Evolution of predictive tools for in situ bioremediation and natural attenuation evaluations

Proving the viability of in situ bioremediation technologies and gathering data for its full‐scale implementation typically involves collecting multiple rounds of data and often completing microcosm studies. Collecting these data is cumbersome, time‐consuming, costly, and typically difficult to scale. A new method of completing microcosm studies in situ using an amendable sampling device deployed and incubated in groundwater monitoring wells provides actionable data to expedite site cleanup. The device, referred to as a Bio‐Trap® sampler, is designed to collect actively colonizing microbes and dissolved organic compounds from groundwater for analysis using conventional analytical techniques and advanced diagnostic tools that can answer very specific design and viability questions relating to bioremediation. Key data that can be provided by in situ microcosm studies using Bio‐Trap® samplers include definitively demonstrating contaminant destruction by using compound‐specific isotope analysis and providing data on the mechanism of the degradation by identifying the responsible microbes. Three case studies are presented that demonstrate the combined flexibility of Bio‐Trap® samplers and advanced site diagnostics. The applications include demonstrating natural attenuation of dissolved chlorinated solvents, demonstrating natural attenuation of dissolved petroleum compounds, and using multiple Bio‐Trap® samplers to comparatively assess the viability of bioaugmentation at a chlorinated solvent release site. At each of these sites, the in situ microcosm studies quickly and cost‐effectively answered key design and viability questions, allowing for regulatory approval and successful full‐scale implementation. © 2010 Wiley Periodicals, Inc.     

A systematic approach to in situ bioremediation in groundwater

In situ bioremediation (ISB) melds an understanding of microbiology, chemistry, hydrogeology, and engineering into a strategy for planned and controlled microbial degradation of specific contaminants. ISB creates subsurface environmental conditions, typically through reduction oxidation manipulation, which induce the degradation of contaminants via microbial catalyzed biochemical reactions. In turn, the microbes produce enzymes that are utilized to derive energy and that are instrumental in the degradation of target chemicals. To accomplish this chain of events, the type of microorganisms, contaminant, and the geological conditions at the site must be considered. Since in situ conditions are manipulated by engineered means, the most important consideration is the ability to transmit and mix liquids in the subsurface. The Interstate Technology Regulatory Council (ITRC)–ISB Team has recently completed a guidance document that describes a systematic approach to ISB in groundwater. ITRC is a state‐led coalition of more than 40 states working together with industry and stakeholders to achieve regulatory acceptance of environmental technologies. © 2003 Wiley Periodicals, Inc.     

Nitrate enhancement of in-situ bioremediation of monoaromatic compounds in groundwater

Removal of benzene, toluene, and the isomers of xylene (BTX) from gasoline-contaminated groundwater under denitrifying conditions was investigated. In laboratory microcosms, benzene removal was found to be significantly stimulated by phosphorus addition. For total xylenes, removal followed a similar response, but toluene disappearance was unaffected by phosphorus enrichment. An in-situ bioremediation project was conducted to extend this laboratory work to an actual field-scale cleanup of gasoline-contaminated groundwater. The flow of groundwater from two extraction wells to an infiltration gallery created a mostly closed loop to recycle the groundwater enriched with added nutrients and the electron acceptor (nitrate). The coincident occurrence of BTX loss (greater than 90 percent) in situ, nitrate (as well as phosphorus and ammonia) appearance, and increased levels of denitrifying bacteria at a downgradient well all suggested that denitrification may play a significant role in BTX remediation at this site.     

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.     

