Successful UV/oxidation of VOC-contaminated groundwater

Ultraviolet light/oxidation has proven its effectiveness in destroying volatile organic chemicals (VOCs) found in groundwater during a U.S. Environmental Protection Agency (EPA) field study. Under the Superfund Innovative Technology Evaluation (SITE) program, PRC Environmental Management, Inc., and EPA monitored the performance of a system employing advanced oxidation techniques at the Lorentz Barrel & Drum (LB&D) Superfund site in San Jose, California. The firm of Ultrox International (Santa Ana, CA) demonstrated its technology for combining ultraviolet light, hydrogen peroxide and ozone to oxidize toxic organic chemicals found in water. All evaluation criteria were successfully met in the study's results. Greater than 90% of the VOCs were removed. The applicable discharge standards (National Pollution Discharge Elimination System) were attained, and there were no emissions.     

Effect of Changing VOC Influent Composition on the Microbial Community Structure of TBABs

Microbial communities in trickle bed air biofilters (TBABs) were evaluated under conditions of interchanging the feed volatile organic compounds (VOCs) and VOC mixtures. Three independent TBABs (Biofilter “A,” “B,” and “C”) were run under interchanging VOCs conditions with different initial VOCs. Two aromatic compounds (toluene and styrene) and two oxygenated compounds (methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK)) were interchanged as single solutes. Two other TBABs “D” and “E” were run for two VOC mixtures. Biofilter “D” had a VOC mixture with equal molar ratio of the four components and Biofilter “E” received a VOC mixture with its composition based on EPA 2003 emission report. Denaturing gradient gel electrophoresis (DGGE) analysis of 16S rRNA genes was used to assess the microbial richness in TBABs for treating the VOC mixtures and the impact of interchanging VOCs on the bacterial community structure in the biofilters. The results from DGGE indicated that the microbial community structure in the biofilter was different after each interchange of VOCs. Some bands of microbial species faded and some bands were strengthened. For the two TBABs treating VOC mixtures, the microbial species did not show significant difference, but the richness among these species was different from each other.     

Low waste feed concentrations and destruction removal efficiency

In the early 1980s, the Environmental Protection Agency (EPA) funded research on destruction and removal efficiencies (DREs) at eight hazardous waste incinerators. This research appeared to show that DREs of 99.99% could not be achieved at low waste feed principal hazardous organic constituent (POHC) concentrations. During the mid 1980s and 1990s however, testing at Superfund sites has indicated that DREs of 99.9999% or greater can be achieved at low waste feed POHC concentrations. This paper will summarize testing which includes 32 test runs at five Superfund sites and the EPA's incineration research facility. The tests include POHC concentrations from 6552 parts per million down to 28 parts per million at typical DREs of 6–9 s or greater.     

Trace-level measurement of complex combustion effluents and residues using multidimensional gas chromatography-mass spectrometry (MDGC-MS)

The identification and quantitation of non-method-specific target analytes have greater importance with respect to EPA's current combustion strategy. The risk associated with combustion process emissions must now be characterized. EPA has recently released draft guidance on procedures for the collection of emissions data to support and augment site-specific risk assessments (SSRAs) as part of the hazardous waste incineration permitting process. This guidance includes methodology for quantifying total organic (TO) emissions as a function of compound volatility. The ultimate intent is to compare the amount of organic material identified and quantified by target analyte-specific methodologies to organic emissions quantified by the TO methodology. The greater the amount accounted for by the target analyte-specific methodologies, the less uncertainty may be associated with the SSRAs. A limitation of this approach is that the target analyte-specific methodologies do not routinely quantify compounds of low toxicological interest; nor do they target products of incomplete combustion (PICs). Thus, the analysis can miss both toxic and non-toxic compounds. As a result, it is unknown whether the uncharacterized fraction of the TO emission possesses toxic properties. The hypothesis that we propose to test is that organic emissions and organics extracted from particulate matter (PM) are more complex than standard GC-MS-based instrumentation can currently measure. This complexity can affect quantitation for toxic compounds, thereby potentially affecting risk assessments. There is a pressing need to better characterize these organic emissions from hazardous waste incinerators and PM extracts from various other combustion sources. We will demonstrate that multidimensional gas chromatography-mass spectrometry (MDGC-MS) procedures significantly improve chromatographic separation for complex environmental samples. Sequential repetitive heart-cutting MDGC, with coupled mass spectrometry will be shown to be a complete analysis technique. The ability of this technique to disengage components from complex mixtures taken from hazardous and municipal waste incinerators will be shown.     

