Recovery and Microbial Remediation of Organic Wood Preservatives in Groundwater at a Former Wood Treating Plant

Well-recovery networks coupled to immobilized microbe bioreactors (IMBRs) were installed at a 172-acre former wood preserving facility for the bioremediation of organic wood preservatives present in site groundwater. Free-phase creosote from the hardpan and soluble preservative fractions contained in subsurface groundwater were pumped separately to different holding tanks. Trace creosote fractions contained in the subsurface groundwater were further gravity separated in the holding tank. Immobilized microbial isolates evaluated in earlier laboratory and field pilot tests were established into two 40, 000-liter bioreactors for the biodegradation of all targeted consitituents. Microbial growth, dissolved oxygen, pH, nutrients, flow rate, and temperature were monitored in this in situ/ex situ bioremediation system. The process was used to remove the polycyclic aromatic hydrocarbon (PAH) and phenolic components of creosote and pentachlorophenol from contaminated groundwater. Data generated during the past 2 1/2 years indicate that 26 target compounds consistently are reduced to levels acceptable for discharge. Currently operating in Baldwin, Florida, this full-scale prototype is remediating the former wood preserving facility and is being used as a model system for the design and construction of new bioreactor systems needed at similar industrial sites in the United States and abroad.     

Bioremediation treatability studies of contaminated soils at wood preserving sites

Bioremediation has been used frequently at sites contaminated with organic hazardous chemicals where releases from processing vessels and the mismanagement of reagents and generated waste have contributed to significant impairment of the environment. At wood treater sites, process reagents such as pentachlorophenol (PCP), and creosote have adversely impacted the surrounding soil and groundwater. When PCP has been used at these sites, polychlorinated dibenzo‐p‐dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are typically found. Where creosote has been used as the wood preservative of choice, polynuclear aromatic hydrocarbons (PAHs) are commonly found. Many of these compounds are considered to be persistent, bioaccumulative, and toxic (PBT) and are particularly recalcitrant.     

Status and trends in bioremediation treatment technology

This article is a critical analysis of the treatment potential of bioremediation technology to degrade eight major environmental pollutants, polycyclic aromatic hydrocarbons, phenols, pentachlorophenols, creosote, polychlorinated biphenyls, trichloroethylene, chlorobenzoates, and chlorophenols. The discussion includes information on transformation mechanisms, identification of intermediate metabolites, elucidation of partial or complete pathways, effects of environmental parameters, as well as current and future industrial application. Results indicate that bioremediation used in conjunction with other physical and chemical treatment methodologies can effectively transform most prevalent nonchlorinated organic contaminants and some chlorinated contaminants, such as creosote and pentachlorophenol, into innocuous materials. Successful biodegradation of several other chlorinated organic compounds, notably polychlorinated biphenyls and trichloroethylene, is currently possible only under controlled laboratory conditions. Future successful field applications, however, appear promising.     

Natural attenuation of chlorinated solvent plumes at Texas dry cleaners

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

Methodology and model for performance and cost comparison of innovative treatment technologies at wood preserving sites

Wood preserving facilities have used a variety of compounds, including pentachlorophenol (PCP), creosote, and certain metals, to extend the useful life of wood products. Past operations and waste management practices resulted in soil and water contamination at a portion of the more than 700 wood preserving sites in the United States (EPA, 1997). Many of these sites are currently being addressed under federal, state, or voluntary cleanup programs. The U.S. Environmental Protection Agency (EPA) National Risk Management Research Laboratory (NRMRL) has responded to the need for information aimed at facilitating remediation of wood preserving sites by conducting treatability studies, issuing guidance, and preparing reports. This article presents a practical methodology and computer model for screening the performances and comparing the costs of seven innovative technologies that could be used for the treatment of contaminated soils at user‐specified wood preserving sites. The model incorporates a technology screening function and a cost‐estimating function developed from literature searches and vendor information solicited for this study. This article also provides background information on the derivation of various assumptions and default values used in the model, common contaminants at wood preserving sites, and recent trends in the cleanup of such sites. © 2001 John Wiley & Sons, Inc.     

