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Rapid denitrification of nitrate-contaminated groundwater in a low-gradient blackwater stream valley

Leaching of excess nitrogen (N) to groundwater in fertilized landscapes can overwhelm natural biogeochemical processes and cause long-term eutrophication of aquatic systems. We investigated N fate and transport from an intensively managed short-rotation woody crop (Pinus taeda) plantation through the riparian zone of an intermittent, low-gradient blackwater stream. Fertilization of the P. taeda plantation on the uplands resulted in contamination of groundwater with nitrate concentrations between 0.9 and 1.9 mg N L -1 . No corresponding increase in nitrate was observed in stream water or shallow groundwater in the riparian zone. Groundwater travel-time modeling predicted that N from near-stream, upland plantation areas should have reached streams during the monitoring period. Two years of measuring N species in well water in contrasting landscape positions (within the plantation, swale, riparian edge, forested hillslope, and valley), indicated rapid nitrate transformation and denitrification within the forested wetland valleys. Denitrification in the shallow groundwater system within the toeslopes and the riparian zone was estimated to have removed > 90% of nitrate. Finally, these results highlight the importance of riparian zones as pathways for the removal of N and for controlling downstream N loads.

54 ENVIRONMENTAL SCIENCES↗

Predicting the effectiveness of different mulching techniques in reducing post-fire runoff and erosion at plot scale with the RUSLE, MMF and PESERA models

Highlights: • RUSLE, MMF and PESERA, were able to predict the erosive response in burned areas and their mitigation. • These models can be calibrated at a small spatial scale and provide accurate results at greater spatial scales. • RUSLE model ideal for fast and simple risk assessment. • MMF or PESERA models could be the base of a post-fire management decision tool. Wildfires have become a recurrent threat for many Mediterranean forest ecosystems. The characteristics of the Mediterranean climate, with its warm and dry summers and mild and wet winters, make this a region prone to wildfire occurrence as well as to post-fire soil erosion. This threat is expected to be aggravated in the future due to climate change and land management practices and planning. The wide recognition of wildfires as a driver for runoff and erosion in burnt forest areas has created a strong demand for model-based tools for predicting the post-fire hydrological and erosion response and, in particular, for predicting the effectiveness of post-fire management operations to mitigate these responses. In this study, the effectiveness of two post-fire treatments (hydromulch and natural pine needle mulch) in reducing post-fire runoff and soil erosion was evaluated against control conditions (i.e. untreated conditions), at different spatial scales. The main objective of this study was to use field data to evaluate the ability of different erosion models: (i) empirical (RUSLE), (ii) semi-empirical (MMF), and (iii) physically-based (PESERA), to predict the hydrological and erosive response as well as the effectiveness of different mulching techniques in fire-affected areas. The results of this study showed that all three models were reasonably able to reproduce the hydrological and erosive processes occurring in burned forest areas. In addition, it was demonstrated that the models can be calibrated at a small spatial scale (0.5 m{sup 2}) but provide accurate results at greater spatial scales (10 m{sup 2}). From this work, the RUSLE model seems to be ideal for fast and simple applications (i.e. prioritization of areas-at-risk) mainly due to its simplicity and reduced data requirements. On the other hand, the more complex MMF and PESERA models would be valuable as a base of a possible tool for assessing the risk of water contamination in fire-affected water bodies and for testing different land management scenarios.

