Construction of a permeable reactive barrier in a residential neighborhood

In June 2001, the Massachusetts Department of Environmental Protection (DEP) installed a permeable reactive barrier (PRB) within a roadway in Needham, Massachusetts, to treat a plume of chlorinated solvents migrating toward two public water‐supply wells located in the adjacent town of Wellesley, Massachusetts. The solvents originated from an electronics manufacturer located approximately 2,300 feet upgradient of the roadway and 5,200 feet upgradient of the public supply wells. Chlorinated solvents, primarily trichloroethene (TCE), had migrated past the roadway to within 300 feet of the public supply wells. Two contaminant transport models prepared by the DEP's design contractor and the EPA indicated that the plume would reach the well field if no response actions were taken. To mitigate the future impact to the municipal well field, the DEP decided to install a PRB composed of zero‐valent granular iron across the path of the plume along Central Avenue in Needham. Though several dozen PRBs have been installed at sites worldwide and the technology is no longer considered innovative, the application of the technology in a roadway that receives 17,000 vehicles per day within a residential neighborhood is unique and presented difficulties not typically associated with PRB installations. The Needham PRB was also one of the first zero‐valent iron PRBs installed using the slurry trench method to treat chlorinated compounds. © 2002 Wiley Periodicals, Inc.     

Long‐term evaluation of an EHC injection permeable reactive barrier in a sulfate‐rich,high‐flow aquifer

Permeable reactive barriers (PRBs) have traditionally been constructed via trenching backfilled with granular, long‐lasting materials. Over the last decade, direct push injection PRBs with fine‐grained injectable reagents have gained popularity as a more cost‐efficient and less‐invasive approach compared to trenching. A direct push injection PRB was installed in 2005 to intercept a 2,500 feet (760 meter) long carbon tetrachloride (CT) groundwater plume at a site in Kansas. The PRB was constructed by injecting EHC^® in situ chemical reduction reagent slurry into a line of direct push injection points. EHC is composed of slow‐release plant‐derived organic carbon plus microscale zero‐valent iron (ZVI) particles, specifically formulated for injection applications. This project was the first full‐scale application of EHC into a flow‐through reactive zone and provided valuable information about substrate longevity and PRB performance over time. Groundwater velocity at the site is high (1.8 feet per day) and sulfate‐rich (~120 milligrams per liter), potentially affecting the rate of substrate consumption and the PRB reactive life. CT removal rates peaked 16 months after PRB installation with >99% removal observed. Two years post‐installation removal rates decreased to approximately 95% and have since stabilized at that level for the 12 years of monitoring data available after injection. Geochemical data indicate that the organic carbon component of EHC was mostly consumed after 2 years; however, reducing conditions and a high degree of chloromethane treatment were maintained for several years after total organic carbon concentrations returned to background. Redox conditions are slowly reverting and have returned close to background conditions after 12 years, indicating that the PRB may be nearing the end of its reactive life. Direct measurements of iron have not been performed, but stoichiometric demand calculations suggest that the ZVI component of EHC may, in theory, last for up to 33 years. However, the ZVI component by itself would not be expected to support the level of treatment observed after the organic carbon substrate had been depleted. A longevity of up to 5 years was originally estimated for the EHC PRB based on the maximum expected longevity of the organic carbon substrate. While the organic carbon was consumed faster than expected, the PRB has continued to support a high degree of chloromethane treatment for a significantly longer time period of over 12 years. Recycling of biomass and the contribution from a reduced iron sulfide mineral zone are discussed as possible explanations for the sustained reducing conditions and continued chloromethane treatment.     