Full‐scale in‐situ biobarrier demonstration for containment and treatment of MTBE

The Naval Facilities Engineering Service Center (NFESC), Arizona State University, and Equilon Enterprises LLC are partners in an innovative Environmental Security Technology Certification Program cleanup technology demonstration designed to contain dissolved MTBE groundwater plumes. This full‐scale demonstration is being performed to test the use of an oxygenated biobarrier at Naval Base Ventura County, in Port Hueneme, California. Surprisingly, few cost‐effective in‐situ remedies are known for the cleanup of MTBE‐impacted aquifers, and remediation by engineered in‐situ biodegradation was thought to be an unlikely candidate just a few years ago. This project demonstrates that MTBE‐impacted groundwater can be remediated in‐situ through engineered aerobic biodegradation under natural‐flow conditions. With respect to economics, the installation and operation costs associated with this innovative biobarrier system are at least 50 percent lower than those of a conventional pump and treat system. Furthermore, although it has been suggested that aerobic MTBE biodegradation will not occur in mixed MTBE‐BTEX dissolved plumes, this project demonstrates otherwise. The biobarrier system discussed in this article is the largest of its kind ever implemented, spanning a dissolved MTBE plume that is over 500 feet wide. This biobarrier system has achieved an in‐situ treatment efficiency of greater than 99.9 percent for dissolved MTBE and BTEX concentrations. Perhaps of greater importance is the fact that extensive performance data has been collected, which is being used to generate best‐practice design and cost information for this biobarrier technology. © 2001 John Wiley & Sons, Inc.     

THE POTENTIAL FOR RE-USE OF PRESERVATIVE-TREATED UTILITY POLES REMOVED FROM SERVICE

This study investigates the feasibility of re-using or recycling utility poles or parts of poles for solid wood products. Four hundred and fifty-six poles or pole sections, removed from service in Ontario and Quebec, Canada, were characterized by age, wood species, preservative type, residual preservative, dimensions and condition. Based on this characterization, the potential for re-use as round poles or posts, sawn posts, timber, lumber and cedar roof shingles was evaluated. About 8% of the poles can be re-used without reprocessing, 15% of the pole volume can be used for cedar shingles, and about 35% of the pole volume can be converted to sawn products based on the selected hierarchy of preferred uses. Most of the poles removed from service had been treated with pentachlorophenol. The average levels of treatment decreased with age of the poles and approached the toxic threshold retentions in 25-year-old (or older) poles. For older poles (>35 years), creosote was the predominant treatment. Creosote levels were about 50% of the assumed levels when fresh treated. Creosote extracted from these poles contained fewer polynuclear aromatic hydrocarbon components than “new” creosote. The poles treated with chromated copper arsenate (CCA) retained high levels of preservative, even after many years in service. Used poles can be sawn into lumber of a good grade (#2 and better) using a small portable bandsaw. Special sawdust handling and disposal provisions must be made if this use is to be adopted. Treated poles with depleted reserves of creosote or pentachlorophenol could be re-treated with CCA or creosote preservatives to acceptable retentions. The quality of re-treatment was as good or better than that observed with new wood, and the re-treatment should ensure several decades of protection for guide-rail posts and other high decay hazard applications.     

Creosote DNAPL Recovery‐Well Design for Mass Removal

Sites with dense nonaqueous‐phase liquid (DNAPL) contamination present significant remediation challenges in terms of technical practicability and cost. Remedial approaches to DNAPL sites often follow a management approach rather than removal or eradication approaches, particularly due to the uncertainties associated with the benefits of partial source mass removal, as complete source removal is unlikely. Mass‐removal technologies should be evaluated for all DNAPL sites, although implementation of recovery technologies will be limited to a few sites based upon site‐specific factors. Sitewide remedial strategies that employ source reduction, where applicable, and incorporate associated risk‐reduction technologies, including monitored natural attenuation, are advised. Creosote DNAPL sites are particularly challenging, as they are predominantly composed of low‐solubility polycyclic aromatic hydrocarbons that form long‐term continuing sources. Additionally, the physical properties of creosote DNAPL, including high viscosity and relatively low density, result in significant migration potential and considerable dissolved‐phase groundwater impacts. An innovative creosote DNAPL source recovery well design was developed to achieve separate‐phase removal of pooled creosote DNAPL. The design presented herein employs modified circulation‐well technology to mobilize DNAPL to the engineered recovery well, where it is gravity‐settled into a sump to permit separate‐phase mass removal of the emplaced DNAPL source without groundwater production or treatment. A discharge mass flux protocol was developed to verify dissolved‐phase plume stability and the benefit of the source mass removal. © 2013 Wiley Periodicals, Inc.     

