Use of mixed technologies to remediate chlorinated DNAPL at a Brownfields site

A former chlorofluorocarbon manufacturing facility in northern New Jersey was purchased for redevelopment as a warehousing/distribution center as part of the New Jersey Department of Environmental Protection's Brownfields redevelopment initiative. Soil and groundwater at the site were impacted with dense nonaqueous‐phase liquids (chlorinated organic compounds) and light nonaqueous‐phase liquids (petroleum hydrocarbons). The initial remedial strategy (excavation and offsite disposal) developed by prior site owners would have been cost‐prohibitive to the new site owners and made redevelopment infeasible. Mixed remedial technologies were employed to reduce the cost of remediation while meeting regulatory contaminant levels that are protective of human health and the environment. The most heavily impacted soils (containing greater than 95 percent of the contaminant mass) were excavated and treated onsite by the addition of calcium oxide and lime kiln dust coupled with physical mixing. Treated soils were reused onsite as part of the redevelopment. Residual soil and groundwater contamination was treated via in situ injections of emulsified oil to enhance anaerobic biodegradation, and emulsified oil/zero‐valent iron to chemically reduce residual contaminants. Engineering (cap) and administrative (deed restriction) controls were used as part of the final remedy. The remedial strategy presented in this article resulted in a cost reduction of 50 percent of the initial remedial cost estimate. © 2008 Wiley Periodicals, Inc.     

Optimizing remediation strategies for a former dry‐cleaner site

Residual tetrachloroethene (PCE) contamination at the former Springvilla Dry Cleaners site in Springfield, Oregon, posed a potential risk through the vapor intrusion, direct contact, and off‐site beneficial groundwater uses. The Oregon Department of Environmental Quality utilized the State Dry Cleaner Program funds to help mitigate the risks posed by residual contamination. After delineation activities were complete, the source‐area soils were excavated and treated on‐site with ex situ vapor extraction to reduce disposal costs. Residual source‐area contamination was then chemically oxidized using sodium permanganate. Dissolved‐phase contamination was subsequently addressed with in situ enhanced reductive dechlorination (ERD). ERD achieved treatment goals across more than 4 million gallons of aquifer impacted with PCE concentrations up to 7,800 micrograms per liter prior to remedial activities. The ERD remedy introduced electron donors and nutrient amendments through groundwater recirculation and slug injection across two aquifers over the course of 24 months. Adaptive and mass‐targeted strategies reduced total remedy costs to approximately $18 per ton within the treatment areas. © 2010 Wiley Periodicals, Inc.     

Preliminary studies on potential remediation of acid mine drainage‐impacted soils by amendment with drinking‐water treatment residuals

Mining operations result in a wide range of environmental impacts: acid mine drainage (AMD) and acid sulfate soils being among the most common. Due to their acidic pH and high soluble metal concentrations, both AMD and acid sulfate soils can severely damage the local ecosystems. Proper post‐mining management practices are necessary to control AMD‐related environmental issues. Current AMD‐impacted soil treatment technologies are rather expensive and typically not environmentally sustainable. We conducted a 60‐day bench‐scale study to evaluate the potential of a cost‐effective and environment‐friendly technology in treating AMD‐impacted soils. The metal binding and acid‐neutralizing capacity of an industrial by‐product, drinking water treatment residuals (WTRs) were used for AMD remediation. Two types of locally generated WTRs, an aluminum‐based WTR (Al‐WTR) and a lime‐based WTR (Ca‐WTR) were used. Highly acidic AMD‐impacted soil containing very high concentrations of metals and metalloids, such as iron, nickel, and arsenic, was collected from the Tab‐Simco coal mine in Carbondale, Illinois. Soil amendment using a 1:1 Al‐ and Ca‐WTR mix, applied at 5 and 10 percent rates significantly lowered the soluble and exchangeable fractions of metals in the AMD‐impacted soil, thus lowering potential metal toxicity. Soil pH increased from an extremely acidic 2.69 to a near‐neutral 6.86 standard units over the 60‐day study period. Results from this preliminary study suggest the possibility of a successful scale‐up of this innovative, cost‐effective, and environmentally sustainable technology for remediating AMD‐impacted acid sulfate soils.     