54 ENVIRONMENTAL SCIENCES↗

Tin Oxynitride Anodes by Atomic Layer Deposition for Solid-State Batteries

Major advances in thin-film solid-state batteries (TFSSBs) may capitalize on 3D structuring using high-aspect-ratio substrates such as nanoscale pits, pores, trenches, flexible polymers, and textiles. This will require conformal processes such as atomic layer deposition (ALD) for every active functional component of the battery. In this paper, we explore the deposition and electrochemical properties of SnO 2 , SnN y , and SnO x N y thin films as TFSSB anode materials, grown by ALD using tetrakisdimethylamido(tin), H 2 O, and N 2 plasma as precursors. By controlling the dose ratio between H 2 O and N 2 , the N–O fraction can be tuned between 0% N and 95% N. The electrochemical properties of these materials were tested across a composition range varying from pure SnO 2 , to SnON intermediates, and pure SnNy. In TFSSBs, the SnNy anodes are found to be more stable during cycling than the SnO 2 or SnO x N y films, with an initial reversible capacity beyond that of Li–Sn alloying, retaining 75% of their capacity over 200 cycles compared to only 50% for SnO 2 . Lastly, the performance of the SnO x N y anodes indicates that SnN y anodes should not be negatively impacted by small levels of O contamination.

36 MATERIALS SCIENCE↗

Iodine-129 and Iodine-127 speciation in groundwater at the Hanford Site, U.S.: iodate incorporation into calcite

The Hanford Site, the most contaminated nuclear site in the United States, has large radioactive waste plumes containing high 129I levels. The geochemical transport and fate of radioiodine depends largely on its chemical speciation that is greatly affected by environmental factors. This study reports, for the first time, the speciation of stable and radioactive iodine in the groundwater from the Hanford Site. Iodate was the dominant species and accounts for up to 84%, followed by organo-iodine and minimal levels of iodide. The relatively high pH and oxidizing environment may have prevented iodate reduction. Our results identified that calcite precipitation caused by degassing of CO2 during deep groundwater sampling incorporated between 7 to 40% of dissolved iodine (including 127I and 129I) that was originally in the groundwater, transforming dissolved to particulate iodate during sampling. In order to understand the mechanisms underlying iodine incorporation by calcite, laboratory experiments were carried out to replicate this iodine sequestering processes. Two methods were utilized in this study, 1) addition of sodium carbonate; 2) addition of calcium chloride followed by sodium carbonate where the pH was well controlled at ~8.2, which is close to the average pH of Hanford Site groundwater. It was demonstrated that iodate was the main species incorporated into calcite and this incorporation process could be impeded by elevated pH and decreasing ionic strength in groundwater. This study provides critical information for predicting the long-term fate and transport of 129I at the Hanford Site and reveals a potential means for improved remediation strategies of 129I.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Deposition of novel nanocomposite films by a newly developed differential pumping co-sputtering system

A differential pumping co-sputtering system was developed to facilitate a controlled, but flexible fabrication of multifunctional nanocomposite films with compositions not limited by thermodynamic restrictions. This system features a multichamber design with a differential pumping system. Dividing atmospheres with this set up greatly reduced the cross-contamination between chambers, and each material could be co-deposited by rapid rotation of the substrate. The clearance between the substrate holder and the chamber was set at 1-2 mm, and the conductance of the clearance was examined roughly using conductance equations for typical types of orifices. It was found that the potential difference (PD) value of the clearance between the two chambers was less than 0.01; the gas flow between the two chambers through the clearance thus appears to be a practical molecular flow. The PD value, where P is a pressure (Pa) and D is a diameter of an orifice or a pipe (m), is a gas flow indicator or parameter obtained from an equation of Knudsen number. The changes in the oxygen partial pressure and glow discharge plasma in the left chamber were investigated using a process gas monitor (PGM) and optical emission spectroscope (OES) by introducing different gases to each chamber. The PGM results revealed that the cross-contamination of oxygen from the other chamber was suppressed to 10 {+-} 3% of the original. In addition, the OES measurement for glow discharge plasma did not detect substantial oxygen contamination from the other chamber. Using the newly developed system, an AlN/SiO{sub x} nanocomposite film consisting of B4-type AlN and amorphous SiO{sub x} was obtained successfully.

