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At least 109 records · Page 6

Multivariate analysis of progressive thermal desorption coupled gas chromatography-mass spectrometry.

Thermal decomposition of poly dimethyl siloxane compounds, Sylgard{reg_sign} 184 and 186, were examined using thermal desorption coupled gas chromatography-mass spectrometry (TD/GC-MS) and multivariate analysis. This work describes a method of producing multiway data using a stepped thermal desorption. The technique involves sequentially heating a sample of the material of interest with subsequent analysis in a commercial GC/MS system. The decomposition chromatograms were analyzed using multivariate analysis tools including principal component analysis (PCA), factor rotation employing the varimax criterion, and multivariate curve resolution. The results of the analysis show seven components related to offgassing of various fractions of siloxanes that vary as a function of temperature. Thermal desorption coupled with gas chromatography-mass spectrometry (TD/GC-MS) is a powerful analytical technique for analyzing chemical mixtures. It has great potential in numerous analytic areas including materials analysis, sports medicine, in the detection of designer drugs; and biological research for metabolomics. Data analysis is complicated, far from automated and can result in high false positive or false negative rates. We have demonstrated a step-wise TD/GC-MS technique that removes more volatile compounds from a sample before extracting the less volatile compounds. This creates an additional dimension of separation before the GC column, while simultaneously generating three-way data. Sandia's proven multivariate analysis methods, when applied to these data, have several advantages over current commercial options. It also has demonstrated potential for success in finding and enabling identification of trace compounds. Several challenges remain, however, including understanding the sources of noise in the data, outlier detection, improving the data pretreatment and analysis methods, developing a software tool for ease of use by the chemist, and demonstrating our belief that this multivariate analysis will enable superior differentiation capabilities. In addition, noise and system artifacts challenge the analysis of GC-MS data collected on lower cost equipment, ubiquitous in commercial laboratories. This research has the potential to affect many areas of analytical chemistry including materials analysis, medical testing, and environmental surveillance. It could also provide a method to measure adsorption parameters for chemical interactions on various surfaces by measuring desorption as a function of temperature for mixtures. We have presented results of a novel method for examining offgas products of a common PDMS material. Our method involves utilizing a stepped TD/GC-MS data acquisition scheme that may be almost totally automated, coupled with multivariate analysis schemes. This method of data generation and analysis can be applied to a number of materials aging and thermal degradation studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Identifying Sources of Volatile Organic Compounds and Aldehydes in a High Performance Building

The developers of the Paharpur Business Center (PBC) and Software Technology Incubator Park in New Delhi, India offer an environmentally sustainable building with a strong emphasis on energy conservation, waste minimization and superior indoor air quality (IAQ). To achieve the IAQ goal, the building utilizes a series of air cleaning technologies for treating the air entering the building. These technologies include an initial water wash followed by ultraviolet light treatment and biolfiltration using a greenhouse located on the roof and numerous plants distributed throughout the building. Even with the extensive treatment of makeup air and room air in the PBC, a recent study found that the concentrations of common volatile organic compounds and aldehydes appear to rise incrementally as the air passes through the building from the supply to the exhaust. This finding highlights the need to consider the minimization of chemical sources in buildings in combination with the use of advanced air cleaning technologies when seeking to achieve superior IAQ. The goal of this project was to identify potential source materials for indoor chemicals in the PBC. Samples of building materials, including wood paneling (polished and unpolished), drywall, and plastic from a hydroponic drum that was part of the air cleaning system, were collected from the building for testing. All materials were collected from the PBC building and shipped to the Lawrence Berkeley National Laboratory (LBNL) for testing. The materials were pre-conditioned for two different time periods before measuring material and chemical specific emission factors for a range of VOCs and Aldehydes. Of the six materials tested, we found that the highest emitter of formaldehyde was new plywood paneling. Although polish and paint contribute to some VOC emissions, the main influence of the polish was in altering the capacity of the surface to accumulate formaldehyde. Neither the new nor aged polish contributed significantly to formaldehyde emissions. The VOC emission stream (excluding formaldehyde) was composed of up to 18 different chemicals and the total VOC emissions ranged in magnitude from 7 mu g/m2/h (old wood with old polish) to>500 mu g/m2/h (painted drywall). The formaldehyde emissions from drywall and old wood with either new or old polish were ~;;15 mu g/m2/h while the new wood material emitted>100 mu g/m2/h. However, when the projected surface area of each material in the building was considered, the new wood, old wood and painted drywall material all contributed substantially to the indoor formaldehyde loading while the coatings contributed primarily to the VOCs.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