Development of a waterjet system for direct delivery of granular iron and activated carbon to remediate contaminated aqueous sediments

While the techniques and technologies associated with contaminated sediment remediation are relatively mature, there are several issues associated with these practices that make them unattractive. The inability of currently used mechanical mixing implements to place amendments in aqueous environments and their intrusive behavior toward benthic communities are just two examples of a necessity for an improved delivery method. Waterjets may be a viable option for placement of particulate remediation amendments, such as activated carbon and granular iron, at depth. A custom waterjet nozzle and injection system has been fabricated by the authors to examine this delivery concept. The developed injection system's performance was tested by characterizing the waterjet‐delivered amendment (activated carbon and granular iron) distributions in a surrogate sediment. The delivered amendment distributions followed similar patterns for a range of injection times and a variety of amendments. The injection depths, however, were dependent upon the type of amendment being injected. These findings have led to a better understanding of what occurs during an amendment injection, which can be used for a more controlled placement of remediation amendments using this technique in the future. The laboratory results indicate that the subject waterjet system may have the potential for field‐scale applications, especially for granular iron delivery, as the authors were able to place between 60 and 70 wt percent into a surrogate sediment bed along the path of injection. © 2011 Wiley Periodicals, Inc.     

Enhanced dichloroethene biodegradation in fractured rock under biostimulated and bioaugmented conditions

Significant microbial reductive dechlorination of [1,2 ¹⁴C] cis‐dichloroethene (DCE) was observed in anoxic microcosms prepared with unamended, fractured rock aquifer materials, which were colonized in situ at multiple depths in two boreholes at the Naval Air Warfare Center (NAWC) in West Trenton, New Jersey. The lack of significant reductive dechlorination in corresponding water‐only treatments indicated that chlororespiration activity in unamended, fractured rock treatments was primarily associated with colonized core material. In these unamended fractured rock microcosms, activity was highest in the shallow zones and generally decreased with increasing depth. Electron‐donor amendment (biostimulation) enhanced chlororespiration in some but not all treatments. In contrast, combining electron‐donor amendment with KB1 amendment (bioaugmentation) enhanced chlororespiration in all treatments and substantially reduced the variability in chlororespiration activity both within and between treatments. These results indicate (1) that a potential for chlororespiration‐based bioremediation exists at NAWC Trenton but is limited under nonengineered conditions, (2) that the limitation on chlororespiration activity is not entirely due to electron‐donor availability, and (3) that a bioaugmentation approach can substantially enhance in situ bioremediation if the requisite amendments can be adequately distributed throughout the fractured rock matrix. © 2012 Wiley Periodicals, Inc.*     

Treatment of mercury‐contaminated soils with activated carbon: A laboratory,field, and modeling study

A series of laboratory batch leaching tests was conducted to evaluate the performance of different activated carbons in stabilizing mercury in soils. Based on the results of these experiments, an amendment application rate of 5 percent powdered activated carbon (PAC) was selected for in situ field application at a former industrial facility. A geochemical model was also developed to simulate the interactions between mercury and activated carbon in vadose‐zone soils. Modeling was used to (1) better understand possible mercury sequestration mechanisms and (2) predict the in situ performance of PAC. Model results indicate dissolved mercury concentrations observed in batch tests are consistent with equilibrium partitioning of mercury between dissolved organic matter, soil organic matter, and PAC. Activated carbon is predicted to reduce dissolved mercury concentrations via two mechanisms: (1) the formation of stable mercury complexes on PAC surfaces and (2) the direct adsorption of dissolved organic matter that would otherwise be available for mercury dissolution. Study results demonstrate PAC effectiveness for site soils with mercury concentrations below 200 mg/kg. © 2010 Wiley Periodicals, Inc.     

