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At least 1,117 records · Page 62

Am(VI) Extraction Final Report: FY16

This report summarizes activities related to hexavalent Am extraction for FY16, in completion of FCR&D Milestone M3FT-16IN030103027. Activities concentrated on three areas of research: 1) centrifugal contactor hot testing, 2) Am(VI) stability studies, and 3) alternative oxidant studies. A brief summary of each task follows. Hot Testing: A new engineering-scale oxidation and solvent extraction test bed was built at Idaho National Laboratory to allow for solvent extraction testing of minor actinide separation concepts. The test bed consists of an oxidation vessel, filtration apparatus, four, 3D printed, 2-cm diameter centrifugal contactors, feed/product vessels, and sample ports. This system replaced the previous 3 stage, 5-cm contactor test bed that was used for the initial testing in FY14. In the FY16 hot test, a feed simulant was spiked with 243Am and 139Ce and treated with 60 g/L sodium bismuthate for two hours to oxidize the Am(III) to Am(VI). This solution was then pumped through a filter and into the four-stage centrifugal contactor setup. The organic phase solvent formulation was 1 M diethylhexylbutyramide (DEHBA)/dodecane. The test showed that Am(VI) was produced by bismuthate oxidation and the residual oxidant was successfully filtered without back pressure buildup. Sixty-four percent of Am was extracted in the contactors using DEHBA. Both Am and Ce were quantitatively stripped by 0.1 M H2O2. Successful demonstration of the utility of small, printable contactors suggests that hot testing of separations concepts can now be conducted more often, since it is cheaper, generates less waste, and entails much less radcon risk than previous testing. Am(VI) stability: A rigorous examination of reagents was conducted to determine if contaminants could interfere with Am oxidation and extraction. An series of DAm measurements showed that bismuthate particle size, water source, acid quality, and DAAP batch or pre-treatment had little effect on extraction efficiency, with a mean distribution ratio of 3.74 ± 0.5, using 1 M DAAP extraction. Additionally, the purposeful addition of millimolar amounts of nitrite or H2O2 to bismuthate-treated Am solutions did not prevent oxidation, as long as residual solid bismuthate was present. Finally, a series of irradiation experiments using a Nordion Gammacell 220E 60Co source was performed, and kinetic data for the radiolytic reduction of Am(VI) were obtained. Unsurprisingly, it was found that radiolysis reduces Am(VI), but that the presence of Ce(IV) acts as a radioprotection agent, to scavenge radiolytically-produced reducing agents, thereby enhancing the stability of the higher Am oxidation state. Alternative oxidants: To date, sodium bismuthate is the only practical oxidant for Am with utility in solvent extraction. While successful oxidation has been demonstrated with sodium peroxydisulfate, it is impractical for solvent extraction because it is only useful in dilute acid and it introduces sulfate into the process. Oxidation has been demonstrated using silver and cobalt catalyzed ozone, however, reduction upon contact with an organic phase is instantaneous. Oxidation is successful using Cu(III) periodate, and marginally successful in initial testing using DAAP extraction. However, the distribution ratios for the oxidized Am are marginal, because Cu(III) is also rapidly reduced by the organic phase. The possibility may exist that this can be optimized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of the ICET Test Stand to Assess the Performance of a Range of Ceramic Media Filter Elements in Support of ASME AG-1 Subsection FO

High Efficiency Particulate Air (HEPA) filters are defined as extended-medium, dry-type filters with: (1) a minimum particle removal efficiency of no less than 99.97 percent for 0.3 micrometer particles, (2) a maximum, clean resistance of 1.0 inch water column (in. WC) when operated at 1,000 cubic feet per minute (CFM), and (3) a rigid casing that extends the full depth of the medium. Specifically, ceramic media HEPA filters provide better performance at elevated temperatures, are moisture resistant and nonflammable, can perform their function if wetted and exposed to greater pressures, and can be cleaned and reused. This paper describes the modification and design of a large scale test stand which properly evaluates the filtration characteristics of a range of ceramic media filters challenged with a nuclear aerosol agent in order to develop Section FO of ASME AG-1.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Analysis of a Radioactive Release in a Nuclear Waste Disposal Facility

