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.     

The treatment of contaminated water at remedial wood preserving sites

Contaminated groundwater and surface water have posed a great challenge in restoring wood preserving sites to beneficial use. Often contaminated groundwater plumes extend far beyond the legal property limits, adversely impacting drinking water supplies and crop lands. To contain, treat, and/or remediate these valuable resources is an important part of restoring these impacted sites. Various options are available for remediating the groundwater and other affected media at these sites. Frequently, pump and treat technologies have been used that can provide well‐head treatment at installed extraction wells. This approach has shown to be costly and excessively time consuming. Some of the technologies used for pump and treat are granular activated carbon (GAC), biotreatment, and chemical oxidation. Other approaches use in‐situ treatment applications that include enhanced bioremediation, monitored natural attenuation (biotic and abiotic), and chemical reduction/fixation. Ultimately, it may only be feasible, economically or practicably, to use hydraulic containment systems. Depending upon site‐specific conditions, these treatment approaches can be used in various combinations to offer the best remedial action. A comparison of water treatment system costs extrapolated from the treatability studies performed on contaminated groundwater from the McCormick/Baxter Superfund site in Stockton, California, yielded operation and maintenance costs of $1.19/1,000 gal. for carbon treatment and $7.53/1,000 gal. for ultraviolet (UV) peroxidation, respectively.     

Land treatment and the toxicity response of soil contaminated with wood preserving waste

Soils contaminated with wood preserving wastes, including pentachlo-rophenol (PCP) and creosote, are treated at field-scale in an engineered prepared-bed system consisting of two one-acre land treatment units (LTUs). The concentration of selected indicator compounds of treatment performance included PCP, pyrene, and total carcinogenic polycyclic aromatic hydrocarbons (TCPAHs) was monitored in the soil by taking both composited soil samples at multiple points in time, and discrete soil samples at two points in time. The mean concentration of the indicator compounds and the 95-percent confidence interval (CI) of the composite and discrete samples agreed relatively well, and first-order degradation rate kinetics satisfactorily represented the mean chemical concentration loss of indicator compounds in the LTU. Toxicity of the soil, as measured by Microtox^TM assay of the soil extracts, indicated that toxicity reduction corresponded with indicator compound disappearance. No toxicity effects were observed with time in treated layers of soil (lifts) buried beneath highly contaminated lifts of newly applied soil. This indicated that vertical migration of soluble contaminants from such lifts had little effect on the microbial activity in the underlying treated soil.     

Identification of pyrene‐degradation pathways: Bench‐scale studies using Pseudomonas fluorescens 29L

This article summarizes the bench‐scale studies to identify pyrene‐degradation pathways using an environmental microbial isolate, Pseudomonas fluorescens 29L. Strain 29L was grown on 50 mg of pyrene per liter of mineral medium. At a pyrene biodegradation rate of 14.7 mg/L of medium/day, 82.38 percent of pyrene was degraded in six days. Naphthalene and phenanthrene accounted for 1.09 percent and 3.69 percent, respectively, of the carbon mass from pyrene in the late log phase. Substituted benzene compounds accounted for 26.10 percent of the carbon mass from pyrene in the late log phase. In the stationary phase, carboxylic acids accounted for 10.44 percent of the carbon mass from pyrene. Strain 29L mutants were used for enzyme assays. Pyrene is oxidized by monoxygenases and dioxygenases, and the oxidized ring is cleaved. These enzymes were induced in the presence of pyrene and their activities peaked in the late log phase. No gentisate 1,2‐dioxygenase activity was detected in Strain 29L wild type (WT), whereas mutant M15 did not show any catechol 2,3‐dioxygenase activity. This indicates the possibility of multiple branchings in the pyrene‐biodegradation pathways. In conclusion, multiple degradative pathways are operating concurrently in this strain. The study shows the versatility of Pseudomonas fluorescens Strain 29L for pyrene degradation. It also emphasizes the need to study pyrene‐degradation pathways in other microorganisms so as to enhance the bioremediation potential for the in situ treatment of pyrene‐contaminated sites. © 2008 Wiley Periodicals, Inc.     