Rotary drum soil blending for source zone remediation: Various application scenarios

Mechanical blending of contaminated soil with amendments has recently reemerged as an important treatment technology. From its original application using large‐diameter augers in the early 1990s to the current use of rotary drum blenders, soil blending is being used as an alternative to other remediation technologies like amendment injection and soil vapor and groundwater extraction. Shallow (approximately 10 m below ground surface [bgs] or less) soil blending also offers an alternative to excavation and disposal. Soil blending has been used to remediate a site with various contaminants including, but not limited to, chlorinated solvents, petroleum, and metals. The types of soils susceptible to soil blending vary from sands and gravels to silts and clays to fractured rock and combinations of all of these. The types of amendments blended include oxidants, reducing agents, biological enhancements, and stabilizing amendments. Soil blending systems deliver the power to the mixing head to adequately mix the soil and amendment to enhance remediation effectiveness. Since long‐term contamination is often a result of heterogeneously distributed residual contaminant in localized source zones that are difficult to access, the typical aim of soil blending is to homogenize the soil while effectively distributing amendment to these zones made accessible by blending. By effectively homogenizing the soil, however, soil blending will increase the void ratio and disrupt the shear strength and bearing capacity of the soil so an important component of a soil blending technology is proper recovery of these geotechnical parameters. This can be achieved by using well‐known soil improvement techniques such as amending all or a portion of the blended area with Portland cement or lime. Several case studies of soil blending treatments of different contaminants and amendments in various soil types are provided.     

Use of bio‐traps with multiple substrates and electron acceptors to optimize remediation

Bio‐Traps® were used to investigate biodegradation of benzene, methyl tertiary butyl ether (MTBE), and tertiary butyl alcohol (TBA) under different conditions at a fractured rock site to aid the selection of a bioremediation approach. The Bio‐Traps were amended with the ¹³C‐labeled constituent of interest and sampled sequentially at 15‐, 30‐, 60‐, and 90‐day intervals. The conditions tested were biodegradation during operation of an air sparge system, amendment with nitrate during the air sparge operation, anaerobic biodegradation with the system turned off, and anaerobic biodegradation with nitrate amendment. There was increased biomass with nitrate amendment whether the air sparge system was on or off for all the constituents of interest. The diversity of the microbial community, determined by phospholipid fatty acid analysis, decreased with nitrate amendment as more specialized degraders were selected. The most negative indicators of potential biodegradation performance were observed with the anaerobic control. There was less biomass overall, less incorporation of ¹³C into biomass, and decreased membrane permeability. As testing with additional amendments continues at the site, it is not yet certain which treatment might be selected for bioremediation, but the Bio‐Trap tests thus far have identified that the in situ, natural attenuation condition is least favorable for biodegradation. © 2009 Wiley Periodicals, Inc.     

Evaluation of Risk from Using Poultry Litter to Remediate and Reuse Contaminated Estuarine Sediments

The availability of heavy metals in contaminated sediment evaluated for beneficial reuse, before and after chemical amendment, was evaluated using poultry manure as the amendment. The dredged sediment was only slightly contaminated with heavy metals. Availability tests on the amended sediment showed an increase in heavy metals, most likely because of poultry feed amendments passed to the manure. There would be difficulty finding one chemical amendment to reduce the availability of a number of heavy metals because the metals exhibit different chemical properties. © 2001 John Wiley & Sons, Inc.     

Evaluation of a soil‐amendment process demonstration for reducing the bioavailability of lead

The U.S. Environmental Protection Agency (EPA) evaluated an in‐situ application of a soil‐amendment process at a residential site that was contaminated with lead. The goal of the evaluation was to determine if the soil‐amendment process resulted in lower concentrations of bioavailable lead in the contaminated soils. The relative bioavailability of lead (bioaccessible lead) was measured by an in vitro test procedure that uses a highly acidic extraction procedure to simulate human digestive processes. The soil‐amendment demonstration showed that the 11.2 percent mean reduction in bioavailable lead concentration between untreated and treated soils was not statistically different. © 2002 Wiley Periodicals, Inc.     