Seven‐year performance evaluation of a permeable reactive barrier

In June and July 2001, the Massachusetts Department of Environmental Protection (MassDEP) installed a permeable reactive barrier (PRB) to treat a groundwater plume of chlorinated solvents migrating from an electronics manufacturer in Needham, Massachusetts, toward the Town of Wellesley's Rosemary Valley wellfield. The primary contaminant of concern at the site is trichloroethene (TCE), which at the time had a maximum average concentration of approximately 300 micrograms per liter directly upgradient of the PRB. The PRB is composed of a mix of granular zero‐valent iron (ZVI) filings and sand with a pure‐iron thickness design along its length between 0.5 and 1.7 feet. The PRB was designed to intercept the entire overburden plume; a previous study had indicated that the contaminant flux in the bedrock was negligible. Groundwater samples have been collected from monitoring wells upgradient and downgradient of the PRB on a quarterly basis since installation of the PRB. Inorganic parameters, such as oxidation/reduction potential, dissolved oxygen, and pH, are also measured to determine stabilization during the sampling process. Review of the analytical data indicates that the PRB is significantly reducing TCE concentrations along its length. However, in two discrete locations, TCE concentrations show little decrease in the downgradient monitoring wells, particularly in the deep overburden. Data available for review include the organic and inorganic analytical data, slug test results from nearby bedrock and overburden wells, and upgradient and downgradient groundwater‐level information. These data aid in refining the conceptual site model for the PRB, evaluating its performance, and provide clues as to the reasons for the PRB's underperformance in certain locations. © 2008 Wiley Periodicals, Inc.     

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.     

Long-term Performance of a Permeable Reactive Barrier in Acid Sulphate Soil Terrain

Deep drainage technique utilised for flood mitigation in low-land coastal areas of Australia during the late 1960s has resulted in the generation of sulphuric acid in soil by the oxidation of pyritic materials. Further degradation of the subsurface environment with widespread contamination of the underlying soil and groundwater presents a major and challenging environmental issue in acid sulphate soil (ASS) terrains. Although several ASS remediation techniques recently implemented in the floodplain of Southeast Australia including operation of gates, tidal buffering and lime injections could significantly control the pyrite oxidation, they could not improve the long-term water quality. More recently, permeable reactive barriers (PRBs) filled with waste concrete aggregates have received considerable attention as an innovative, cost-effective technology for passive in situ clean up of groundwater contamination. However, long-term efficiency of these PRBs for treating acidic groundwater has not been established. This study analyses and evaluates the performance of a field PRB for treating the acidic water over 2.5 years. The pilot-scale alkaline PRB consisting of recycled concrete was installed in October 2006 at a farm of southeast New South Wales for treating ASS-impacted groundwater. Monitoring data of groundwater quality over a 30 month period were assessed to evaluate the long-term performance of the PRB. Higher pH value (~pH 7) of the groundwater immediately downstream of the PRB and higher rates of iron (Fe) and aluminium (Al) removal efficiency (>95%) over this study period indicates that recycled concrete could successfully treat acidic groundwater. However, the overall pH neutralising capacity of the materials within the barrier declined with time from an initial pH 10.2 to pH 7.3. The decline in the performance with time was possibly due to the armouring of the reactive material surface by the mineral precipitates in the form of iron and aluminium hydroxides and oxyhydroxides as indicated by geochemical modelling.     

Considerations for the design of organic mulch permeable reactive barriers

Organic mulch consists of insoluble carbon biopolymers that are enzymatically hydrolyzed during decomposition to release aqueous total organic carbon (TOC). The released TOC is utilized by microorganisms as an electron donor to transform electrophilic contaminants via reductive pathways. Over the last decade, organic mulch permeable reactive barriers (PRBs), or biowalls, have received increased interest as a relatively inexpensive slow‐release electron donor technology for addressing contaminated groundwater. To date, biowalls have been installed to enhance the passive bioremediation of groundwater contaminated with a variety of electrophilic compounds, including chlorinated solvents, explosives, and perchlorate. In addition, several mulch biowall projects are currently under way at several U.S. Department of Defense facilities. However, at the present time, the guidelines available for the design of mulch PRBs are limited to a few case studies published in the technical literature. A biowall design, construction, and operation protocol document is expected to be issued by the Air Force Center for Environmental Excellence in 2007. In this publication, three technical considerations that can have a significant impact on the design and performance of mulch PRBs are presented and discussed. These technical considerations are: (1) hydraulic characteristics of the mulch bed; (2) biochemical characteristics of different types of organic amendments used as mulch PRB fill materials; and (3) a transport model that can be used to estimate the required PRB thickness to attain cleanup standards. © 2007 Wiley Periodicals, Inc.     