Volatilization and Biodegradation of VOCs in Membrane Bioreactors (MBR)

Volatilization and biodegradation are major competitive volatile organic compound (VOC) removal mechanisms in biological wastewater treatment process, which depend on compound specific properties and system design/operational parameters. In this study, a mathematical model was used to determine major removal pathways at various organic loading rates (OLR), solids residence time (SRT) and dissolved oxygen (DO) concentrations in a biological process for vinyl acetate. Model results showed that biological treatment process should be designed with long SRT, high OLR and low DO concentrations to maximize biodegradation and minimize volatilization of VOCs. Unless a VOC is toxic to microorganisms under the given conditions, low VOC emission rates are an inherent advantage of MBRs, which operate at higher OLR and longer SRT compared to conventional activated sludge process. A lab scale membrane bioreactor (MBR) was operated at varying OLR to investigate the relative volatilization and biodegradation rates for acetaldehyde, butyraldehyde and vinyl acetate. Synthetic wastewater containing three VOCs was introduced to the MBR. The DO concentration and SRT was maintained at 2.0 mg L^{− 1} and 100 days, respectively. The overall VOC removal rate was more than 99.7% for three VOCs at all the OLR. For vinyl acetate, the biodegradation rate increased from 93.87 to 99.40% and the volatilization removal rate decreased from 6.09 to 0.59% as OLR was increased from 1.1 to 2.0 kg COD m^{− 3} d^{− 1}. It was confirmed that a MBR can be a promising solution to reduce VOC emissions from wastewater.     

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.     

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.     

Application of the US decision support tool for materials and waste management

The US Environmental Protection Agency (US EPA) launched the Resource Conservation Challenge (RCC) in 2002 to help reduce waste and move towards more sustainable resource consumption. The objective of the RCC is to help communities, industries, and the public think in terms of materials management rather than waste disposal. Reducing cost, finding more efficient and effective strategies to manage municipal waste, and thinking in terms of materials management requires a holistic approach that considers life-cycle environmental tradeoffs. The US EPA's National Risk Management Research Laboratory has led the development of a municipal solid waste decision support tool (MSW-DST). The computer software can be used to calculate life-cycle environmental tradeoffs and full costs of different waste management or materials recovery programs. The environmental methodology is based on the use of life-cycle assessment and the cost methodology is based on the use of full-cost accounting. Life-cycle inventory (LCI) environmental impacts and costs are calculated from the point of collection, handling, transport, treatment, and disposal. For any materials that are recovered for recycling, offsets are calculated to reflect potential emissions savings from use of virgin materials. The use of the MSW-DST provides a standardized format and consistent basis to compare alternatives. This paper provides an illustration of how the MSW-DST can be used by evaluating ten management strategies for a hypothetical medium-sized community to compare the life-cycle environmental and cost tradeoffs. The LCI results from the MSW-DST are then used as inputs into another US EPA tool, the Tool for the reduction and assessment of chemical and other environmental impacts, to convert the LCI results into impact indicators. The goal of this paper is to demonstrate how the MSW-DST can be used to identify and balance multiple criteria (costs and environmental impacts) when evaluating options for materials and waste management. This type of approach is needed in identifying strategies that lead to reduced waste and more sustainable resource consumption. This helps to meet the goals established in the US EPA's Resource Conservation Challenge.     

Contaminated land clean-up using composted wastes and impacts of VOCs on land

This paper describes experiments that demonstrate the effects and potential for remediation of a former steelworks site in Wales polluted with polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs). Under field conditions, PAH-contaminated soil was composted in-vessel, with or without organic feedstocks, receiving forced aeration for 80 days followed by 4 months maturation. Treatments compared PAH removal in contaminated soil to contaminated soil mixed with three different organic waste mixes after composting and after composts were spread to land. After composting, PAH concentrations declined in all treatments, by up to 38%. Sixteen months after the composts were landspread and vegetation was established, only those containing contaminated soil with organic additions exhibited further PAH removal, by up to 29%. Composting resulted in a decline in the relative concentration of small PAHs, whereas the landspreading-vegetation phase saw a decline in the relative concentration of medium PAHs in two of the three composts exhibiting PAH removal. Under controlled glasshouse conditions, vegetated soil columns of differing depths were exposed to VOCs from beneath. VOC vapour affected both shoot and root growth and soil microbial activity; effects varied with distance from the VOC source. This work demonstrated that on-site remediation of aged PAH-contaminated land can be successfully initiated by in-vessel co-composting followed by land spreading and vegetation, within a practical timeframe.     