Effects of cement on redistribution of trace metals and dissolution of organics in sewage sludge and its inorganic waste-amended products

The suitability of using cement-stabilized sludge products as artificial soils in earth works was evaluated. The sludge products investigated were cemented sludge, cement-treated clay-amended sludge (SS+MC), and cement-treated copper slag-amended sludge (SS+CS). The leachability of lead (Pb), zinc (Zn), copper (Cu), and chromium (Cr) were assessed using the sequential extraction technique, toxicity characteristic leaching procedure (TCLP), NEN 7341 availability test, and column leaching test. The results indicated that Zn leachability was reduced in all the cement-stabilized sludge products. In contrast, Cu was transferred from the organic fraction to the readily leachable phases in the cement-stabilized sludge products and therefore exhibited increased leachability. The increased Cu leachability could be attributed to dissolution of humic substances in the sludge as a result of elevated pH. Good correlation between dissolved organic carbon (DOC) and heavy metal leaching from the cement-stabilized sludge products was observed in the column leaching experiment. Even with a cement percentage as small as 12.5%, calcium silicate hydrate (C-S-H) was formed in the SS+MC and SS+CS products. Inclusion of the marine clay in the SS+MC products could reduce the leaching potentials of Zn, and this was the great advantage of the marine clay over the copper slag for sludge amendment.     

Iron‐mediated abiotic degradation of RDX in a contaminated aquifer

The influence of aqueous‐ and mineral‐phase iron on royal demolition explosive (RDX) destruction has been previously investigated in theoretical settings and bench‐scale tests by various practitioners. The feasible use of in situ redox manipulation to create reactive Fe(II) is contingent upon the aquifer containing enough iron oxides and iron‐bearing clay minerals for the treated zone to remain effective. The following is a summary of a bench‐scale assessment of this relationship using aquifer material from an ongoing groundwater remediation effort at the Iowa Army Ammunition Plant (IAAP). A bench‐scale study was designed to determine the relative contributions of the biotic and iron‐mediated abiotic degradation processes to the net decrease in RDX observed at the site using saturated aquifer samples collected from within the RDX plume. Sterilized samples with a sufficient stoichiometric excess of both soluble and mineral‐phase iron reduced concentrations of RDX in both the soil and water fractions to the same extent as the samples containing native biota. These results indicate that in situ, abiotic degradation of RDX is feasible in areas unsuitable to biotic degradation processes, yielding an additional alternative for in situ RDX remediation. © 2012 Wiley Periodicals, Inc.     

Chemical immobilisation of arsenic in contaminated soils using iron(II)sulphate—advantages and pitfalls

Chemical immobilisation of inorganic contaminants by increasing the sorption capacity of soils and/or promoting the formation of sparingly soluble precipitates may be a cost-effective approach to counteract groundwater pollution. This study focuses on the enhanced retention of arsenic in two contaminated soils by addition of solid iron(II)sulphate. Four lab-scale column experiments were performed under unsaturated conditions with subsoil material sampled at a former timber preservation site and a pigment production plant. Arsenic effluent concentrations indicated 89.9 to 99.8% immobilisation in the treated columns. Sequential extractions showed a shift in contaminant binding forms towards the iron(hydr)oxide and residual fractions. Possible immobilisation mechanisms are the precipitation of FeAs phases, the formation of inner sphere complexes, and/or the occlusion of arsenic in newly formed amorphous/crystalline iron oxides. Bromide breakthrough curves point to the fact that the addition of iron(II)sulphate only moderately affects soil hydraulic properties. In contrast to reduced emissions of arsenic, increased seepage water concentrations were observed for other trace elements (e.g., cobalt, nickel, zinc). Mass balances indicate that this effect is primarily related to the temporary pH-drop caused by the oxidation of ferrous iron. The results show that chemical immobilisation using iron(II)sulphate is a promising way to protect groundwater quality at sites contaminated with timber preservation and pigment production remnants. As a prerequisite, optimum amendment levels need to be established and practical/field tests should be accompanied by a monitoring for a broad range of relevant trace elements.     