New Air Cleaning Strategies for Reduced Commercial Building Ventilation Energy

Approximately ten percent of the energy consumed in U.S. commercial buildings is used by HVAC systems to condition outdoor ventilation air. Reducing ventilation rates would be a simple and broadly-applicable energy retrofit option, if practical counter measures were available that maintained acceptable concentrations of indoor-generated air pollutants. The two general categories of countermeasures are: 1) indoor pollutant source control, and 2) air cleaning. Although pollutant source control should be used to the degree possible, source control is complicated by the large number and changing nature of indoor pollutant sources. Particle air cleaning is already routinely applied in commercial buildings. Previous calculations indicate that particle filtration consumes only 10percent to 25percent of the energy that would otherwise be required to achieve an equivalent amount of particle removal with ventilation. If cost-effective air cleaning technologies for volatile organic compounds (VOCs) were also available, outdoor air ventilation rates could be reduced substantially and broadly in the commercial building stock to save energy. The research carried out in this project focuses on developing novel VOC air cleaning technologies needed to enable energy-saving reductions in ventilation rates. The minimum required VOC removal efficiency to counteract a 50percent reduction in ventilation rate for air cleaning systems installed in the HVAC supply airstream is modest (generally 20percent or less).

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Impact of Heavy Duty Vehicle Emissions Reductions on Global Climate

The impact of a specified set of emissions reductions from heavy duty vehicles on climate change is calculated using the MAGICC 5.3 climate model. The integrated impact of the following emissions changes are considered: CO2, CH4, N2O, VOC, NOx, and SO2. This brief summarizes the assumptions and methods used for this calculation.

03 NATURAL GAS↗

Effects of Carbonate Minerals on Shale-Hydraulic Fracturing Fluid Interactions in the Marcellus Shale

Natural gas extracted from tight shale formations, such as the Marcellus Shale, represents a significant and developing front in energy exploration. By fracturing these formations using pressurized fracturing fluid, previously unobtainable hydrocarbon reserves may be tapped. While pursuing this resource, hydraulic fracturing operations leave chemically complex fluids in the shale formation for at least two weeks. This provides a substantial opportunity for the hydraulic fracturing fluid (HFF) to react with the shale formation at reservoir temperature and pressure. In this study, we investigated the effects of the carbonates on shale-HFF reactions with a focus on the Marcellus Shale. We performed autoclave experiments at high temperature and pressure reservoir conditions using a carbonate-rich and a decarbonated or carbonate-free version of the same shale sample. We observed that carbonate minerals buffer the pH of the solution, which in turn prevents clay dissolution. Carbonate and bicarbonate ions also scavenge reactive oxidizing species (ROS), which prevents oxidation of shale organic matter and volatile organic compounds (VOCs). Carbonate-free samples also show higher pyrite dissolution compared to the carbonate-rich sample due to chelation reactions. This study demonstrates how carbonate minerals (keeping all other variables constant) affect shale-HFF reactions that can potentially impact porosity, microfracture integrity, and the release of heavy metals and volatile organic contaminants in the produced water.

