy performance. The apparent practice of (1) not regularly assessing anthro-influenced hydrological (termed here as anthrohydrology) or biogeochemical characteristics (collectively hydrobiogeochemistry) of a site and (2) rarely accounting for future climatic shifts as design factors in remedy design may be due, in part, to the general practice-level view that groundwater remediation systems (whether in situ or ex situ) have seldom been anticipated to last more than a few years (or one or two decades at the most). Second, methods to reliably and quantitatively estimate site-specific, climate-future shifts in groundwater conditions using global and/or regional climate models and the resultant impacts on contaminant plume characteristics have not been readily available. The authors here suggest that while the concept of remedy design resilience and durability, within an envelope of climate change and anthropogenic influence, has been discussed in some technical circles as a component of “sustainable remediation,” we have found that direct application of these technical concepts in quantifiable terms remains rare. By incorporating the potential influence of future hydrobiogeochemical scenarios into remedy design, however, the design process could account for reasonable climate-induced influence on the groundwater system for a given site. These scenarios could then be applied within the remedy selection process to assess performance durability under potentially changing hydrologic, biological, and chemical conditions.     

The in situ treatment of PFAS within porewater at the air–water interface of a PFAS source zone

The treatment of per- and polyfluoroalkyl substances (PFAS) within groundwater is an emerging topic, with various technologies being researched and tested. Currently, PFAS-impacted groundwater is typically treated ex situ using sorptive media such as activated carbon and ion exchange resin. Proven in situ remedial approaches for groundwater have been limited to colloidal activated carbon (CAC) injected into aquifers downgradient of the source zones. However, treatment of groundwater within the source zones has not been shown to be feasible to date. This study evaluated the use of CAC to treat dissolved PFAS at the air–water interface within the PFAS source zone. Studies have shown that PFAS tends to preferentially accumulate at the air–water interface due to the chemical properties of the various PFAS. This accumulation can act as a long-term source for PFAS, thus making downgradient treatment of groundwater a long-term requirement. A solution of CAC was injected at the air–water interface within the source zone at a site with PFAS contamination using direct push technology. A dense injection grid that targeted the interface between the air and groundwater was used to deliver the CAC. Concentrations of PFAS within the porewater and groundwater were collected using a series of nine lysimeters installed within the vadose and saturated water columns. A total of six PFAS were detected in the porewater and groundwater including perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA). Detectable concentrations of PFAS within the pore and groundwater before treatment ranged from values greater than 300 µg/L for PFPeA to less than 3 µg/L for PFNA. Following the injection of the CAC, monitoring of the porewater and groundwater for PFAS was conducted approximately 3, 6, 9, 12, and 18 months postinjection. The results indicated that the PFAS within the porewater and groundwater at and near the air–water interface was effectively attenuated over the 1.5-year monitoring program, with PFAS concentrations being below the method detection limits of approximately 10 ng/L, with the exception of PFPeA, which was detected within the porewater during the 18-month sampling event at concentrations of up to 55 ng/L. PFPeA is a five carbon-chained PFAS that has been shown to have a lower affinity for sorption onto activated carbon compared to the longer carbon-chained PFAS such as PFOA. Examination of aquifer cores in the zone of injection indicated that the total organic carbon concentration of the aquifer increased by five orders of magnitude postinjection, with 97% of the samples collected within the target injection area containing activated carbon, indicating that the CAC was successfully delivered into the source zone.