Triad case study: Marine Corps Base Camp Pendleton

The U.S. Navy Public Works Center (PWC) Environmental Department, San Diego, California, is home to the Navy West Coast Site Characterization and Analysis Penetrometer System (SCAPS). SCAPS has been extensively used at several Navy sites since 1995 to provide real‐time, high‐density data sets. The U.S. Environmental Protection Agency's Triad approach provided an ideal framework for optimizing the use of the Navy SCAPS during a volatile organic compound (VOC) source investigation at Installation Restoration Site 1114 at Marine Corps Base Camp Pendleton. All three elements of Triad—systematic planning, dynamic work strategy, and use of real‐time measurement tools—were implemented to manage decision uncertainty and expedite the site management process. The investigation was conducted using the Navy SCAPS, outfitted with a cone penetrometer, membrane interface probe, and a direct sampling ion trap mass spectrometry detector, which allowed for real‐ time collection of over 690 feet of continuous lithologic information and VOC concentration data. These data were used collaboratively with 24‐hour turnaround US EPA 8260B VOC groundwater results from temporary direct‐ push wells to support the conclusion of a limited source area. Implementation of the Triad approach for this investigation provided an expedited high‐density data set and a refined conceptual site model (CSM) in real time that resulted in cost savings estimated at $2.5M and reduction of the site characterization and cleanup schedule by approximately three years. This project demonstrates how the US EPA's Triad approach can be applied to streamline the site characterization and cleanup process while appropriately managing decision uncertainty in support of defensible site decisions. © 2004 Wiley Periodicals, Inc.     

Remediation of groundwater contamination through conjunctive use of landfill gas management and soil vapor extraction

The recently completed performance testing of a conjunctive-use operation has demonstrated the applicability of combined landfill gas and Volatile Organic Compound (VOC) removal with overall contaminant migration management. The extraction of landfill gas (with subsequent control of off-site gas migration) and the removal of VOCs from the landfill gas/soil air environment will minimize VOC solubilization in the underlying groundwater. This, in turn, will permit cost efficient management of contaminant migration at the site.     

Look at groundwater quality to set VOC cleanup levels

In 1981, the Arizona Department of Health Services (ADHS) discovered groundwater contamination by solvents and chromium at the Phoenix Goodyear Airport (PGA), just outside the city of Phoenix. ADHS and the U.S. EPA sampled the site for the next two years, finding that eighteen of their wells were contaminated with trichloroethene (TCE), six exceeding ADHS's action level of five micrograms per liter (μg/l). In 1983, the PGA site was added to the National Priorities List, and, in 1984, EPA began a $3 million remedial investigation, focusing on soils and groundwater. This article discusses how that investigation inspired the authors to develop a stream-lined evaluation method for PGA's volatile organic compounds (VOCs), the process for establishing VOC cleanup levels, and the $26 million of remediation work needed to be done at the site. The heart of this effort is a computer program called VLEACH, loosely standing for VOC-LEACHing, which anticipates the influence of VOCs on PGA's groundwater, even as remediation proceeds.     

Determination of inorganic and organic priority pollutants in biosolids from meat processing industry

The biosolids (BS) generated in the wastewater treatment process of a meat processing plant were monitored and the priority pollutant content was characterized. The trace metal and organic pollutant content – polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDF) – were determined quantitatively and compared to guideline limits established by the US EPA and EU. PCBs were not detected in the solid samples, while trace metals, PAHs and PCDD/PCDF were detected in concentrations below the limits established by international standards. Toxic equivalent factors were evaluated for the biosolids, and the results proved that these wastes can be safely deposited on land or used in combustion/incineration plants. Since no previous data were found for meat processing waste, comparisons were made using municipal sewage sludge data reported in the literature. Since, this report monitored part of the priority pollutants established by the US EPA for meat and poultry processing wastewater and sludge, the results verified that low pollution loads are generated by the meat processing plant located in the southern part of Brazil. However, the BS generated in the treatment processes are in accordance with the limits established for waste disposal and even for soil fertilizer.     