58 GEOSCIENCES↗

Measurements of volatile organic compounds at a suburban ground site (T1) in Mexico City during the MILAGRO 2006 campaign: Measurement comparison, emission ratios, and source attribution

Volatile organic compound (VOC) mixing ratios were measured with two different instruments at the T1 ground site in Mexico City during the Megacity Initiative: Local and Global Research Observations (MILAGRO) campaign in March of 2006. A gas chromatograph with flame ionization detector (GC-FID) quantified 18 light alkanes, alkenes and acetylene while a proton-transfer-reaction ion-trap mass spectrometer (PIT-MS) quantified 12 VOC species including oxygenated VOCs (OVOCs) and aromatics. A GC separation system was used in conjunction with the PIT-MS (GC-PIT-MS) to evaluate PIT-MS measurements and to aid in the identification of unknown VOCs. The VOC measurements are also compared to simultaneous canister samples and to two independent proton-transfer-reaction mass spectrometers (PTR-MS) deployed on a mobile and an airborne platform during MILAGRO. VOC diurnal cycles demonstrate the large influence of vehicle traffic and liquid propane gas (LPG) emissions during the night and photochemical processing during the afternoon. Emission ratios for VOCs and OVOCs relative to CO are derived from early-morning measurements. Average emission ratios for non-oxygenated species relative to CO are on average a factor of {approx}2 higher than measured for US cities. Emission ratios for OVOCs are estimated and compared to literature values the northeastern US and to tunnel studies in California. Positive matrix factorization analysis (PMF) is used to provide insight into VOC sources and processing. Three PMF factors were distinguished by the analysis including the emissions from vehicles, the use of liquid propane gas and the production of secondary VOCs + long-lived species. Emission ratios to CO calculated from the results of PMF analysis are compared to emission ratios calculated directly from measurements. The total PIT-MS signal is summed to estimate the fraction of identified versus unidentified VOC species.

54 ENVIRONMENTAL SCIENCES↗

Summertime photochemistry during CAREBeijing-2007: ROx budgets and O3 formation

We analyze summertime photochemistry near the surface in Beijing, China, using a 1-D photochemical model (Regional chEmical and trAnsport Model, REAM-1D) constrained by in situ observations, focusing on the budgets of ROx (OH + HO2 + RO2) radicals and O3 formation. While the modeling analysis focuses on near-surface photochemical budgets, the implications for the budget of O3 in the planetary boundary layer are also discussed. In terms of daytime average, the total ROx primary production rate near the surface in Beijing is 6.6 ppbv per hour (ppbv h{sup 1}, among the highest found in urban atmospheres. The largest primary ROx source in Beijing is photolysis of oxygenated volatile organic compounds (OVOCs), which produces HO2 and RO2 at 2.5 ppbv h{sup 1}1 and 1.7 ppbv h{sup 1}, respectively. Photolysis of excess HONO from an unknown heterogeneous source is the predominant primary OH source at 2.2 ppbv h{sup 1}, much larger than that of O1D+H2O (0.4 ppbv h{sup 1}). The largest ROx sink is via OH + NO2 reaction (1.6 ppbv h{sup 1}), followed by formation of RO2NO2 (1.0 ppbv h{sup 1}) and RONO2 (0.7 ppbv h{sup 1}). Due to the large aerosol surface area, aerosol uptake of HO2 appears to be another important radical sink, although the estimate of its magnitude is highly variable depending on the uptake coefficient value used. The daytime average O3 production and loss rates near the surface are 32 ppbv h{sup 1} and 6.2 ppbv h{sup 1}, respectively. Assuming NO2 to be the source of excess HONO, the NO2 to HONO transformation leads to considerable O3 loss and reduction of its lifetime. Our observation-constrained modeling analysis suggests that oxidation of VOCs (especially aromatics) and heterogeneous reactions (e.g. HONO formation and aerosol uptake HO2) play potentially critical roles in the primary radical budget and O3 formation in Beijing. One important ramification is that O3 production is neither NOx nor VOC limited, but in a transition regime where reduction of either NOx or VOCs could result in reduction of O3 production. The transition regime implies more flexibility in the O3 control strategies than a binary system of either NOx or VOC limited regime. The co-benefit of concurrent reduction of both NOx and VOCs in reducing column O3 production integrated in the planetary boundary layer is significant. Further research on the spatial extent of the transition regime over the polluted eastern China is critically important for controlling regional O3 pollution.