Enhanced aerobic bioremediation of a gasohol release in a fractured bedrock aquifer

In January 2005, a gasoline tanker carrying approximately 8,500 gallons of gasohol (gasoline containing 10 percent ethanol) overturned and caught fire in the front yard of a residence. Emergency response crews responded to the accident, extinguished the fire, and recovered residual gasoline on the ground surface. Soil impacted by the release was then removed and disposed of off‐site and free‐phase gasohol was recovered using a combination of vacuum recovery, pumping, and bailing to the extent practicable. Following free product recovery efforts, a feasibility evaluation was completed to select a technology to address the remaining dissolved‐phase contaminants that resulted in biosparging pilot testing and, ultimately, the installation of a full‐scale biosparging system. The full‐scale system has been operating for approximately 21 months, and contaminant concentrations within the heart of the plume have decreased dramatically over a short period of time—in most cases, to below applicable cleanup standards. Despite the complex hydrogeologic conditions and significant initial concentrations, biosparging has proven to be an effective technology to remediate this gasohol release, and it is anticipated that drinking‐water standards can be achieved following two to three years of biosparging (i.e., an additional 3 to 15 months of operations). © 2010 Wiley Periodicals, Inc.     

Screening method for locating groundwater monitoring wells

The traditional approach to characterizing the extent of groundwater contamination is often phased over a period of several years. A screening method has been developed that allows the investigation process to be reduced to a single phase. Existing data are used to develop a preliminary estimate of the extent of contamination, which is refined by the screening method using groundwater data collected and analyzed in the field. The screening method is applicable at sites with volatile organic compound contamination. Groundwater samples are collected using direct push or drill rig assisted methods, and the groundwater headspace gas is analyzed for the contaminant of interest. The refined estimate is used to locate all of the groundwater monitoring wells necessary to finalize the estimate of the extent of contamination. Therefore, only one investigation phase is required, and time and cost savings are realized with respect to the traditional multiphase approach. The screening method was successfully applied at a CERCLA site in Nebraska with two distinct plumes of TCE-contaminated groundwater. The Nebraska remedial investigation was completed approximately 18 months earlier than the estimated completion of a comparable phased investigation, with a corresponding cost reduction estimated at approximately 10 percent. If data from the screening method were used instead of data from monitoring wells, the estimated cost savings would be over 50 percent. Additional applications and evaluations may lead to industry and regulatory acceptance of the method as a primary characterization tool.     

Pilot‐scale evaluation of in situ cometabolic bioremediation of TCE in groundwater using PHOSter® technology

A study was conducted to evaluate the efficacy of PHOSter® technology for treating groundwater contaminated with trichloroethene (TCE) at Edwards Air Force Base, California. The technology consists of injecting a gaseous mixture of air, methane, and nutrients into groundwater with the objective of stimulating the growth of methanotrophs, a naturally occurring microbial group that is capable of catalyzing the aerobic degradation of chlorinated solvents into nontoxic products. Injection operations were performed at one well for a period of three months. Six monitoring wells were utilized for groundwater and wellhead vapor monitoring and for groundwater and microbial sampling. In the five monitoring wells located within 44 feet of the injection well, the following results were observed: dissolved oxygen concentrations increased to a range between 6 and 8 milligrams per liter (μg/L); the biomass of target microbial groups increased by one to five orders of magnitude; and TCE concentrations decreased by an average of 92 percent, and to below the California primary maximum contaminant level (MCL; 5 micrograms per liter [µg/L]) in the well closest to the injection well. © 2008 Wiley Periodicals, Inc. *

1 This article is a U.S. Government work and, as such, is in the public domain of the United States of America.

     

Environmentally Friendly Oil-Modified Polyesters as Polymeric Plasticizers for Poly(vinyl chloride)

Oil-modified polyesters were synthesized to serve as polymeric plasticizers for PVC. A total of four polymeric plasticizers with different average molecular weights were prepared. Characterizations were done using Fourier-transformed infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and gel permeation chromatography. Some of the tests conducted on PVC films include thermal stability test using thermogravimetric analyser, determination of glass transition temperature (T_g), plasticizer migration and leaching resistance test, morphology study of plasticized PVC films using field emission scanning microscope, toxicity test, and tensile test. Owing to the plasticizing effect of the palm oil-based compound, T_g of the plasticized PVC has decreased to an average of 65 °C at 20 wt% loading. The polymeric plasticizer is also able to contribute positively to the thermal stability and mechanical properties of the PVC films. Some of the advantages of incorporating polymeric plasticizer with high molecular weight includes lower rate of leaching from plastic, and improved tensile strength and elongation at break. Besides, thermal stability of the plastic studied using Kissinger’s and Flynn–Wall–Ozawa’s approaches shows that PVC blended with high molecular weight oil-modified polyester is more thermally stable, evidenced by the increase in the activation energy of decomposition, E_d. Toxicity test using brine shrimp egg shows encouraging results, where the oil-based plasticizer is considerably less toxic compared to some of the commercial plasticizers.     