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

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

The Reduction of Stranded Oil by In Situ Shoreline Treatment Options

The Svalbard Shoreline Field Trials quantified the effectiveness of sediment relocation, mixing, bioremediation, bioremediation combined with mixing, and natural attenuation as options for the in situ treatment of oiled mixed-sediment (sand and pebble) shorelines. These treatments were applied to oiled plots located in the upper beach at three experimental sites, each with different sediment character and wave-energy exposure. Systematic monitoring was carried out over a 400-day period to quantify oil removal and to document changes in the physical character of the beach, oil penetration, oil loading, movements of oil to the subtidal environment, biodegradation, toxicity, and to validate oil-mineral aggregate formation.The results of the monitoring confirmed that sediment relocation significantly accelerated the rate of oil removal and reduced oil persistence where oil was stranded on the beach face above the level of normal wave activity. Where the stranded oil was in the zone of wave action, sediment relocation accelerated the short-term (weeks) rate of oil loss from the intertidal sediments.Oil removal rates on a beach treated by mechanical mixing or tilling were not significantly higher than those associated with natural recovery. However there is evidence that mixing/tilling may have enhanced microbial activity for a limited period by increasing the permeability of the sediment.Changes in the chemical composition of the oil demonstrated that biodegradation was significant in this arctic environment and a bioremediation treatment protocol based on nutrient enrichment effectively doubled the rate of biodegradation. However, on an operational scale, the success of this treatment strategy was limited as physical processes were more important in causing oil loss from the beaches than biodegradation, even where this oil loss was stimulated by the bioremediation protocols.     

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.     

Integrated bioremediation of soil and groundwater at a superfund site

The soil and two aquifers under an active lumber mill in Libby, Montana, had been contaminated from 1946 to 1969 by uncontrolled releases of creosote and pentachlorophenol (PCP). In 1983, because the contaminated surface soil and the shallower aquifer posed immediate risks to human health and the natural environment, the U.S. Environmental Protection Agency placed the site on its National Priorities List. Feasibility studies in 1987 and 1988 determined that in situ bioremediation would help clean up this aquifer and that biological treatment would help clean up the contaminated soils. This article outlines the studies that led to a 1988 EPA record of decision and details the EPA-approved remedial plan implemented starting in 1989; EPA estimates a total cost of about $15 million (in 1988 dollars). The plan involves extensive excavation and biological treatment of shallow contaminated soils in two lined and bermed land treatment units, extraction of heavily contaminated groundwater, an aboveground bioreactor treatment system, and injection of oxygenated water to the contaminant source area, as well as to other on-site areas affected by the shallower aquifer's contaminant plume.     

An In Situ Bioreactor for the Treatment of Petroleum Hydrocarbons in Groundwater

Two pilot tests of an aerobic in situ bioreactor (ISBR) have been conducted at field sites contaminated with petroleum hydrocarbons. The two sites differed with respect to hydrocarbon concentrations. At one site, concentrations were low but persistent, and at the other site concentrations were high enough to be inhibitory to biodegradation. The ISBR unit is designed to enhance biodegradation of hydrocarbons by stimulating indigenous microorganisms. This approach builds on existing Bio‐Sep^® bead technology, which provides a matrix that can be rapidly colonized by the active members of the microbial community and serves to concentrate indigenous degraders. Oxygen and nutrients are delivered to the bioreactor to maintain conditions favorable for growth and reproduction, and contaminated groundwater is treated as it is circulated through the bed of Bio‐Sep^® beads. Groundwater moving through the system also transports degraders released from Bio‐Sep^® beads away from the bioreactor, potentially increasing biodegradation rates throughout the aquifer. Groundwater sampling, Bio‐Traps, and molecular biological tools were used to assess ISBR performance during the two pilot tests. Groundwater monitoring indicated that contaminant concentrations decreased at both sites, and the microbial data suggested that these decreases were due to degradation by indigenous microorganisms rather than dilution or dispersion mechanisms. Taken together, these lines of evidence showed that the ISBR system effectively increased the number and activity of indigenous microbial degraders and enhanced bioremediation at the test sites. © 2013 Wiley Periodicals, Inc.     