54 ENVIRONMENTAL SCIENCES↗

Cryogenic particle collection on a cometary mission

The present investigation is concerned with research related to the design of a method for capturing effectively particulate matter and volatiles from the tail of a comet for the purpose of chemical analysis. It is envisaged to conduct a space mission with a means of propulsion which would make it possible to maneuver the space probe into the coma of the comet. The collecting medium has to be chemically inert and easily distinguishable from the particles being collected. It is proposed to employ a film of solid xenon at a temperature of 65 K as the collecting medium. Sublimation of this film and the resultant pressure will be used to concentrate the particles on a small area suitable for analysis. Attention is given to the laboratory apparatus, the experimental work, the experimental results, and the cryogenic requirements for a space mission.

Szara, R. J.↗

Emission Characteristics of an Axially Staged Sector Combustor for a Small Core High OPR Subsonic Aircraft Engine

Gaseous (NOx, CO) and non-volatile particulate matter (nvPM) emissions from a small-core high-pressure Axially Controlled Stoichiometry (ACS) combustor are reported. NOx and CO emissions characteristics are similar to a previous version of ACS combustor. Emissions of nvPM at low-power (fuel-rich front end) was found to procude significantly higher nvPM emissions compared to a high-power configuration (fuel-lean front end). NOx emissions for the ACS combustor were 82-89% below the ICAO CAEP/6 standard for aggressive NASA N+3 high-pressure cycles based on NOx correlations developed from experimental measurements.

He, Zhuohui J.↗

Low NOx Fuel-Flex Combustor Summary

Combustion and emissions testing of United Technologies Research Center’s (UTRC’s) small core combustor in NASA GRC’s CE-5 flametube test facility comprising of LTO and cruise conditions has been completed. Sufficient NOx emissions data was collected to formulate correlation equations for assessing reductions in NOx for LTO against CAEP/6 and cruise against 2005 best-in-class. Back-to-back testing of Jet-A fuel and a 50/50 blend of Jet-A with an alternative fuel demonstrated a measurable effect of fuel composition on non-volatile particulate matter emissions. Post-test analysis indicates LTO NOx emissions >80% below CAEP6 in UTRC single-sector tests of small-core N+3 combustor. Documentation describing N+3 combustor concept selected, design approach, initial flametube test & analysis results; and preferred concept recommended for higher fidelity research has also been completed. This Lean Burn combustor concept shows potential to meet/exceed NASA’s Far Term LTO NOX reduction goals, but further investigation of dynamic characteristics of the combustor concept are required to ensure good operability over the entire flight regime conditions.

Angela D Surgenor↗

Use of 2nd and 3rd Level Correlation Analysis for Studying Degradation in Polycrystalline Thin-Film Solar Cells

The correlation of stress-induced changes in the performance of laboratory-made CdTe solar cells with various 2nd and 3rd level metrics is discussed. The overall behavior of aggregated data showing how cell efficiency changes as a function of open-circuit voltage (Voc), short-circuit current density (Jsc), and fill factor (FF) is explained using a two-diode, PSpice model in which degradation is simulated by systematically changing model parameters. FF shows the highest correlation with performance during stress, and is subsequently shown to be most affected by shunt resistance, recombination and in some cases voltage-dependent collection. Large decreases in Jsc as well as increasing rates of Voc degradation are related to voltage-dependent collection effects and catastrophic shunting respectively. Large decreases in Voc in the absence of catastrophic shunting are attributed to increased recombination. The relevance of capacitance-derived data correlated with both Voc and FF is discussed.