Natural attenuation with varying degrees of aquifer heterogeneity: Implications for groundwater monitoring

This study evaluated the effect of heterogeneity in hydraulic conductivity on the tendency for contaminant plumes to attenuate via dilution, hydrodynamic dispersion, and molecular diffusion in simulated aquifers. Simulations included one homogeneous and four increasingly heterogeneous hydraulic conductivity fields. A numerical mass transport model generated an initial contaminant plume for each case; all initial plumes had the same mass. Next, the model simulated plume migrations through the simulated aquifers. Results suggest that highly heterogeneous settings are potentially effective at plume attenuation. Low‐velocity zones in heterogeneous settings delay plume travel, enabling more time for natural processes to lower contaminant concentrations in groundwater. © 2012 Wiley Periodicals, Inc.     

Nucleophilic substitution of poly(vinyl chloride) with iminoacetic acid and n-dodecanethiol

The modification of poly(vinyl chloride) was carried out with iminodiacetic acid (IDA, C₄H₇NO₄) and iminodiacetic acid dimethylester (IDADM, C₆H₁₁NO₄), as well as with n-dodecanethiol (DT, C₁₂H₂₆S) in the presence of K₂CO₃. The reaction was carried out at different temperatures below 100 °C with dimethyl formamide (DMF) and cyclohexanone as solvents. IDA did not show any reactivity, probably due to the dipolar character of the molecule. IDADM caused the elimination of HCl, while only substitution ratios of about 3 % were observed. However, the modification of PVC with DT resulted in a substitution rate of 18 % without elimination. DT-PVC showed excellent thermal properties, comparable with those of the unmodified polymer.     

Upgrading of poly(vinyl chloride) by chemical modifications using sodium sulfide

The recycling of poly(vinyl chloride) (PVC) is one of the most important issues in the treatment of waste plastics. To improve PVC recycling, it is necessary to develop new recycling techniques, including new techniques for the dechlorination of chlorine-containing polymers. It has been established that wet dechlorination of PVC in NaOH/ethylene glycol solution is more effective than dry dechlorination. In this study, the wet process was used, and the chemical modification of PVC by nucleophilic substitution was considered for upgrading waste PVC. Chlorine was substituted in solution by several nucleophilic reagents, thus changing the properties of PVC. The reaction of PVC in Na2S/ethylene glycol solution at 170°C resulted in the formation of a mixture comprising 32% elimination and 26% substitution products. The scanning electron microscopy/energy dispersive X-ray spectroscopy mappings and elementary analysis of PVC indicated that this chlorine-substitution process led to cross-linking by sulfur.     

Laboratory validation study of new vapor‐phase‐based approach for groundwater monitoring

Recent improvements in field‐portable analytical equipment allow accurate on‐site measurement of VOCs present in air at concentrations of less than 0.1 parts per million volume (ppmv). The objective of this project is to determine if the use of these instruments for vapor‐phase measurements of headspace in a monitoring well can serve as a reliable and accurate method for monitoring volatile organic compound (VOC) concentrations in groundwater under equilibrium conditions. As part of a comprehensive research project investigating the utility of this proposed monitoring method, the authors have completed a laboratory validation study to identify instruments and sample‐collection methods that will provide accurate measurement of VOC concentrations in groundwater. This laboratory validation study identified two field‐portable instruments (a gas chromatograph and a photoionization detector) with sufficient sensitivity to measure VOCs in groundwater at concentrations below typical monitoring standards (i.e., 1 to 5 μg/L). The accuracy and precision of these field instruments was sufficient to satisfy typical data‐quality objectives for laboratory‐based analysis. In addition, two sample‐collection methods were identified that yield vapor‐phase samples in equilibrium with water: direct headspace sampling and passive diffusion samplers. These sample‐collection methods allow the field instruments (which measure VOC concentrations in vapor‐phase samples) to be used to measure VOC concentrations in water. After further validation of these sample‐collection methods in the field, this monitoring method will provide a simple way to obtain accurate real‐time measurements of VOC concentrations in groundwater using inexpensive field‐portable analytical instruments. © 2009 Wiley Periodicals, Inc.     