Assessing detoxification and degradation of wood preserving and petroleum wastes in contaminated soil

This study was undertaken to evaluate in-situ soil bioremediation processes, including degradation and detoxification, for two types of wood preserving wastes and two types of petroleum refining wastes at high concentrations in an unacclimated soil. The soil solid phase, water soluble fractions of the soil, and column leachates were evaluated. Two bioassays, a mutagenic potential asay (Ames assay) and an aqueous toxicity assay (Microtox^™ assay) were used to evaluate detoxification; high performance liquid chromatography was used to evaluate chemical concentration and degradation for eight polynuclear aromatic hydrocarbons (PAHs). The group of non-carcinogenic PAHs studied demonstrated greater degradation, ranging from 54–90% of mass added for the four wastes; the carcinogenic group of PAHs studied exhibited degradation ranging from 24–53% of mass added. Although no mutagenicity was observed in waste/soil mixtures after one year of treatment, Microtox^™ toxicity was observed in water soluble fractions and in leachate samples. An integration of information concerning degradation of hazardous constituents with bioassay information represents an approach for designing treatability studies and for evaluating the effectiveness of in-situ bioremediation of contaminated soil/waste systems. When combined with information from waste, site and soil characterization studies, the data generated in treatability studies may be used in predictive mathematical models to: (1) evaluate the effectiveness of use of on-site bioremediation for treatment of wastes in soil systems; (2) develop appropriate containment structures to prevent unacceptable waste transport from the treatment zone; and (3) design performance monitoring strategies.     

Bench‐ and pilot‐scale applications of electrochemical peroxidation: A new remedial concept

Electrochemical peroxidation (ECP) is a proprietary process that utilizes sacrificial iron electrodes and stochiometrically balanced applications of hydrogen peroxide to efficiently destroy aqueous phase contaminants. In laboratory trials it has been successful in reducing, often to non‐detectable levels, BTEX, fuel additives, chlorinated solvents, and polychlorinated biphenyls in ground waters. The process has also been found effective in reducing the chemical and biological oxygen demand of industrial waste water. Agency‐approved pilot tests will be conducted at two gasoline spill sites during 2000 where traditional pump and treat methods have proven ineffectual because of ground water chemistry or subsurface hydrologic conditions. The ECP process utilizes a tripartite treatment strategy consisting of 1) ex situ chemical oxidation; 2) in situ oxidation by reinjection of treated water with residual oxidants at the head of the plume; and 3) reestablishment of aerobic biodegradation by alteration of subsurface redox conditions. In contrast to other in situ oxidation treatment methods, dissolved iron is derived electrochemically, negating the need for ferrous salt addition. Dilute hydrogen peroxide (3 percent) is incrementally added to maximize oxidation efficiency and eliminate safety and environmental concerns accompanying the use of highly concentrated solutions. Results of laboratory trials and the geological and geochemical considerations of upcoming pilot‐scale applications are presented. Other potential applications currently under investigation include combination with other remedial processes (e.g. permeable barriers and hydrogen release compounds) to insure complete and rapid contaminant mineralization.     

Treatment technology for remediation of wood preserving sites: Overview

This is the first in a series of five articles describing the applicability, performance, and cost of technologies for the remediation of contaminated soil and water at wood preserving sites. Site‐specific treatability studies conducted under the supervision of the United States Environmental Protection Agency (US EPA), National Risk Management Research Laboratory (NRMRL), from 1995 through 1997 constitute much of the basis for the evaluations presented, although data from other treatability studies, literature sources, and actual site remediations have also been included to provide a more comprehensive evaluation of remediation technologies. This article provides an overview of the wood preserving sites studied, including contaminant levels, and a summary of the performance of the technologies evaluated. The subsequent articles discuss the performance of each technology in more detail. Three articles discuss technologies for the treatment of soils, including solidification/stabilization, biological treatment, solvent extraction and soil washing. One article discusses technologies for the treatment of liquids, water and nonaqueous phase liquids (NAPLS), including biological treatment, carbon adsorption, photolytic oxidation, and hydraulic containment. The reader should be aware that other technologies including, but not limited to, incineration, thermal desorption, and base catalyzed dehalogenation, also have application for treating contaminants on wood preserving sites. They are not discussed in these five articles since the focus was to evaluate lesser known and hopefully lower cost approaches. However, the reader should include consideration of these other technologies as part of any evaluation or screening of technologies applicable to remediation of wood preserving sites.     

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.     

Novel pilot-scale washing process and equipment for removing Cr(VI) from contaminated soil

In this study, a novel horizontal rotating soil washing process and equipment were developed and tested for pilot-scale remediation of soils from a site polluted by chromium ore process residue. Operating parameters, including cylinder rotational velocity, cylinder tilt angle, heating temperature and liquid/soil ratio, were investigated. The Taguchi method was used for the experiment design, and the standard L16 orthogonal array with four parameters and four levels was selected for optimising the operating parameters. Optimal removal efficiency was achieved at cylinder rotational velocity of 2.5 rpm, cylinder tilt angle of 2.6°, heating temperature of 200 °C and liquid/soil ratio of 8. The efficiency of citric acid as an extractant in the novel process was compared with that of water. The analysis of the residual Cr(VI) concentration of the soil shows that citric acid could efficiently remove 22.89 % more Cr(VI) than water in one-stage washing. The residual Cr(VI) concentration in the soil after the three-stage washing is as low as 26.16 mg/kg, which meets the screening levels for soil environmental risk assessment of sites in Beijing City (30 mg/kg). Further study is currently underway to optimise the novel process and equipment for commercial-scale use.     