Intrinsic and Stimulated In Situ Biodegradation of Hexachlorocyclohexane (HCH)

The feasibility of the biodegradation of HCH and its intermediates has been investigated. A recent characterisation of two sites in The Netherlands has shown intrinsic biodegradation of HCH. At one site, breakdown products (monochlorobenzene, benzene and chlorophenol) were found in the core of the HCH-plume, whereas the HCH-concentration decreased over time and space. Characterisation of a second, industrial site indicated less intrinsic biodegradation and the need to stimulate biodegradation. In the laboratory, enhanced HCH degradation was tested with soil and groundwater material from both sites, and the required conversion to the intermediates benzene and monochlorobenzene was demonstrated. Furthermore, the biodegradation of these intermediates could be initiated by adding low amounts of oxygen (<5%). Adding nitrate enhanced this degradation. We hypothesise that this occurs through anaerobic nitrate reducing conversion of oxidised intermediates.At the non-industrial other site, intrinsic degradation took place, as shown in the laboratory experiments. Interpretation of the field data with computer codes Modflow and RT3D was performed. As a result of the modelling study, it has been proposed to monitor natural attenuation for several years before designing the final approach.At the industrial site, the results of the batch experiments are applied. Anaerobic HCH degradation to monochlorobenzene and benzene is stimulated via the addition of an electron donor.Infiltration facilities have been installed at the site to create an anaerobic infiltration zone in which HCH will be degraded, and these facilities are combined with the redevelopment of the site.     

In-situ Treatment of Oiled Sediment Shorelines

Experimental oil spill studies were conducted to quantify the effectiveness of selected in-situ shoreline treatment options to accelerate natural oil removal processes on mixed-sediment (sand and pebble) shorelines. At each of three distinct shoreline sites, treatment test plots and control plots were established within a 40-, 80- and 143-m continuous stretch of oiled shoreline. A total of 5500 l of oil was deposited along a 3-m wide swath in the upper intertidal zone at each site. Approximately one week after oiling, a different treatment technique was applied to each plot. The treatment techniques were: sediment relocation (surf washing), mixing (tilling), bioremediation (fertilizer application), and bioremediation combined with mixing. One plot at each site was monitored for natural attenuation. The quantity of oil removed from the plots was measured six times up to 60 days post-treatment and then again one year later. Changes in the physical character of the beach, oil penetration, movement of oil to the subtidal environment, toxicity, and biodegradation were monitored over the 400-day period.The results verified quantitatively that relocation of oiled sediments significantly accelerated the rate of oil removal from the shoreline by more than one year. Microscopic observations and image analyses confirmed that the oil-mineral aggregate formation process was active and was increased by sediment relocation. Oil biodegradation occurred in this arctic environment, both in the oiled sediments and on the fine mineral particles removed from the sediment by natural physical processes. The biodegradation of oil in sediment was significantly stimulated by simple bioremediation protocols. Mixing (by tilling) did not clearly stimulate oil loss and natural recovery in the context of this experimental design. None of the treatment techniques elevated toxicity in the nearshore environment to unacceptable levels, nor did they result in consequential alongshore or nearshore oiling.     

Matrix Diffusion Modeling Applied to Long‐Term Pump‐and‐Treat Data: 2. Results From Three Sites

The data mining/groundwater modeling methodology developed in McDade et al. (2013) was performed to determine if matrix diffusion is a plausible explanation for the lower‐concentration but persistent chlorinated solvent plumes in the groundwater‐bearing units at three different pump‐and‐treat systems. Capture‐zone maps were evaluated, and eight wells were identified that did not draw water from any of the historical source areas but captured water from the sides of the plume. Two groundwater models were applied to study the persistence of the plumes in the absence of contributions from the historical source zones. In the wells modeled, the observed mass discharge generally decreased by about one order of magnitude or less over 4 to 10 years of pumping, and 1.8 to 17 pore volumes were extracted. In five of the eight wells, the matrix diffusion model fit the data much better than the advection dispersion retardation model, indicating that matrix diffusion better explains the persistent plume. In the three other wells, confounding factors, such as a changing capture zone over time (caused by changes in pumping rates in adjacent extraction wells); potential interference from a high‐concentration unremediated source zone; and limited number of pore volumes removed made it difficult to confirm that matrix diffusion processes were active in these areas. Overall, the results from the five wells indicate that mass discharge rates from the pumping wells will continue to show a characteristic “long tail'' of mass removal from zones affected by active matrix diffusion processes. Future site management activities should include matrix diffusion processes in the conceptual site models for these three sites. © 2013 Wiley Periodicals, Inc.     