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.     

The process and potential of bioremediation

Bioremediation has proven to be a powerful weapon in cleaning up contaminated soils and aquifers. This article gives the perspective of time, cost, and extent of remediation. It warns that disappointment will follow unless adequate site assessments are made and that the support of nutrients and supply of oxygen must be assured. Bioremediation cannot deal with all contaminants and the process is not instantaneous. However, the method is fail safe. In spite of any mistakes we may make, nature will eventually come to our rescue.     

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

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

Natural Fiber Reinforced Poly(vinyl chloride) Composites: Effect of Fiber Type and Impact Modifier

Poly(vinyl chloride) (PVC) and natural fiber composites were prepared by melt compounding and compression molding. The influence of fiber type (i.e., bagasse, rice straw, rice husk, and pine fiber) and loading level of styrene-ethylene-butylene-styrene (SEBS) block copolymer on composite properties was investigated. Mechanical analysis showed that storage modulus and tensile strength increased with fiber loading at the 30% level for all composites, but there was little difference in both properties among the composites from various fiber types. The use of SEBS decreased storage moduli, but enhanced tensile strength of the composites. The addition of fiber impaired impact strength of the composites, and the use of SEBS led to little change of the property for most of the composites. The addition of fiber to PVC matrix increased glass transition temperature (T_g), but lowered degradation temperature (T_d) and thermal activation energy (E_a). After being immersed in water for four weeks, PVC/rice husk composites presented relatively smaller water absorption (WA) and thickness swelling (TS) rate compared with other composites. The results of the study demonstrate that PVC composites filled with agricultural fibers had properties comparable with those of PVC/wood composite.     

Use of lignin degrading fungi in bioremediation

The use of lignin degrading fungi for decomposition of a wide variety of xenobiotics has become an area of intensive research. One distinct advantage of lignin degrading fungi over bacteria is that they do not require preconditioning to a particular pollutant prior to transformation. This degradative ability has been attributed to a nonspecific and nonstereoselective extracellular lignin-degrading enzymatic system (ligninase) which is induced by the fungi under nitrogen or carbon-limiting conditions (Reid, 1979). Ligninases (lignin-peroxidases) are responsible for the initial oxidative attack on lignin and other complex molecules via formation of a free radical thereby leading to depolymerization of complex molecular structures. Potential degradative ability of peroxidases may extend to include (1) sorbed contaminants, (2) high molecular-weight, hydrophobic contaminants, and (3) complex mixtures of chemicals typical of a contaminated site.     

Continuous water‐level monitoring in the assessment of groundwater remediation and refinement of a conceptual site model

An Erratum has been published for this article in Remediation 16(1) 2005, 155–157. Water‐level data collection is a fundamental component of groundwater investigations and remediation. While the locations and depths of monitored wells are important, the frequency of data collection may have a large impact on conclusions made about site hydrogeology. Data‐logging water‐level probes may be programmed to record water levels at frequent intervals, providing site decision makers with abundant, detailed information on the response of an aquifer to both anticipated and unforeseen stresses. In this study, a network of movable probes has provided several years of hourly water‐ level data. The understanding of the site's phytoremediation system has been enhanced by the continuous data, but subsequent insights into an unexpected situation regarding the site's infrastructure have been the most valuable result of the monitoring program. © 2005 Wiley Periodicals, Inc.     

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.