36 MATERIALS SCIENCE↗

Data Assimilation Cycling for Weather Analysis

This software package runs the atmospheric model MM5 in data assimilation cycling mode to produce an optimized weather analysis, including the ability to insert or adjust a hurricane vortex. The program runs MM5 through a cycle of short forecasts every three hours where the vortex is adjusted to match the observed hurricane location and storm intensity. This technique adjusts the surrounding environment so that the proper steering current and environmental shear are achieved. MM5cycle uses a Cressman analysis to blend observation into model fields to get a more accurate weather analysis. Quality control of observations is also done in every cycle to remove bad data that may contaminate the analysis. This technique can assimilate and propagate data in time from intermittent and infrequent observations while maintaining the atmospheric field in a dynamically balanced state. The software consists of a C-shell script (MM5cycle.driver) and three FORTRAN programs (splitMM5files.F, comRegrid.F, and insert_vortex.F), and are contained in the pre-processor component of MM5 called "Regridder." The model is first initialized with data from a global model such as the Global Forecast System (GFS), which also provides lateral boundary conditions. These data are separated into single-time files using splitMM5.F. The hurricane vortex is then bogussed in the correct location and with the correct wind field using insert_vortex.F. The modified initial and boundary conditions are then recombined into the model fields using comRegrid.F. The model then makes a three-hour forecast. The three-hour forecast data from MM5 now become the analysis for the next short forecast run, where the vortex will again be adjusted. The process repeats itself until the desired time of analysis is achieved. This code can also assimilate observations if desired.

Tran, Nam↗

Evaluation of Various Radar Data Quality Control Algorithms Based on Accumulated Radar Rainfall Statistics

The primary function of the TRMM Ground Validation (GV) Program is to create GV rainfall products that provide basic validation of satellite-derived precipitation measurements for select primary sites. A fundamental and extremely important step in creating high-quality GV products is radar data quality control. Quality control (QC) processing of TRMM GV radar data is based on some automated procedures, but the current QC algorithm is not fully operational and requires significant human interaction to assure satisfactory results. Moreover, the TRMM GV QC algorithm, even with continuous manual tuning, still can not completely remove all types of spurious echoes. In an attempt to improve the current operational radar data QC procedures of the TRMM GV effort, an intercomparison of several QC algorithms has been conducted. This presentation will demonstrate how various radar data QC algorithms affect accumulated radar rainfall products. In all, six different QC algorithms will be applied to two months of WSR-88D radar data from Melbourne, Florida. Daily, five-day, and monthly accumulated radar rainfall maps will be produced for each quality-controlled data set. The QC algorithms will be evaluated and compared based on their ability to remove spurious echoes without removing significant precipitation. Strengths and weaknesses of each algorithm will be assessed based on, their abilit to mitigate both erroneous additions and reductions in rainfall accumulation from spurious echo contamination and true precipitation removal, respectively. Contamination from individual spurious echo categories will be quantified to further diagnose the abilities of each radar QC algorithm. Finally, a cost-benefit analysis will be conducted to determine if a more automated QC algorithm is a viable alternative to the current, labor-intensive QC algorithm employed by TRMM GV.