Investigation of NAPL transport through a model sand cap during ebullition

Nonaqueous‐phase liquid (NAPL) migration from sediments to the surface of water bodies has been reported frequently at sites with sediments contaminated with NAPLs, such as coal tar and creosote. Commonly, transport of NAPL from sediment is facilitated by gas ebullition caused by anaerobic biodegradation of organic matter in the sediment. A remedy often specified for these sites is a sand cap, and sand caps amended with sorbent materials (such as organoclays) are being pilot‐tested. This article discusses a laboratory study to assess the effectiveness of a sand layer for controlling NAPL migration. The study used a test column composed of a Plexiglas tube containing a tar source that was buried beneath a 30‐cm‐thick layer of fine sand. Water was added to the column until 5 cm of standing water covered the sand layer. To simulate ebullition, air was injected into the base of the sand column at approximately 200 mL/min. It was observed that the gas and NAPL migrated primarily through channels and fractures in the sand, and was not filtered through a network of stable pores. Tar migrated through the sand layer in 12 hours and accumulated on the water surface for several hours before losing its buoyancy and settling back down to the sand surface. After ending the tar migration experiment, the test column was frozen to preserve structures in the sand. The study showed that the tar migrated through the simulated sand cap in small (2‐mm) channels only a few sand grains thick. The results of this laboratory work call into question the effectiveness of sand caps for controlling NAPL migration from sediment in the presence of ebullition. © 2009 Wiley Periodicals, Inc.     

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

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

Assessment and monitoring tools for aerobic bioremediation of vinyl chloride in groundwater

Direct aerobic biodegradation of vinyl chloride (VC) offers a remedial solution for persistent vinyl chloride plumes that are not amenable to the anaerobic process of reductive dechlorination because of either prevailing geochemical conditions or the absence of active Dehalococcoides ethenogenes. However, tools are needed to evaluate and optimize aerobic VC bioremediation. This article describes the development and testing of two techniques—a microbiological tool and a molecular tool—for this purpose. Both methods are based on detection of bacteria that can use vinyl chloride and ethene as growth substrates in the presence of oxygen. The microbiological tool is an activity assay that indicates whether bacteria capable of degrading ethene under aerobic conditions are present in a groundwater sample. This activity assay gave positive results in the area of active VC degradation of an aerobic VC bioremediation test site. A rapid semiquantitative genetic assay was also developed. This molecular tool, based on polymerase chain reaction (PCR) detection of a gene involved in the metabolism of both ethene and VC, revealed the presence of potential VC degraders in an enrichment culture and site groundwater. These tools could provide a basis for judging the potential of aerobic VC degradation by ethenotrophs at other sites in addition to offering a mechanism for treatment monitoring and system optimization. © 2009 Wiley Periodicals, Inc.     

Modeling remediation time using natural attenuation at a dry‐cleaner site

Contaminants from dry‐cleaning sites, primarily tetrachloroethene (PCE), trichloroethene (TCE), cis‐dichloroethene (cis‐DCE), and vinyl chloride (VC), have become a major concern because of the limited funds and regulatory programs to address them. Thus, natural attenuation and its effectiveness for these sites needs to be evaluated as it might provide a less costly alternative to other remediation methods. In this research, data from a site in Texas were analyzed and modeled using the Biochlor analytical model to evaluate remediation times using natural attenuation. It was determined that while biodegradation and source decay were occurring at the site, the resulting attenuation rates were not adequate to achieve cleanup in a reasonable time frame without additional source remediation or control strategies. Cleanup times exceeded 100 years for all constituents at the site boundary and 800 years at the source for PCE, assuming cleanup levels of 0.005 mg/L for PCE and TCE and 0.07 mg/L and 0.002 mg/L for cis‐DCE and VC, respectively. © 2005 Wiley Periodicals, Inc.