Effect of industrial by-products containing electron acceptors on mitigating methane emission during rice cultivation

Three industrial by-products (fly ash, phosphogypsum and blast furnace slag), were evaluated for their potential re-use as soil amendments to reduce methane (CH₄) emission resulting from rice cultivation. In laboratory incubations, CH₄ production rates from anoxic soil slurries were significantly reduced at amendment levels of 0.5%, 1%, 2% and 5% (wt wt⁻¹), while observed CO₂ production rates were enhanced. The level of suppression in methane production was the highest for phosphogypsum, followed by blast slag and then fly ash. In the greenhouse experiment, CH₄ emission rates from the rice planted potted soils significantly decreased with the increasing levels (2–20 Mg ha⁻¹) of the selected amendments applied, while rice yield simultaneously increased compared to the control treatment. At 10 Mg ha⁻¹ application level of the amendments, total seasonal CH₄ emissions were reduced by 20%, 27% and 25%, while rice grain yields were increased by 17%, 15% and 23% over the control with fly ash, phosphogypsum, and blast slag amendments, respectively. The suppression of CH₄ production rates as well as total seasonal CH₄ flux could be due to the increased concentrations of active iron, free iron, manganese oxides, and sulfate in the amended soil, which acted as electron acceptors and controlled methanogens’ activity by limiting substrates availability. Among the amendments, blast furnace slag and fly ash contributed mainly to improve the soil nutrients balance and increased the soil pH level towards neutral point, but soil acidity was developed with phosphogypsum application. Conclusively, blast slag among the selected amendments would be a suitable soil amendment for reducing CH₄ emissions as well as sustaining rice productivity.     

Theoretical assessment of phosphate amendments for stabilization of (Pb + Zn) in polluted soil

Contamination of the environment with toxic metals, such as lead (Pb), represents a serious concern for human health. Most of the studies on Pb stabilization were performed using various phosphorus-containing amendments that can reduce Pb mobility and bioavailability by the sorption and precipitation of new, stable pyromorphite-type minerals, presenting very low solubility and bioaccessibility. However, the presence of competing ions, such as zinc (Zn), can reduce stabilization efficacy. The role of chemical composition on the stability of immobilization products of Pb and Zn by the addition of hydroxyapatite (HAP) or fluoroapatite (FAP) has been examined in this paper. In this analysis we used a theoretical criterion which is based on calculation of the ion–ion interaction potential, representing the main term of the cohesive energy of the matrix/pollutant system. It has been demonstrated that the stability of the HAP matrix decreases and that the stability of the FAP matrix increases with the Pb immobilization in the presence of Zn. The results of this analysis point out FAP as an advantageous amendment for the immobilization of Pb in the presence of Zn.     

Sustained treatment: Implications for treatment timescales associated with source‐depletion technologies

Sustained treatment is an emerging concept used to describe enhancements in attenuation capacity after the conclusion of the active treatment period for a given source‐depletion technology. The term includes mechanisms that lead to contaminant transformation or destruction over extended periods of time, such as endogenous biomass decay, slow diffusion of remedial amendments from low‐permeability zones, and the formation of reactive mineral species. This “value‐added” treatment continues after the end of capital expenditures at a site, and it provides additional insight in determining if monitored natural attenuation is a viable long‐term option for a site. This article identifies several sustained treatment mechanisms, examines technology‐specific factors that contribute to sustained treatment, and explores the potential timescales of sustained treatment relative to active treatment. As demonstrated in post‐treatment site data obtained during a comprehensive source‐depletion technology performance survey, enhanced bioremediation is the most promising in promoting sustained treatment, and this beneficial effect can extend for several years due to factors such as slow biomass decay. There is little evidence that other commonly used technologies (thermal treatment, in situ chemical oxidation, surfactant‐enhanced remediation, or cosolvent flushing) result in any significant sustained treatment. An exception would be a cosolvent flushing project where large quantities of biodegradable cosolvent are left in the subsurface at the end of the project, which could result in sustained long‐term dechlorination activity. In the case of in situ chemical oxidation, factors that contribute to a higher incidence of concentration rebound mask any potential sustained treatment effects. © 2011 Wiley Periodicals, Inc.     