Robinson, Michael↗

Development of In-Situation Radioactivity Inspection System for Food Materials

The impacts on the ocean of releases of radionuclides from the Fukushima nuclear power plants remain unclear. Korean people worry about radioactive contamination of Japanese and Korean sea products. Radioactive contamination of processed foodstuffs, livestock, sea products, farm products imported from Japan and fishes caught in coastal oceans of Korea has become an important social issue. Recently, there are also needs of inspection system for monitoring of public meals such like school feedings of kindergarten, elementary/middle/high school and university. Radioactivity inspections of food materials have been executed manually with portable measuring instruments or at labs using their samples. But, it's very important the radioactivity inspection should be performed at the field of feeding facilities. To protect the health of people from radioactivity contained in Japanese marine products imported to Korea, a system to inspect radioactivity in real time has been developed. The system is to measure the radioactivity level of farm and marine products and public meals continuously and automatically at inspection sites of an agency checking radiation of imported foodstuffs or school. The performance test of NaI(Tl) detector was examined using the quantified Cs-137 source 10 Bq/kg, 30 Bq/kg, 50 Bq/kg, 300 Bq/kg and 900 Bq/kg at Korea Research Institute of Standards and Science(KRISS). Source was put in a box and radioactivity was measured in the middle of the box. First of all, Background was measured and calibration was performed using the Cs-137 300 Bq and Ba-133 3700 Bq for 60 minutes. After setting the background and calibration data, tests of the Cs-137 10, 30, 50, 300, 900 Bq/kg were executed for 10 minutes. A peak-shaped graph is shown at the location of 662 KeV (80∼100 channel). This is due to the gamma radiation energy with 662 KeV emitted by the Cs-137. Because through KRISS examination, the MDA (minimum detectable activity) is about 23 Bq/kg, it is reasonable Cs-137 10 Bq/kg cannot be measured. And in cases of Cs-137 300 Bq/kg and 900 Bq/kg, there are some peak movement on the graph. It can be adjusted by controlling gain or high voltage. The examination was identified through the performance test (Cs-137 10, 30, 50, 300, 900 Bq/kg) at KRISS. In order to increase the measurement efficiency of Cs-137 and the system performance, database will be built up based on radioactivity measurement results from 10 to 300 Bq/kg with the unit 10. Thus, Cs-137 concentration of food materials can be identified below the maximum permissible concentration of 100 Bq/kg on a basis of the spectrum characteristic of Cs-137. Also, anxiety about radioactive contamination of foods after the Fukushima nuclear accident will be eased and trust of the radioactive inspection is expected definitely. (authors)

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Montane Conifer, Aspen, Meadow, and Sagebrush Metagenome Resolved Genomes and Traits in East River Watershed, Colorado, USA

Climate change is driving vegetation shifts in mountain watersheds, with unknown impacts on biogeochemical cycles. We hypothesize that these shifts will reshape soil microbiomes and associated biogeochemical processes. As a part of Lawrence Berkeley National Laboratory (LBNL) Watershed Science Focus Area (SFA), we assessed microbiome and microbial functional trait differences between soils under conifer, aspen, forby meadows, and sagebrush across the East River Watershed, CO, controlling for elevation and aspect.Here we present metagenome assembled genomes (MAGs) for the bacterial and archaeal communities from soils 0-20cm in depth across three locations in the watershed—Headwaters, Upper Reaches, and Lower Reaches from August 3-11th 2016. Each location was further subdivided into two blocks, with one block on a west facing aspect, and two on the east aspect of the valley. Within blocks, two samples per vegetation type were taken (one at each depth). This resulted in 66 samples, which were sequenced at JGI and can be found under the Joint Genome Institute (JGI) Genomes Online Database (GOLD) sequencing project Gs0118068. Metagenomes were assembled through an inhouse pipeline (see methods), binned using four autobinners (concoct, maxbin2, metabat2, and vamb) and consolidated using dastool. The consolidated bins from all metagenomes were pooled, filtered by completeness (>75%) and contamination (<25%), and dereplicated at 95% ANI using drep. The dataset includes a zip file of 687 genomes (Vegtype_MAGS.zip), the accession numbers for the underlying metagenomes, a csv file with MAG quality metrics and taxonomy from Genome Taxonomy Database (GTDB) and National Center for Biotechnology Information (NCBI) taxonomic representative genome proteins (EastRiver_Vegtype_drep_genome_info.csv), and a file containing MAG quality metrics and taxonomy (gtdb_drep_bin_taxonomy.csv). The dataset additionally includes a sample metadata file (EastRiver_Vegtype_sample_metadata.csv), a metadata file used to register associated samples with IGSNs (International Generic Sample Numbers) (samples.csv), a Google KML file for the sampled locations (sample_collection_sites.kml), a location metadata file (locations.csv), a file-level metadata file (flmd.csv), and a data dictionary (dd.csv) file.This work was supported by the Watershed Function Science Focus Area at Lawrence Berkeley National Laboratory funded by the US Department of Energy, Office of Science, Biological and Environmental Research under Contract No. DE-AC02-05CH11231.