Field and laboratory evaluation of the treatment of DNAPL source zones using emulsified zero‐valent iron

Emulsified zero‐valent iron (EZVI) is a surfactant‐stabilized, biodegradable emulsion that forms droplets consisting of a liquid‐oil membrane surrounding zero‐valent iron (ZVI) particles in water. This article summarizes the results obtained during the first field‐scale deployment of EZVI at NASA's Launch Complex 34 (LC34) located on Cape Canaveral Air Force Station, Florida, in August 2002 and presents the results of recent follow‐on laboratory tests evaluating the mechanisms, which contribute to the performance of the technology. The field‐scale demonstration evaluated the performance of EZVI containing nanoscale zero‐valent iron (NZVI) when applied to dense, nonaqueous phase liquid (DNAPL) trichloroethylene (TCE) in the saturated zone. Results of the field demonstration indicate substantial reductions in TCE soil concentrations (greater than 80 percent) at all but two soil boring locations and significant reductions in TCE groundwater concentrations (e.g., 60 percent to 100 percent) at all depths targeted with EZVI. Laboratory tests conducted in 2005 suggest that both NZVI particles and EZVI containing NZVI can provide significant reductions in TCE mass when used to treat TCE DNAPL in small test reactors. However, EZVI was able to reduce TCE concentrations to lower levels than were obtained with NZVI alone, likely as a result of the combined impact of sequestration of the TCE into the oil phase and degradation of the TCE with the NZVI. © 2006 Wiley Periodicals, Inc.     

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。     

Utilization of nanoscale zero‐valent iron for source remediation—A case study

A pilot‐scale study was performed using a palladium‐catalyzed and polymer‐coated nanoscale zero‐valent iron (ZVI) particle suspension at the Naval Air Station in Jacksonville, Florida. A total of 300 pounds of nanoscale ZVI particle suspension was injected via a gravity feed and recirculated through a source area containing chlorinated volatile organic compounds (VOCs). The recirculation created favorable mixing and distribution of the iron suspension and enhanced the mass transfer of sorbed and nonaqueous constituents into the aqueous phase, where the contaminants could be reduced. Between 65 and 99 percent aqueous‐phase VOC concentration reduction occurred, due to abiotic degradation, within five weeks of the injection. The rapid abiotic degradation processes then yielded to slower biological degradation as subsequent decreases in ‐elimination parameters were observed—yet favorable redox conditions were maintained as a result of the ZVI treatment. Post‐treatment analyses revealed cumulative reduction of soil contaminant concentrations between 8 and 92 percent. Aqueous‐phase VOC concentrations in wells side gradient and downgradient of the source were reduced up to 99 percent and were near or below applicable regulatory criteria. These reductions, coupled with the generation of innocuous by‐products, indicate that nanoscale ZVI effectively degraded contamination and reduced the mass flux from the source, a critical metric identified for source treatment. A summary of this project was recently presented at the US EPA Workshop on Nanotechnology for Site Remediation in Washington, D.C., on October 21–22, 2005. This case study supplied evidence that nanoscale zero valent iron, an emerging remediation technology, has been implemented successfully in the field. More information about this workshop and this presentation can be found at www.frtr.gov/nano/index.htm. © 2006 Wiley Periodicals, Inc.     