Phytoremediation of arsenic‐contaminated soil as affected by the chelating agent CDTA and different levels of soil pH

Elevated levels of arsenic can pose a major threat to both human health and the environment. The phytoremediation of heavy metals from soil is emerging as a cost‐effective technology for the remediation of contaminated soils. The present greenhouse study was undertaken to identify plants capable of tolerating and accumulating high concentrations of arsenic. Asparagus fern and rye grass were found to tolerate and accumulate more than 1,100 ppm of arsenic in plant tissue. Arsenic uptake as affected by different levels of the chelating agent trans‐1, 2‐ cyclohexylenedinitrilotetraacetic acid (CDTA) and soil pH were also studied. The application of 5 mmol kg^?1 of CDTA to arsenic‐contaminated medium loam field soil enhanced the accumulation of arsenic by the test plants. Under these conditions, plants accumulated up to 1,400 ppm of arsenic as compared to 950 ppm by the plants grown in soil containing 1,200 ppm of arsenic but without any amendment of the chelating agent. Plants grown in field soil of pH 5 containing 300 ppm of arsenic absorbed higher concentrations of arsenic than at other tested pH levels. Corresponding reductions in arsenic content of soil after plant harvests were observed. © 2001 John Wiley & Sons, Inc.     

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

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

Field‐scale uranium (VI) bioimmobilization monitored by lipid biomarkers and 13C‐acetate incorporation

At the Old Rifle uranium mill‐tailing site in eastern Colorado, a test of subsurface amendment with acetate to stimulate the reductive immobilization of uranium was monitored by using lipid biomarker analysis and incorporation of ¹³C‐labeled acetate into lipid biomarkers. Both sediment and groundwater samples were analyzed. Within 7 days of acetate addition, groundwater microbial biomass increased by a factor of 5, and remained higher than control values in most samples for the 28 days sampled. At 29 days after the beginning of acetate amendment, 4 of 12 sediment samples had microbial biomass greater than the 95 percent confidence interval of controls. The mole percents of the phospholipid fatty acids 16:1ω7c and 16:1ω5c increased over control values upon acetate amendment, and incorporated high levels of ¹³C from labeled acetate in groundwater and sediment samples. 16:1ω7c is a biomarker for Geobacter, and evidence is provided that 16:1ω5c represents an unidentified iron‐reducing bacterium, probably a member of the Desulfobulbaceae. Biomarkers for organisms other than iron‐reducing bacteria, iso‐ and anteiso‐branched fatty acids and 18:1ω9c, decreased upon acetate amendment, and had their highest stable isotope incorporation at least 4 days after labeled acetate amendment ended, evidence for carbon‐sharing between iron‐reducers and other microorganisms. © 2011 Wiley Periodicals, Inc.     

Sequestration of metals in active cap materials: A laboratory and numerical evaluation

Active capping involves the use of capping materials that react with sediment contaminants to reduce their toxicity or bioavailability. Although several amendments have been proposed for use in active capping systems, little is known about their long‐term ability to sequester metals. Recent research has shown that the active amendment apatite has potential application for metals‐contaminated sediments. The focus of this study was to evaluate the effectiveness of apatite in the sequestration of metal contaminants through the use of short‐term laboratory column studies in conjunction with predictive, numerical modeling. A breakthrough column study was conducted using North Carolina apatite as the active amendment. Under saturated conditions, a spike solution containing elemental As, Cd, Co, Se, Pb, Zn, and a nonreactive tracer was injected into the column. A sand column was tested under similar conditions as a control. Effluent water samples were periodically collected from each column for chemical analysis. Relative to the nonreactive tracer, the breakthrough of each metal was substantially delayed by the apatite. Furthermore, breakthrough of each metal was substantially delayed by the apatite compared to the sand column. Finally, a simple 1‐D, numerical model was created to qualitatively predict the long‐term performance of apatite based on the findings from the column study. The results of the modeling showed that apatite could delay the breakthrough of some metals for hundreds of years under typical groundwater flow velocities. © 2012 Wiley Periodicals, Inc.