54 ENVIRONMENTAL SCIENCES↗

Composite Sampling of a Bacillus anthracis Surrogate with Cellulose Sponge Surface Samplers from a Nonporous Surface

A series of experiments was conducted to explore the utility of composite-based collection of surface samples for the detection of a Bacillus anthracis surrogate using cellulose sponge samplers on a nonporous stainless steel surface. Two composite-based collection approaches were evaluated over a surface area of 3716 cm 2 (four separate 929 cm 2 areas), larger than the 645 cm 2 prescribed by the standard Centers for Disease Control (CDC) and Prevention cellulose sponge sampling protocol for use on nonporous surfaces. The CDC method was also compared to a modified protocol where only one surface of the sponge sampler was used for each of the four areas composited. Differences in collection efficiency compared to positive controls and the potential for contaminant transfer for each protocol were assessed. The impact of the loss of wetting buffer from the sponge sampler onto additional surface areas sampled was evaluated. Statistical tests of the results using ANOVA indicate that the collection of composite samples using the modified sampling protocol is comparable to the collection of composite samples using the standard CDC protocol (p = 0.261). Most of the surface-bound spores are collected on the first sampling pass, suggesting that multiple passes with the sponge sampler over the same surface may be unnecessary. The effect of moisture loss from the sponge sampler on collection efficiency was not significant (p = 0.720) for both methods. Contaminant transfer occurs with both sampling protocols, but the magnitude of transfer is significantly greater when using the standard protocol than when the modified protocol is used (p<0.001). The results of this study suggest that composite surface sampling, by either method presented here, could successfully be used to increase the surface area sampled per sponge sampler, resulting in reduced sampling times in the field and decreased laboratory processing cost and turn-around times.

59 BASIC BIOLOGICAL SCIENCES↗

Sensor and numerical simulator evaluation for porous medium desiccation and rewetting at the intermediate laboratory scale

Soil desiccation, in conjunction with surface infiltration control, is considered at the Hanford Site as a potential technology to limit the flux of technetium and other contaminants in the vadose zone to the groundwater. An intermediate-scale experiment was conducted to test the response of a series of instruments to desiccation and subsequent rewetting of porous media. The instruments include thermistors, thermocouple psychrometers, dual-probe heat pulse sensors, heat dissipation units, and humidity probes. The experiment was simulated with the multifluid flow simulator STOMP, using independently obtained hydraulic and thermal porous medium properties. All instrument types used for this experiment were able to indicate when the desiccation front passed a certain location. In most cases the changes were sharp, indicating rapid changes in moisture content, water potential, or humidity. However, a response to the changing conditions was recorded only when the drying front was very close to a sensor. Of the tested instruments, only the heat dissipation unit and humidity probes were able to detect rewetting. The numerical simulation results reasonably match the experimental data, indicating that the simulator captures the pertinent gas flow and transport processes related to desiccation and rewetting and may be useful in the design and analysis of field tests.

54 ENVIRONMENTAL SCIENCES↗

EVA-Compatible Microbial Swab Tool

When we send humans to search for life on Mars, we'll need to know what we brought with us versus what may already be there. To ensure our crewed spacecraft meet planetary protection requirements—and to protect our science from human contamination—we'll need to know whether micro-organisms are leaking/venting from our ships and spacesuits. This is easily done by swabbing external vents and suit surfaces for analysis, but requires a specialized tool for the job. Engineers at the National Aeronautics and Space Administration (NASA) recently developed an Extravehicular Activity (EVA)-compatible swab tool that can be used to sample current space suits and life support systems. Data collected now will influence Mars life support and EVA hardware early in the planning process, before design changes become difficult and expensive.NASA’s EVA swab tool pairs a Space Shuttle-era tool handle with a commercially available swab tip mounted into a custom-designed end effector. A glove-compatible release mechanism allows the handle to quickly switch between swab tips, much like a shaving razor handle can snap onto a disposable blade cartridge. Swab tips are stowed inside individual sterile containers, each fitted with a microbial filter that allows the container to equalize atmospheric pressure, but prevents cabin contaminants from rushing into the container when passing from the EVA environment into a pressurized cabin. A bank of containers arrayed inside a tool caddy allows up to six individual samples to be collected during a given spacewalk.NASA plans to use the tool in 2016 to collect samples from various spacesuits during ground testing to determine what (if any) human-borne microbial contamination leaks from the suit under simulated thermal vacuum conditions. Next, the tool will be used on board the International Space Station to assess the types of microbial contaminants found on external environmental control and life support system vents. Data will support advanced EVA and life support system maturation studies, helping to answer questions such as “how close can an EVA-suited crew member approach an area of scientific interest without compromising the science?”