Remediation of a Former Dry Cleaner Using Nanoscale Zero Valent Iron

Nanoscale zero valent iron (nZVI) was evaluated in a laboratory treatability study and subsequently injected as an interim measure to treat source area groundwater impacts beneath a former dry cleaner located in Chapel Hill, North Carolina (the site). Dry cleaning operations resulted in releases of tetrachloroethene (PCE) that impacted site soil at concentrations up to 2,700 mg/kg and shallow groundwater at concentrations up to 41 mg/L. To achieve a design loading rate of 0.001 kg of iron per kilogram of aquifer material, approximately 725 kg of NanoFe? (PARS Environmental) was injected over a two‐week period into a saprolite and partially weather rock aquifer. Strong reducing conditions were established with oxidation–reduction potential (ORP) values below –728 mV. pH levels remained greater than 8 standard units for a period of 12 months. Injections resulted in near elimination of PCE within one month. cis‐1,2‐Dichloroethene accumulated at high concentrations (greater than 65 mg/L) for 12 months. MAROS software (Version 2.2; AFCEE, 2006 ) was used to calculate mass reduction of PCE and total ethenes at 96 percent and 58 percent, respectively, compared to baseline conditions. Detections of acetylene confirmed the presence of the beta‐elimination pathway. Detections of ethene confirmed complete dechlorination of PCE. Based on hydrogen gas generation, iron reactivity lasted 15 months. © 2013 Wiley Periodicals, Inc.     

Pilot scale testing composite swellable organosilica nanoscale zero‐valent iron—Iron‐Osorb®—for in situ remediation of trichloroethylene

Iron‐Osorb^® is a solid composite material of swellable organosilica with embedded nanoscale zero‐valent iron that was formulated to extract and dechlorinate solvents in groundwater. The unique feature of the highly porous organosilica is its strong affinity for chlorinated solvents, such as trichloroethylene (TCE), while being impervious to dissolved solids. The swellable matrix is able to release ethane after dechlorination and return to the initial state. Iron‐Osorb^® was determined to be highly effective in reducing TCE concentrations in bench‐scale experiments. The material was tested in a series of three pilot scale tests for in situ remediation of TCE in conjunction with the Ohio Environmental Protection Agency at a site in central Ohio. Results of these tests indicate that TCE levels were reduced for a period of time after injection, then leveled out or bounced back, presumably due to depletion of zero‐valent iron. Use of tracer materials and soil corings indicate that Iron‐Osorb^® traveled distances of at least 20 feet from the injection point during soil augmentation. The material appears to remain in place once the injection fluid is diluted into the surrounding groundwater. Overall, the technology is promising as a remediation method to treat dilute plumes or create diffuse permeable reactive barriers. Keys to future implementation include developing injection mechanisms that optimize soil distribution of the material and making the system long‐lasting to allow for continual treatment of contaminants emanating from the soil matrix. © 2011 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.     

Chemical and Biological Reduction of PCE by Pneumatic Fracturing and Injection of ZVI in Saprolite

This article presents a case study of the source‐area treatment of tetrachloroethene (PCE) in a low‐permeability formation using zero‐valent iron (ZVI). Evidence of the stimulation of biological reduction processes within the treatment zone occurred. Pneumatic fracturing and injection of microscale ZVI slurry in the overburden and weathered bedrock zones was performed at a commercial brownfields redevelopment site in Maryland. A 20,000‐square‐foot source area impacted with PCE at concentrations greater than 15,000 µg/L was treated at depths ranging from 10 to 70 feet bgs. An average ZVI dosage of 0.0024 iron‐to‐soil mass ratio within the overburden zone led to a 75 percent decrease in PCE mass in less than one year. For the weathered bedrock zone, an average 0.0045 iron‐to‐soil mass ratio resulted in a 92 percent decrease in PCE mass during the same period. The reducing environment and hydrogen generated by the ZVI may have stimulated Dehalobacter populations, as evidenced by concentrations up to 10⁴ cells per milliliter measured within the treatment area despite a groundwater pH as high as 9. The biological reductive dechlorination of the chlorinated ethenes explains the temporary increase in trichloroethene and cis‐1,2‐dichloroethene concentrations. © 2013 Wiley Periodicals, Inc.     

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.     