Increase in remediation processes of oil‐contaminated soils

A study was conducted in the region of the Lena River, in northeast Russia, where oil‐contaminated soil remediation is compromised due to the reduced natural attenuation mechanisms in northern eco‐systems. The goal of the study was to analyze the effectiveness of different biological methods for remediating the permafrost soil cover contaminated with high concentrations of oil. For the remediation of the areas with approximately similar levels of contamination (in the range of 10 to 14 grams per kilogram [g/kg] of soil) different biological remediation schemes were applied: site 1: sowing plant seeds of meadow clover grass; site 2: introducing a consortium of hydrocarbon oxidizing microorganisms (HOM); and, site 3: introducing the same consortium of HOM with simultaneously sowing grass mixture. The third scheme, applied for the first time, led to the most favorable results, which might be explained by the synergistic effect based on the principle of positive inverse development.     

Operation of a 27‐m3 biopile for the treatment of petroleum‐contaminated soil

Soil and groundwater contamination due to petroleum hydrocarbon spills is a frequent problem worldwide. In Mexico, even when programs oriented to the diminution of these undesirable events exist, in 2000, a total of 1,518 petroleum spills were reported. Exploration zones, refineries, and oil distribution and storage stations frequently are contaminated with total petroleum hydrocarbons (TPH); diesel fraction; gasoline fraction; benzene, toluene, ethyl benzene, and xylenes (BTEX); and polycyclic aromatic hydrocarbons (PAHs). Among the many methodologies available for the treatment of this kind of contaminated soil, bioremediation is the most favorable, because it is an efficient/low‐cost option that is environmentally friendly. This article discusses the capability of using a biopile to treat soils contaminated with about 40,000 mg/kg of TPH. Design and operation of a 27‐m³ biopile is described in this work, including microbiological and respirometric aspects. Parameters such as TPH, diesel fraction, BTEX, and PAHs considered by the U.S. Environmental Protection Agency were measured in biopile samples at 0, 2, 4, 6, 8, 10, and 22 weeks. A final average TPH concentration of 7,300 mg/kg was achieved in 22 weeks, a removal efficiency of 80 percent. © 2007 Wiley Periodicals, Inc.     

Remediation of PCB‐Contaminated Soil Using Extraction and Destruction: Bench‐Scale Test

Polychlorinated biphenyls (PCBs) are a persistent environmental issue worldwide. This study summarizes the results obtained from a bench‐scale test of remediating PCB‐impacted soil. The research aimed to evaluate the effectiveness of extracting the PCB Aroclor 1260 from soil, transferring it to a liquid matrix, and then treating the PCB‐containing liquid using an Activated Metal Treatment System, a technology developed by NASA based on zero valent magnesium (ZVMg). The soil was from a former electrical plant area impacted by PCBs. The initial concentration of untreated soil contained an average of 4.7 ± 0.15 mg/kg of Aroclor 1260. The results showed that the mass transfer phenomena is possible using ethanol as a liquid matrix, reaching transfer results up to 93 percent. The ZVMg enabled the destruction of the Aroclor 1260, which reached 20 percent without any buildup of undesirable by‐products, such as less chlorinated PCBs.  ©2016 Wiley Periodicals, Inc.     

Fate of mutagenic chemicals in soil amended with petroleum and wood preserving sludges