14 SOLAR ENERGY↗

Observations of the Temperature Dependent Response of Ozone to NOx Reductions in an Urban Plume

Observations of NO{sub x} in the Sacramento, CA region show that mixing ratios decreased by 30% between 2001 and 2008. Here we use an observation-based method to quantify net ozone production rates in the outflow from the Sacramento metropolitan region and examine the O{sub 3} decrease resulting from reductions in NO{sub x} emissions. This observational method does not rely on assumptions about detailed chemistry of ozone production, rather it is an independent means to verify and test these assumptions. We use an instantaneous steady-state model as well as a detailed 1-D plume model to aid in interpretation of the ozone production inferred from observations. In agreement with the models, the observations show that early in the plume, the NO{sub x} dependence for O{sub x} (O{sub x} = O{sub 3}+NO{sub 2}) production is strongly coupled with temperature, suggesting that temperature dependent biogenic VOC emissions can drive O{sub x} production between NO{sub x}-limited and NO{sub x}-suppressed regimes. As a result, NO{sub x} reductions were found to be most effective at higher temperatures over the 7 year period. We show that violations of the California 1-hour O{sub 3} standard (90 ppb) in the region have been decreasing linearly with decreases in NO{sub x} (at a given temperature) and predict that reductions of NO{sub x} concentrations (and presumably emissions) by an additional 30% (relative to 2007 levels) will eliminate violations of the state 1 hour standard in the region. If current trends continue, a 30% decrease in NO{sub x} is expected by 2012, and an end to violations of the 1 hour standard in the Sacramento region appears to be imminent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oligomeric Dithienopyrrole-Thienopyrrolodione (DTP-TPD) Donor-Acceptor Copolymer for Organic Photovoltaics: Preprint

A new donor-acceptor copolymer system based upon a dithienopyrrole (DTP) donor moiety and a thienopyrrolodione (TPD) accepting moiety has been designed and synthesized for organic photovoltaic (OPV) applications. The TPD accepting moiety has recently gained significant attention in the OPV community and is being incorporated into a number of different polymer systems. In contrast, the DTP donormoiety has received only limited attention, likely due in part to synthetic difficulties relating to the monomer. In our hands, the bis(trimethyltin)-DTP monomer was indelibly contaminated with~5% of the mono-destannylated DTP, which limited the Stille polymerization with the dibromo-TPD monomer (>99% pure) to produce material with Mn~4130 g/mol (PDI = 1.10), corresponding to around eightrepeat units. Despite this limitation, UV-visible absorption spectroscopy demonstrates strong absorption for this material with a band gap of~1.6 eV. Cyclic voltammetry indicates a highest occupied molecular orbital (HOMO) energy level of -5.3 eV, which is much lower than calculations predicted. Initial bulk heterojunction OPV devices fabricated with the fullerene acceptor phenyl C61 butyricacid methyl ester (PCBM) exhibit Voc~700 mV, which supports the deep HOMO value obtained from CV. These results suggest the promise of this copolymer system.

14 SOLAR ENERGY↗

Determining Outdoor CPV Cell Temperature (Presentation)

An accurate method is needed for determining cell temperature when measuring CPV modules outdoors. It has been suggested that cell temperature can be calculated though a procedure that shutters sunlight to the cells while measuring the transients in open-circuit voltage (Voc) and heat sink temperature. This presentation documents application of this shutter procedure to multiple CPV modules atNREL. The challenges and limitations are presented along with an alternate approach to measuring CPV cell operating temperature.

14 SOLAR ENERGY↗

25 Years Of Environmental Remediation In The General Separations Area Of The Savannah River Site: Lessons Learned About What Worked And What Did Not Work In Soil And Groundwater Cleanup