Rapid Cleanup of Chlorinated Solvent Source Zones: Synergies Between Chemical and Biological Degradation

A chlorinated volatile organic compound (cVOC) source area approximately 25 by 100 ft in a heavily industrialized urban area was characterized with groundwater tetrachloroethene (PCE) concentrations up to 9,180 μg/L. This is approximately 6 percent of PCE's aqueous solubility, indicative of the presence of residual dense, nonaqueous phase liquid. The resulting dissolved‐phase plume migrated off‐site. Biotic and abiotic dechlorination using a combination of a food‐grade organic carbon‐based electron donor and zero‐valent iron suspended in a food‐grade emulsifying agent reduced the source area PCE concentrations by 98 percent within 27 weeks, with minimal downgradient migration of daughter products dichloroethene and vinyl chloride. Combining biological dechlorination with iron‐based chemical dechlorination is synergistic, enhancing treatment aggressiveness, balancing pH, and optimizing degradation of both DNAPL and dissolved‐phase cVOCs. © 2013 Wiley Periodicals, Inc.     

Remediating TCE‐contaminated groundwater in low‐permeability media using hydraulic fracturing to emplace zero‐valent iron/organic carbon amendment

A field pilot test in which hydraulic fracturing was used to emplace granular remediation amendment (a mixture of zero‐valent iron [ZVI] and organic carbon) into fine‐grained sandstone to remediate dissolved trichloroethene (TCE)‐contaminated groundwater was performed at a former intercontinental ballistic missile site in Colorado. Hydraulic fracturing was used to enhance the permeability of the aquifer with concurrent emplacement of amendment that facilitates TCE degradation. Geophysical monitoring and inverse modeling show that the network of amendment‐filled fractures extends throughout the aquifer volume targeted in the pilot test zone. Two years of subsequent groundwater monitoring demonstrate that amendment addition resulted in development of geochemical conditions favorable to both abiotic and biological TCE degradation, that TCE concentrations were substantially reduced (i.e., greater than 90 percent reduction in TCE mass), and that the primary degradation processes are likely abiotic. The pilot‐test data aided in re‐evaluating the conceptual site model and in designing the full‐scale remedy to address a larger portion of the TCE‐contaminated groundwater plume. © 2012 Wiley Periodicals, Inc.     

零价铁在废水处理中应用的研究进展

简述了零价铁（ZVI）处理废水的机理。综述了ZVI、纳米零价铁 （nZVI）对焦化废水、军火厂废水、制药废水、橄榄油厂废水、染料废水、含盐类废水及含重金属废水处理的研究进展以及ZVI复合材料处理废水的研究进展。指出将ZVI与超声波、微波及Fenton法等技术联合,形成具有各自优点的新处理技术,将是今后的研究重点。     

Impact of iron concentration and ph on zero‐valent iron dechlorination of DDT for brownfields

Soil contamination with persistent pesticides such as dichloro‐diphenyl‐trichloroethane (DDT) is a major issue at many brownfield sites. A technology that can be used to treat DDT‐contaminated soil using surfactants is to enhance the migration of the contaminants from the soil phase to the liquid phase, followed by the dechlorinating of the mobilized DDT in the liquid phase using zero‐valent iron (ZVI). The DDT degradation using ZVI occurs under anaerobic conditions via reductive reactions. The effect of the iron concentration on the dechlorination rate is assessed in the range of 1 to 40 percent (weight to volume) for remediation of a DDT‐contaminated site in Ontario, Canada. The optimum percentage of iron is found to be 20 percent at which the dechlorination rates of DDT and 1,1‐dichloro‐2,2‐bis(p‐chlorophenyl)ethane (DDD) were 4.5 and 0.6 mg/L/day, respectively. While mixing of the reaction solution is shown to be important in providing the iron surface available for the dechlorination reaction throughout the reaction solution, there is no significant difference between batch and fed‐batch mode of adding iron to the dechlorination process. Low pH values (pH = 3) increased the dechlorination rates of DDT and DDD to 6.03 and 0.75 mg/L/day, respectively at a 20 percent iron concentration, indicating increased dechlorination rates in acidic conditions. © 2010 Wiley Periodicals, Inc.