Rucker, Michelle A.↗

200 West Pump and Treat: The First Three Years - 16473

The 200 West Pump and Treat (P and T), on the U.S. Department of Energy's Hanford Site, has a 9,464 liters per minute capacity designed to capture and treat an 8 km{sup 2} contaminated groundwater plume and reduce the mass of contaminants of concern (COCs) by 95 percent in 25 years. Treatable contaminants include carbon tetrachloride, trichloroethene, chromium, hexavalent chromium, nitrate, iodine-129 (I-129), and technetium-99 (Tc-99). After 3.5 years of continuous operation, the 200 West P and T treated over 10 billion liters of contaminated groundwater and removed over 190,000 kg of nitrate, 9,000 kg of carbon tetrachloride, nearly 5 curies of technetium-99, and smaller quantities of the remaining contaminants. Twenty three extraction wells strategically installed across the plumes pull contamination in from surrounding areas directing contaminated groundwater to the 200 West P and T for treatment. The 200 West P and T successfully removes all contaminants to below cleanup levels which are at (or lower than) the drinking water standard. Twenty one injection wells return treated water to the aquifer providing flow-path control to mitigate migration of contamination toward the Columbia River, a source of drinking water to the communities downstream. Contaminant concentrations in most monitoring wells are declining and the remedy is on target for accomplishing the mass removal goal ahead of schedule. In 2015, the 200 West P and T was expanded to include treatment for uranium from other operable units. With the uranium treatment expansion, the 200 West P and T is capable of cost-effectively treating contaminated groundwater beneath the 194 km{sup 2} Central Plateau. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Short-Term Inhibition and Long-Term Enhancement of Irreversible Trace Metal Binding to Goethite in Multi-Metal Systems

Iron (oxyhydr)oxide minerals are important sorbents of trace metals in aquatic environments. Adsorption–desorption hysteresis has been documented for trace metals after aging, suggesting that they become incorporated over time. We previously found that ion size controls the extent of irreversible metal binding of single metals to goethite. In this study, we evaluate how the presence of multiple metals influences irreversible binding. Mixed Ni–Zn and Ni–Cd solutions were aged with goethite at pH 7 for 2 days, 30 days, and 60 days, after which isotope exchange experiments were performed to assess the lability of the adsorbed metal pools. After 2 days of aging, Ni and Cd in mixed-metal systems were more labile than in single-metal systems, indicating that competitive adsorption may partially block irreversible binding on short time scales. After 60 days, all three metals had larger irreversibly bound fractions than in single-metal systems. X-ray absorption near-edge structure (XANES) spectroscopy indicates that irreversibly bound fractions correlate with incorporation into goethite. This study demonstrates that pools of coadsorbed metals are bioaccessible on a time scale of minutes. Cooperative effects promote the structural sequestration of even large trace metals, causing reactive transport models to likely overpredict metal mobility. Long-term metal entrapment processes hinder micronutrient availability, impact contaminant sequestration and critical mineral recovery, and yield complex pathways through which metal solubilization may be enhanced or hindered during redox cycling.