The Savannah River Site (SRS) is owned and administered by the US Department of Energy (DOE). SRS covers an area of approximately 900 square kilometers. The General Separation Area (GSA) is located roughly in the center of the SRS and includes: radioactive material chemical separations facilities, radioactive waste tank farms, a variety of radioactive seepage basins, and the radioactive waste burial grounds. Radioactive wastes were disposed in the GSA from the mid-1950s through the mid-1990s. Radioactive operations at the F Canyon began in 1954; radioactive operations at H Canyon began in 1955. Waste water disposition to the F and H Seepage Basins began soon after operations started in the canyons. The Old Radioactive Waste Burial Ground (ORWBG) began operations in 1952 to manage solid waste that could be radioactive from all the site operations, and ceased receiving waste in 1972. The Mixed Waste Management Facility (MWMF) and Low Level Radioactive Waste Disposal Facility (LLRWDF) received radioactive solid waste from 1969 until 1995. Environmental legislation enacted in the 1970s, 1980s, and 1990s led to changes in waste management and environmental cleanup practices at SRS. The US Congress passed the Clean Air Act in 1970, and the Clean Water Act in 1972; the Resource Conservation and Recovery Act (RCRA) was enacted in 1976; the Comprehensive Environmental Response Compensation, and Liability Act (CERCLA) was enacted by Congress in 1980; the Federal Facilities Compliance Act (FFCA) was signed into law in 1992. Environmental remediation at the SRS essentially began with a 1987 Settlement Agreement between the SRS and the State of South Carolina (under the South Carolina Department of Health and Environmental Control - SCDHEC), which recognized linkage between many SRS waste management facilities and RCRA. The SRS manages several of the larger groundwater remedial activities under RCRA for facilities recognized early on as environmental problems. All subsequent environmental remediation projects tend to be managed under tri-party agreement (DOE, Environmental Protection Agency, and SCDHEC) through the Federal Facilities Agreement. During 25 years of environmental remediation SRS has stabilized and capped seepage basins, and consolidated and capped waste units and burial grounds in the GSA. Groundwater activities include: pump and treat systems in the groundwater, installation of deep subsurface barrier systems to manage groundwater flow, in situ chemical treatments in the groundwater, and captured contaminated groundwater discharges at the surface for management in a forest irrigation system. Over the last 25 years concentrations of contaminants in the aquifers beneath the GSA and in surface water streams in the GSA have dropped significantly. Closure of 65 waste sites and 4 RCRA facilities has been successfully accomplished. Wastes have been successfully isolated in place beneath a variety of caps and cover systems. Environmental clean-up has progressed to the stage where most of the work involves monitoring, optimization, and maintenance of existing remedial systems. Many lessons have been learned in the process. Geotextile covers outperform low permeability clay caps, especially with respect to the amount of repairs required to upkeep the drainage layers as the caps age. Passive, enhanced natural processes to address groundwater contamination are much more cost effective than pump and treat systems. SRS operated two very large pump and treat systems at the F and H Seepage Basins to attempt to limit the release of tritium to Fourmile Branch, a tributary of the Savannah River. The systems were designed to extract contaminated acidic groundwater, remove all contamination except tritium (not possible to remove the tritium from the water), and inject the tritiated groundwater up-gradient of the source area and the plume. The concept was to increase the travel time of the injected water for radioactive decay of the tritium. The two systems were found to be non-effective and potentially mobilizing more contamination. SRS invested approximately $50 million in construction and approximately $100 million in 6 years of operation. The H Seepage Basin pump and treat system was replaced by a series of subsurface barriers that alters the groundwater velocity; the F Seepage Basin pump and treat system was replaced by subsurface barriers forming a funnel and gate augmented by chemical treatment within the gates. These replacement systems are mostly passive and cost approximately $13 million to construct, and have reduced the tritium flux to Fourmile Branch, in these plumes, by over 70%. SRS manages non-acidic tritiated groundwater releases to Fourmile Branch from the southwest plume of the MWMF with a forest irrigation system. Tritiated water is captured with a sheetpile dam below the springs that caused releases to Fourmile Branch. Water from the irrigation pond is pumped to a filter plant prior to irrigation of approximately 26 hectares of mixed forest and developing pine plantation. SRS has almost achieved a 70% reduction in tritium flux to the Branch from this plume. The system cost approximately $5 million to construct with operation cost of approximately $500K per year. In conclusion, many lessons have been learned in 25 years of relatively aggressive remedial activities in the GSA. Geotextile covers outperform low permeability clay caps, especially with respect to the amount of repairs required to upkeep the drainage layers as the caps age. Passive, enhanced natural processes to address groundwater contamination are much more cost effective than pump and treat systems. In water management situations with non-accumulative contaminants (tritium, VOCs, etc.) irrigation in a forest setting can be very effective.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