Breakthrough in 2D‐CSIA Technology for 1,4‐Dioxane

A dual isotope technology based on compound‐specific stable isotope analysis of carbon and hydrogen (2D‐CSIA) was recently developed to help identify sources and monitor in situ degradation of the contaminant 1,4‐dioxane (1,4‐D) in groundwater. Site investigation and optimized remediation have been the focus of thousands of CSIA applications completed for volatile organic contaminants (VOCs) worldwide. CSIA for the water miscible 1,4‐D, however, has been technically challenging. The most commercially available sample preparation settings “Purge and Trap” for VOC could not efficiently extract 1,4‐D out of water for a reliable CSIA measurement, especially when the concentration is below 100 μg/L. Such a high reporting limit has prevented CSIA from being used for effective site investigation and remediation monitoring at most 1,4‐D contaminated sites, where 1,4‐D is often present at very low ppb levels. This article outlines the recent breakthrough in 2D‐CSIA technology for 1,4‐D in water, reported down to ～1 μg/L for carbon, and ～10 μg/L to 20 μg/L for hydrogen using solid‐phase extraction based on EPA Method 522, and its benefit is highlighted through a case study at a 1,4‐D contaminated site. ©2016 Wiley Periodicals, Inc.     

Inventory and treatment of compost maturation emissions in a municipal solid waste treatment facility

Emissions of volatile organic compounds (VOCs) from the compost maturation building in a municipal solid waste treatment facility were inventoried by solid phase microextraction and gas chromatography–mass spectrometry. A large diversity of chemical classes and compounds were found. The highest concentrations were found for n-butanol, methyl ethyl ketone and limonene (ppm_v level). Also, a range of compounds exceeded their odor threshold evidencing that treatment was needed. Performance of a chemical scrubber followed by two parallel biofilters packed with an advanced packing material and treating an average airflow of 99,300 m³ h^?1 was assessed in the treatment of the VOCs inventoried. Performance of the odor abatement system was evaluated in terms of removal efficiency by comparing inlet and outlet abundances. Outlet concentrations of selected VOCs permitted to identify critical odorants emitted to the atmosphere. In particular, limonene was found as the most critical VOC in the present study. Only six compounds from the odorant group were removed with efficiencies higher than 90%. Low removal efficiencies were found for most of the compounds present in the emission showing a significant relation with their chemical properties (functionality and solubility) and operational parameters (temperature, pH and inlet concentration). Interestingly, benzaldehyde and benzyl alcohol were found to be produced in the treatment system.     

Characterization and pilot‐scale studies for chemical oxidation remediation of fractured shale

The distribution of volatile organic compounds (VOCs) in fractured shale overlain by thin (< 10 feet) overburden at the Watervliet Arsenal near Albany, New York, was initially determined by sampling water from the fracture network using packer systems in boreholes and also using conventional monitoring wells. Furthermore, short‐term pumping and injection tests were conducted and the boreholes were logged using a variety of geophysical and hydrophysical tools. Tetrachloroethene is the dominant VOC in the groundwater, with lesser concentrations of trichloroethene and degradation products (cis‐1,2‐dichloroethene, trans‐1,2‐dichloroethene, and vinyl chloride). The vertical VOC distributions in the rock matrix were obtained from continuous‐cored holes from which small rock samples, collected at many depths between 18 and 150 feet below ground surface, were analyzed. The rock core VOC concentrations were determined by methanol extraction of crushed rock followed by direct methanol injection onto a gas chromatograph and subsequent estimation of rock porewater VOC concentrations. The rock core data support the concept that diffusion‐driven mass transfer has caused nearly all the VOC mass initially present in the fractures to now reside in the rock matrix, which has a porosity three or four orders of magnitude larger than the bulk fracture porosity. The results of the site characterization indicate that an effective site investigation strategy in fractured shale must include characterization of both the fracture and matrix contaminant distribution. These results also indicate that the most favorable remediation technologies for this fractured shale are those that will destroy VOCs in the rock matrix, particularly contaminants in the sorbed phase, and also destroy the VOC mass in the fractures including both dissolved and immiscible phases. The site characterization resulted in the selection of potassium permanganate for an in situ chemical oxidation pilot study. © 2004 Wiley Periodicals, Inc.     