A field study using monoliths (lysimeters) of a sandy clay loam soil was conducted to assess the fate of mutagenic chemicals after refinery and wood preserving bottom sediment sludges were land treated. The Ames Salmonella/microsome assay¹ was used to determine the direct (without metabolic activation, −S9) and indirect (with metabolic activation, + S9) mutagenicity of the wastes, unamended soil, waste amended soils, and leachate. Extracts having a mutagenic ratio (MR) (MR= No. colonies from sample extract/No. colonies from DMSO solvent control) of ⩾ 2 were considered positively mutagenic. Extracts of the wood preserving waste sludge without activation were non-mutagenic (MR < 2) but extracts with activation ( + S9) produced very strong indirect mutagenicity (MR = 7.9). After soil incorporation, the waste amended soil produced very strong direct (MR = 8.9) and indirect (MR = 11.9) mutagenicity by day 180 and remained mutagenic (MR = 5.7, −S9; MR = 3.95, + S9) through day 350. The amount of residue in leachate from the wood preserving waste amended lysimeters was significantly greater (P <0.05) than the unamended soil during the first 90 days after waste application, but was not different after 90 days. The leachate residue from wood preserving waste amended lysimeters in the 90–180-day period produced mutagenic responses both with (MR = 2.24 and 2.51) and without (MR = 2.29) activation. Polynuclear aromatic hydrocarbons were the main constituents identified in the leachate residues that produced a mutagenic response. Soil treatment of the refinery sludge reduced its weak indirect mutagenicity before soil incorporation (MR = 2) to non-mutagenic (MR = 1.4) immediately following soil treatment. The MR of the waste amended soil increased to 1.7 by day 180 but by day 350 decreased to a level equal to that observed at day 0 (MR = 1.4). Leachate from the refinery amended lysimeters had significantly greater (P < 0.05) amounts of organic residue than unamended lysimeters 180 to 350 days after waste application. The leachate from one refinery waste amended lysimeter (90–180 days after waste application) produced a mutagenic response (MR = 3.16). The refinery sludge was detoxified shortly after soil treatment, but the wood preserving sludge required > 350 days to detoxify in the soil environment. The possibility exists that mobile mutagenic chemicals may leach into underlying groundwater from the treatment zone of soils amended with refinery and wood preserving sludges.     

Assessing the potential of using phytoremediation for pyrene‐contaminated soils

Forage crop species representing two biologically distinct families (legumes and grasses) were evaluated on soil spiked with 100 mg/kg of pyrene to determine the potential effectiveness of the rhizospheres of these plants for phytoremediation. In this experiment, pyrene dissipation could not be attributed to the presence of plants. Pyrene dissipation was also not related to rhizosphere biological activity, such as microbial counts and enzyme activity. Planting with reed canarygrass and switchgrass significantly increased the microbial counts in soil; however, the differences in the microbial counts were not correlated to the levels of pyrene dissipation. Reed canarygrass rhizosphere had significantly higher dehydrogenase activity compared to the switchgrass rhizosphere, but this difference in soil dehydrogenase activity was not related to pyrene dissipation. In general, the use of plants was not effective in causing pyrene transformation; however, the presence of vegetation on polycyclic aromatic hydrocarbon–contaminated soils could play a significant role in limiting the spread of contaminants (erosion, leaching) and enhancing ecosystem restoration. © 2004 Wiley Periodicals, Inc.     

A chemox treatment for urea‐ and ammonium‐contaminated groundwater

In a pilot project performed at a fertilizer manufacturing facility, a one‐step chemical oxidation technique successfully treated urea‐ and ammonium‐contaminated groundwater. The oxidation reaction occurred in an 1,100‐gallon batch reactor. The contaminated inflow was buffered by the metered addition of sodium bicarbonate solution and subsequently treated with sodium hypochlorite in an 8:1 weight ratio of Cl₂:N. In an instantaneous reaction, the urea and ammo‐nium‐N were completely oxidized to nitrogen gas that was vented to the atmosphere during mixing. The pH of the reactor discharge was ?6.5. Sodium sulfite was used to reduce residual hypochlorite in the reactor effluent to chloride to provide process water with characteristics suitable for discharge. Oxidation rates were similar with different strengths of hypochlorite; however, a 5 to 6 percent sodium hypochlorite (as Cl₂) solution was the most stable. © 2005 Wiley Periodicals, Inc.     

Evaluation of white‐rot fungi for the remediation of creosote‐contaminated soil

Application of fungal‐based bioaugmentation was evaluated for the remediation of creosote‐contaminated soil at a wood‐preserving site in West Virginia. Soil at the site contained creosote‐range polycyclic aromatic hydrocarbons (PAHs) at concentrations in some areas that exceed industrial risk‐based levels. Two white‐rot fungi (Pleurotus ostreatus and Irpex lacteus) were evaluated for remediation effectiveness in a two‐month bench‐scale treatability test. Both fungi produced similar results, with up to 67.3 percent degradation of total PAHs in 56 days. Pilot‐scale testing was performed at the site using Pleurotus ostreatus grown on two local substrate mixtures. During the 276‐day field trial, total PAHs were degraded by up to 93.2 percent, with all individual PAHs except one achieving industrial risk‐based concentrations. It was recommended that fungal‐based remediation be applied to all contaminated soil at the site. © 2002 Wiley Periodicals, Inc.     