2011 Mound Site Groundwater Plume Rebound Exercise and Follow-Up - 13440

The Mound Site facility near Miamisburg, Ohio, opened in 1948 to support early atomic weapons programs. It grew into a research, development, and production facility performing work in support of the U.S. Department of Energy (DOE) weapons and energy programs. The plant was in operation until 1995. During the course of operation, an onsite landfill was created. The landfill was located over a finger of a buried valley aquifer, which is a sole drinking water source for much of the Miami Valley. In the 1980's, volatile organic compounds (VOCs) were discovered in groundwater at the Mound site. The site was placed on the National Priorities List on November 21, 1989. DOE signed a Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) Federal Facility Agreement with the U.S. Environmental Protection Agency (EPA) and the Ohio Environmental Protection Agency. The agreement became effective in October 1990. The area that included the landfill was designated Operational Unit 1 (OU-1). In 1995, a Record of Decision was signed that called for the installation and operation of a pump and treatment (P and T) system in order to prevent the VOCs in OU-1 groundwater from being captured by the onsite water production wells. In addition to the P and T system, a soil vapor extraction (SVE) system was installed in 1997 to accelerate removal of VOCs from groundwater in the OU-1 area. The SVE system was successful in removing large amounts of VOCs and continued to operate until 2007, when the amount of VOCs removed became minimal. A rebound study was started in February 2003 to determine how the groundwater system and contaminants would respond to shutting down the P and T system. The rebound test was stopped in February 2004 because predetermined VOC threshold concentrations were exceeded down-gradient of the landfill. The P and T and SVE systems were restarted after the termination of the rebound test. In 2006, the remediation of the Mound site was completed and the site was declared to be protective of human health and the environment, as long as the institutional controls are observed. The institutional controls that apply to the OU-1 area include provisions that no soil be allowed to leave the site, no wells be installed for drinking water, and the site may be approved only for industrial use. The onsite landfill with the operating CERCLA remedy remained. However, the Mound Development Corporation lobbied Congress for funds to remediate the remaining onsite landfill to allow for property reuse. In 2007 DOE received funding from Congress to perform non-CERCLA removal actions at OU-1 to excavate the site sanitary landfill. In 2009, DOE received American Recovery and Reinvestment Act funding to complete the project. Excavation of the landfill occurred intermittently from 2006 through 2010 and the majority of the VOC source was removed; however, VOC levels near the P and T system remained greater than the EPA maximum contaminant levels (MCLs). Presently, groundwater is contained using two extraction wells to create a hydraulic barrier to prevent down-gradient migration of VOC-impacted groundwater. Since the primary contamination source has been removed, the feasibility of moving away from containment to a more passive remedy, namely monitored natural attenuation (MNA), is being considered. A second rebound study was started in June 2011. If contaminant and groundwater behavior met specific conditions during the study, MNA would be evaluated and considered as a viable alternative for the groundwater in the OU-1 area. From June through December 2011, the second rebound study evaluated the changes in VOC concentrations in groundwater when the P and T system was not in operation. As the study progressed, elevated concentrations of VOCs that exceeded predetermined trigger values were measured along the down-gradient boundary of the study area, and so the P and T system was restarted. It was determined that a discrete area with VOC concentrations greater than the MCLs was present in groundwater down-gradient of the extraction wells. The source was not identified, but the contamination was thought not to be caused by residually contaminated soil beneath the former landfill. The data collected so far supports the consideration of MNA as a viable alternative to hydraulic containment. Additional investigations are being performed to identify possible sources or pathways of VOCs in groundwater that may be contributing to the elevated VOC levels measured down-gradient of the extraction well system. Data from this additional investigation will be used to determine whether the VOCs detected down-gradient of the hydraulic boundary are the result of residual soil contamination, a previously unknown contribution of VOC-contaminated water entering the groundwater outside the capture zone of the extraction wells, or a pulse of VOC-contaminated groundwater from the OU-1 landfill that occurred during the rebound study. (authors)