Building pressure control test to examine if VOC contamination in indoor air is caused by an interior source or by a subslab source

When determining whether or not remediation of subslab contamination is warranted, it is often important to know if the presence of volatile organic compounds (VOCs) in indoor air is caused primarily by interior sources, or primarily by subslab contamination. With a Building Pressure Control test, the pressure differential across the building envelope and, thereby, also the pressure differential across the slab, can be controlled by a blower. By measuring the indoor air concentrations of VOCs under depressurization (upward pressure gradient over the slab) and under pressurization (downward pressure gradient over the slab), it can be determined if the subslab contamination contributes significantly to the VOC concentrations in indoor air. This technique has been applied at several sites in the Central Denmark Region, and the results show that a Building Pressure Control test is a quick and effective method to examine if VOC contamination in indoor air is caused primarily by interior sources or primarily by subslab sources. With numerous measurement points in the indoor air, at some sites this test method has identified the area where the subslab contamination is located. A pressure differential at ?5/+5 Pa across the building envelope was sufficient at all the test sites to control the pressure gradient across the slab to be uniquely upward/downward.     

Methane–benzene binary mixture destruction in a reverse flow catalytic reactor

An experimental study of methane–benzene binary mixture purification in a bench-scale reverse flow reactor is carried out. Results for catalytic oxidation of the two hydrocarbons with remarkably discrepant chemical properties show that autothermal catalytic combustion of very lean combustible concentration can be achieved with periodic feed reversal. Benzene is well removed, but methane conversion is relatively low and mainly determined by the thermal level of the reactor. If methane is added as auxiliary fuel to maintain autothermal operation when the volatile organic compound (VOC) concentration in the contaminated air is too low, an excess amount is needed. The influences of gas superficial velocity, cycle period, and methane-to-benzene ratio are discussed. A mathematical model is developed and solved using a FORTRAN code, with good correspondence being observed between the two approaches. Results of experimental and numerical study indicate that, during catalytic oxidation of lean VOCs in reverse flow reactor, the mutual inhibition effect between different kinds of hydrocarbon can be neglected.     

Characterizing emissions from open burning of military food waste and ration packaging compositions

Emissions from open burning of military food waste and ration packaging compositions were characterized in response to health concerns from open burning disposal of waste, such as at military forward operating bases. Emissions from current and prototype Meals, Ready-to-Eat (MREs), and material options for their associated fiberboard packaging were quantified to assess contributions of the individual components. MREs account for 67–100% of the particulate matter (PM), volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), and polychlorinated dibenzo-p-dioxins and -furans (PCDDs/PCDFs) emissions when burned in unison with the current fiberboard container and liner. The majority of the particles emitted from these burns are of median diameter 2.5 µm (PM_2.5). Metal emission factors were similar regardless of waste composition. Measurements of VOCs and PAHs indicate that targeted replacement of MRE components may be more effective in reducing emissions than variation of fiberboard-packaging types. Despite MRE composition variation, equivalent emission factors for PM, PAH, VOC, and PCDD/PCDF were seen. Similarly, for fiberboard packaging, composition variations exhibited essentially equivalent PM, PAH, VOC, and PCDD/PCDF emission factors amongst themselves. This study demonstrated a composition-specific analysis of waste burn emissions, assessing the impact of waste component substitution using military rations.     

Mass transport of organic contaminants through a self-sealing/self-healing mineral landfill liner

The self-sealing/self-healing (SS/SH) liner system is based on the fundamental principle that an impermeable seal is self-formed and self-healed by the pozzolanic reaction at the interface between two adjacent reactive layers. The objectives of this study were to evaluate the effect of contaminants on the performance of an SS/SH liner used as a hydraulic barrier, to understand mechanism of volatile organic compound (VOC) sorption on the SS/SH materials, and to estimate the mass transport parameters of contaminants through the SS/SH liner materials. The hydraulic conductivity of the liner material decreased continuously with time, and stabilized at less than 1 × 10^–7cm/s after approximately 15 days. It is known that the seal at the interface between two reactive layers is self-formed over time, and this contributes to the decrease in the hydraulic conductivity of such a liner system. The retardation of the seven target VOCs tested was greater in the SS/SH liner materials than in a clayey soil specimen owing to the higher sorption capacity. An analytical solution developed to test column equipment could reduce the time required to estimate the hydrodynamic dispersion coefficients of organic compounds by using the data on changes in concentration in the upper reservoir of the column.