58 GEOSCIENCES↗

Data Sharing Report for the Quantification of Removable Activity in Various Surveillance and Maintenance Facilities at the Oak Ridge National Laboratory Oak Ridge TN

The U.S. Department of Energy (DOE) Oak Ridge Office of Environmental Management (OR-EM) requested that Oak Ridge Associated Universities (ORAU), working under the Oak Ridge Institute for Science and Education (ORISE) contract, provide technical and independent waste management planning support using American Recovery and Reinvestment Act (ARRA) funds. Specifically, DOE OR-EM requested that ORAU plan and implement a sampling and analysis campaign targeting potential removable radiological contamination that may be transferrable to future personal protective equipment (PPE) and contamination control materials—collectively referred to as PPE throughout the remainder of this report—used in certain URS|CH2M Oak Ridge, LLC (UCOR) Surveillance and Maintenance (S&M) Project facilities at the Oak Ridge National Laboratory (ORNL). Routine surveys in Bldgs. 3001, 3005, 3010, 3028, 3029, 3038, 3042, 3517, 4507, and 7500 continuously generate PPE. The waste is comprised of Tyvek coveralls, gloves, booties, Herculite, and other materials used to prevent worker exposure or the spread of contamination during routine maintenance and monitoring activities. This report describes the effort to collect and quantify removable activity that may be used by the ORNL S&M Project team to develop radiation instrumentation “screening criteria.” Material potentially containing removable activity was collected on smears, including both masselin large-area wipes (LAWs) and standard paper smears, and analyzed for site-related constituents (SRCs) in an analytical laboratory. The screening criteria, if approved, may be used to expedite waste disposition of relatively clean PPE. The ultimate objectives of this effort were to: 1) determine whether screening criteria can be developed for these facilities, and 2) provide process knowledge information for future site planners. The screening criteria, if calculated, must be formally approved by Federal Facility Agreement parties prior to use for ORNL S&M Project PPE disposal at the Environmental Management Waste Management Facility (EMWMF). ORAU executed the approved sampling and analysis plan (SAP) (DOE 2013) while closely coordinating with ORNL S&M Project personnel and using guidelines outlined in the Waste Handling Plan for Surveillance and Maintenance Activities at the Oak Ridge National Laboratory, DOE/OR/01-2565&D2 (WHP) (DOE 2012). WHP guidelines were followed because the PPE waste targeted by this SAP is consistent with that addressed under the approved Waste Lot (WL) 108.1 profile for disposal at EMWMF—this PPE is a “future waste stream” as defined in the WHP. The SAP presents sampling strategy and methodology, sample selection guidelines, and analytical guidelines and requirements necessary for characterizing future ORNL S&M Project PPE waste. This report presents a review of the sample and analysis methods including data quality objectives (DQOs), required deviations from the original design, summary of field activities, radiation measurement data, analytical laboratory results, a brief presentation of results, and process knowledge summaries.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

FX Hg Fogging Fixative Deployment for Mercury Vapor Suppression

Idaho National Laboratory’s (INL) FX Hg fixative solution was deployed at the Y-12 Complex in Oak Ridge, Tennessee to support disposal of mercury-contaminated metal debris. The fixative was dispensed via fogging. Fogging infiltrates non-line-of-sight areas improving fixative coating on complex geometries such as debris piles. FX Hg is the mercury vapor controlling derivative of INL’s FX2 fixative. FX2 was jointly developed with the National Nuclear Laboratory of the United Kingdom, and INL developed the FX Hg derivative to suppress mercury vapor generation. The Y-12 deployment was performed in concert with cleanup contractor UCOR. A dumpster filled with debris was fogged with FX Hg. The material was acceptable as municipal landfill waste, save for the mercury vapor levels measured. If the mercury vapor generation rate could be sufficiently reduced, disposal costs for this waste would be dramatically reduced. FX Hg had previously proven effective at significantly reducing mercury vapor generation rates in bench scale testing at INL. This deployment was the first field scale deployment of the method. Efficacy results were underwhelming, but interpretation of the outcome is complicated by a paucity of hard data. Methods for improving data capture and analysis are analyzed. Operational difficulties associated with scaling the process up and process improvements for future deployments are discussed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Acetate availability and its influence on sustainable bioremediation of uranium-contaminated groundwater