54 ENVIRONMENTAL SCIENCES↗

Regulator Interface Strategies Implemented at the Y-12 National Security Complex Old Salvage Yard Soils Remediation Project, Oak Ridge, TN - 12162

The Oak Ridge Y-12 National Security Complex housed an area known as the Old Salvage Yard (OSY) that was approximately 7 acres. The OSY was used as an area for the accumulation, processing and storage of scrap metal and equipment from Y-12 operations extending from 1968 until 2009. Areas in the northern sections of OSY also have been used for the storage of used oils containing solvents and the accumulation and recycling or de-heading and crushing of 55-gal metal drums. Scrap metal operations historically involved the accumulation, sorting, storage, public sale or disposal of scrap metal and equipment. Non-containerised storage of scrap metal was routine until 1995 when scrap metal received at OSY was placed in B-24 and B-25 boxes. Under the American Recovery and Reinvestment Act (ARRA), approximately 26,759 cubic meters of scrap metal and debris were removed and disposed at both on and off-site disposal facilities including the on-site, Oak Ridge Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) landfill in 2010 and 2011. This removal action was performed in accordance with a CERCLA Record of Decision (ROD) and a close working relationship with both the U.S. Environmental Protection Agency (EPA) Region IV and Tennessee Department of Environment and Conservation (TDEC). Due to efficiencies and the excellent cooperative relationship forged with EPA Region IV and TDEC for Y-12 ARRA Cleanup Projects, a surplus of funding was available for additional remediation work that was completed in fiscal year (FY) 2011. The underlying OSY soils were targeted for characterization and potential remediation. To expedite these important activities, the U.S. Department of Energy Oak Ridge Environmental Management partnered with the regulators during detailed planning sessions through a variety of means to quickly and efficiently characterize and pinpoint areas requiring remediation according to previous ROD commitments. Data Quality Objectives (DQOs), data-sharing, real-time characterization reporting, surface and groundwater modeling and other interface planning activities were utilized to help facilitate and complete characterization and remediation activities. As a result of these strategies, the surgical extraction of one contiguous area of soil approximately 354 cubic meters is planned for FY12. The strategies discussed resulted in a major reduction of footprint remediation (i.e., 2.8% of the original estimate) which was originally estimated at over 26,759 cubic meters. The original estimate was developed using historical data collected at various times over the period of 20 years. By leveraging a hybrid sampling approach that involved both statistically-based and biased sampling locations, the area of contamination was significantly reduced resulting in both a compliant remedial design that is cost effective while mitigating a principle threat sources to surface and groundwater at the Y-12 plant. One remedial action boundary of 354 cubic meters was verified in the northern section of the Western OSY area known as the old drum de-header station for VOCs. The original estimate for disposal was in excess of 26,759 cubic meters. This area is scheduled for waste characterization and profile development in the first half of fiscal year 2012. The anticipated disposal facility is an on-site Oak Ridge CERCLA disposal landfill known as the Environmental Management Waste Management Facility (EMWMF). By utilizing the careful strategic planning, field-based screening and close cooperation of regulatory stakeholders as detailed in this paper, the total area of soil requiring remedial action within the Y-12 OSY footprint was 354 cubic meters or 2.8% of the original planned estimate. A potential waste reduction of 97.2% was realized over the original planned estimate for OSY Soils. Significant cost savings were achieved by - Minimizing the footprint of the remedial action; - Confirmatory analysis of soils instead of use of historical sampling results for waste profile development; - Targeting traditional laboratory analysis for soils that failed field screen protocols for radionuclides, heavy metals and VOCs; - Providing accurate and precise definition of RABs; and - Reduction of target contaminants for focused laboratory analysis instead of broad-range contaminants. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