Incorporating ecology and ecological risk into long‐term stewardship on contaminated sites

The long‐term management of environmental contamination will be a major activity at many sites in the foreseeable future. While human health issues often drive decisions about cleanup, restoration, and long‐term stewardship, ecological considerations are also major driving forces and are of paramount importance to the public. Incorporation of ecological considerations into decisions about environmental protection, both short term and long term, requires (1) understanding public perceptions of ecological values, including aesthetics and existence values, (2) understanding contamination issues within a context of the structure and functioning of ecosystems, (3) developing bioindicators of ecological health (including human), (4) developing indicators of ecosystem functioning, and (5) developing and implementing a biomonitoring plan before, during, and after remediation so that adverse effects can be ascertained before they become irreversible. Both remediation/restoration and long‐term stewardship goals must be informed by public policy mandates that include public participation and healthy human and ecological systems. This article examines these issues as they relate to cost‐effective, long‐term protection of human and ecological health on contaminated lands. © 2002 Wiley Periodicals, Inc.     

Six pilot‐scale studies evaluating the in situ treatment of PFAS in groundwater

Per‐ and polyfluoroalkyl substances (PFAS) have been identified by many regulatory agencies as emerging contaminants of concern in a variety of media including groundwater. Currently, there are limited technologies available to treat PFAS in groundwater with the most frequently applied approach being extraction (i.e., pump and treat). While this approach can be effective in containing PFAS plumes, previous studies of pump and treat programs have met with limited remedial success. In situ treatment studies of PFAS have been limited to laboratory and a few field studies. Six pilot‐scale field studies were conducted in an unconfined sand aquifer coimpacted by petroleum hydrocarbon along with PFAS to determine if a variety of reagents could be used to attenuate dissolved phase PFAS in the presence of petroleum hydrocarbons. The six reagents consisted of two chemical oxidants, hydrogen peroxide (H₂O₂) and sodium persulfate (Na₂S₂O₈), and four adsorbents, powdered activated carbon (PAC), colloidal activated carbon (CAC), ion‐exchange resin (IER), and biochar. The reagents were injected using direct push technology in six permeable reactive zone (PRZ) configurations. Groundwater concentrations of various PFAS entering the PRZs ranged up to 24,000 µg/L perfluoropentanoic acid, up to 6,200 µg/L pentafluorobenzoic acid, up to 16,100 µg/L perfluorohexanoic acid, up to 6,080 µg/L perfluoroheptanoic acid, up to 450 µg/L perfluorooctanoic acid, and up to 140 µg/L perfluorononanoic acid. Performance groundwater sampling within and downgradient of the PRZs occurred for up to 18 months using single and multilevel monitoring wells. Results of groundwater sampling indicated that the PFAS were not treated by either the persulfate nor the peroxide and, in some cases, the PFAS increased in concentration immediately following the injection of peroxide and persulfate. Concentrations of PFAS in groundwater sampled within the PAC, CAC, IER, and biochar PRZs immediately after the injection were determined to be less than the method detection limits. Analyses of groundwater samples over the 18‐month monitoring period, indicated that all the PRZs exhibited partial or complete breakthrough of the PFAS over the 18‐month monitoring period, except for the CAC PRZ which showed no PFAS breakthrough. Analysis of cores for the CAC, PAC, and biochar PRZs suggested that the CAC was uniformly distributed within the target injection zone, whereas the PAC and biochar showed preferential injection into a thin coarse‐sand seam. Similarly, analysis of the sand packs of monitoring wells installed before the injection of the CAC, PAC, and biochar indicated that the sand packs of the PAC and biochar preferentially accumulated the reagents compared with the reagent concentrations within the surrounding aquifer by up to 18 times.     

Cement‐based solidification/stabilization of phenol‐contaminated soil by bentonite and organophilic clay

The performance of ordinary and organophilic clays in the solidification and stabilization process was investigated with respect to the unconfined compressive strength (UCS) and leaching of phenol‐contaminated soil. The samples contained 2,000 mg/kg of phenol. White cement (15 and 30 percent by weight [wt%]) was used as binder, while ordinary and organophilic clays (8, 15, and 30 wt%) were applied as additives for reducing the harmful effects of phenol interference in cement hydration with a 28‐day curing time. The results revealed that the UCS is reduced by increasing the amount of clays. The values of UCS of all samples met the minimum standards specified for disposal in sanitary landfills determined by developed countries. The leaching test demonstrated that the degree of leaching diminished with increased clay content in all samples of both clay types. This reduction was observed to be greater in samples containing organophilic clay than in bentonite clay samples. Furthermore, the best composition of the materials tested was determined to be 30 wt% white cement plus 13.3 wt% organophilic clay with a compressive strength of 3,839 kPa, phenol removal percentage of 80 percent, and a cost of $67 per ton of contaminated soil.