Field biostimulation experiments at the U.S. Department of Energy's Integrated Field Research Challenge (IFRC) site in Rifle, Colorado, have demonstrated that uranium concentrations in groundwater can be decreased to levels below the U.S. Environmental Protection Agency's (EPA) drinking water standard (0.126 {micro}M). During successive summer experiments - referred to as 'Winchester' (2007) and 'Big Rusty' (2008) - acetate was added to the aquifer to stimulate the activity of indigenous dissimilatory metal-reducing bacteria capable of reductively immobilizing uranium. The two experiments differed in the length of injection (31 vs. 110 days), the maximum concentration of acetate (5 vs. 30 mM), and the extent to which iron reduction ('Winchester') or sulfate reduction ('Big Rusty') was the predominant metabolic process. In both cases, rapid removal of U(VI) from groundwater occurred at calcium concentrations (6 mM) and carbonate alkalinities (8 meq/L) where Ca-UO2-CO3 ternary complexes constitute >90% of uranyl species in groundwater. Complete consumption of acetate and increased alkalinity (>30 meq/L) accompanying the onset of sulfate reduction corresponded to temporary increases in U(VI); however, by increasing acetate concentrations in excess of available sulfate (10 mM), low U(VI) concentrations (0.1-0.05 {micro}M) were achieved for extended periods of time (>140 days). Uniform delivery of acetate during 'Big Rusty' was impeded due to decreases in injection well permeability, likely resulting from biomass accumulation and carbonate and sulfide mineral precipitation. Such decreases were not observed during the short-duration 'Winchester' experiment. Terminal restriction fragment length polymorphism (TRFLP) analysis of 16S rRNA genes demonstrated that Geobacter sp. and Geobacter-like strains dominated the groundwater community profile during iron reduction, with 13C stable isotope probing (SIP) results confirming these strains were actively utilizing acetate to replicate their genome during the period of optimal U(VI) removal. Gene transcript levels during 'Big Rusty' were quantified for Geobacter-specific citrate synthase (gltA), with ongoing transcription during sulfate reduction indicating that members of the Geobacteraceae were still active and likely contributing to U(VI) removal. The persistence of reducible Fe(III) in sediments recovered from an area of prolonged (110 day) sulfate reduction is consistent with this conclusion. These results indicate that acetate availability and its ability to sustain the activity of iron- and uranyl-respiring Geobacter strains during sulfate reduction exerts a primary control on optimized U(VI) removal from groundwater at the Rifle IFRC site over extended timescales (>50 days).

54 ENVIRONMENTAL SCIENCES↗

Remediation of AMD using natural and waste material

Acid Mine Drainage (AMD) is highly acidic, sulphate rich and frequently carries a high transition metal and heavy metal burden. These AMD's eventually migrate into streams and rivers and impact negatively on the quality of these water bodies. So it is dire necessary to treat this AMD. Various materials such as ladle furnace slag (LFS), bentonite, zeolite, active carbon and kaolinite are currently available to remove heavy metals from contaminated water. All these materials are capable to rise up the pH value and adsorb heavy metals. The process is divided into two stages; screening test and tank experiment. Screening test is conduct by using Batch Equilibrium Test (BET), X-Ray Fluorescene (XRF) identification also Scanning Electron Microscopic (SEM) characteristic. The results showed that all the concentration of heavy metal are decreasing extremely and pH value rise up except for kaolinite. From screening test only ladle furnace slag, bentonite, zeolite and active carbon are chosen for the tank experiment. Tank experiment design with 18cm (H) X 15cm (L) X 15cm (H) was made by silica glass. All these treatment materials were stirred in the tank for 30 days. Initial pH for all tanks is 2.4 and after 30 days is changing into 6.11, 3.91, 2.98 and 2.71 for LFS, bentonite, active carbon as well as zeolite respectively. LFS is the best material for absorption of Zn, Mn and Cu in the synthetic solution. Meanwhile, bentonite is the best absorbent for Ni, Fe and Cd. The conclusion shows that LFS might have big potentials to control AMD pollution base on neutralize pH resulting in a great improvement in the quality of the water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