The Waste Isolation Pilot Plant (WIPP) is a 655-meter deep mine near Carlsbad, New Mexico, used to dispose the nation’s defense transuranic waste. Limited airborne radioactivity was released from a container of radioactive waste in WIPP on 14 February, 2014. As designed, a mine ventilation filtration system prevented the large scale release of contamination from the underground. However, isolation dampers leaked, which allowed the release of low levels of contaminants after the event until they were sealed. None of the exposed individuals received any recordable dose. While surface contamination was limited, contamination in the ventilation system and portions of the underground was substantial. High efficiency particulate air (HEPA) filters in the operating ventilation system ensure continued containment during recovery and resumption of disposal operations. However, ventilation flow is restricted since the incident, with all exhaust air directed through the filters. Decontamination and natural fixation by the hygroscopic nature of the salt host rock has reduced the likelihood of further contamination spread. Contamination control and ventilation system operability are crucial for resumption of operations. This article provides an operational assessment and evaluation of these two key areas.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mathematical Basis and Test Cases for Colloid-Facilitated Radionuclide Transport Modeling in GDSA-PFLOTRAN

This report provides documentation of the mathematical basis for a colloid-facilitated radionuclide transport modeling capability that can be incorporated into GDSA-PFLOTRAN. It also provides numerous test cases against which the modeling capability can be benchmarked once the model is implemented numerically in GDSA-PFLOTRAN. The test cases were run using a 1-D numerical model developed by the author, and the inputs and outputs from the 1-D model are provided in an electronic spreadsheet supplement to this report so that all cases can be reproduced in GDSA-PFLOTRAN, and the outputs can be directly compared with the 1-D model. The cases include examples of all potential scenarios in which colloid-facilitated transport could result in the accelerated transport of a radionuclide relative to its transport in the absence of colloids. Although it cannot be claimed that all the model features that are described in the mathematical basis were rigorously exercised in the test cases, the goal was to test the features that matter the most for colloid-facilitated transport; i.e., slow desorption of radionuclides from colloids, slow filtration of colloids, and equilibrium radionuclide partitioning to colloids that is strongly favored over partitioning to immobile surfaces, resulting in a substantial fraction of radionuclide mass being associated with mobile colloids.

54 ENVIRONMENTAL SCIENCES↗

Demonstration of Advanced CO 2 Capture Process Improvements for Coal-Fired Flue Gas

This document summarizes the activities of Cooperative Agreement DE-FE0026590, “Demonstration of Advanced CO 2 Capture Process Improvements for Coal-Fired Flue Gas” during the performance period of October 1, 2015 through May 31, 2017. This project was funded by the U.S. Department of Energy (DOE) National Energy Technology Laboratory (NETL). Southern Company Services, Inc. (SCS) was the prime contractor and co-funder of the project. Mitsubishi Heavy Industries America (MHIA) and AECOM were project team members. The overall project objective was to improve costs, energy requirements, and performance of an existing amine-based CO 2 capture process. This will occur via improvements in three areas: 1. Reboiler design – The first objective of the program was to demonstrate performance of an integrated stripper/reboiler (termed Built-in Reboiler, or BIR) to reduce footprint, capital costs, and integration issues of the current technology. 2. Particulate management – The second objective was to carry out a Particulate Matter Management (PMM) test. This has the potential to reduce operating costs and capital costs due to the reduced or eliminated need for mechanical filtration. 3. Solvent – The third objective was to carry out a new solvent test plan (referred to as NSL) to demonstrate a new solvent (termed New Solvent A), which is expected to reduce regeneration steam. The bulk price is also expected to be lower than KS-1, which is the current solvent used in this process. NSL testing would include baseline testing, optimization, long term testing, solvent reclamation testing, and final inspection. These combine to form the Advanced Carbon Capture (ACC) technology. Much of this work will be applicable to generic solvent processes, especially in regards to improved reboiler design, and focused to meet or exceed the DOE’s overall carbon capture performance goals of 90% CO 2 capture rate with 95% CO 2 purity at a cost of $40/tonne of CO 2 by 2025 and at a cost of electricity (COE) 30% less than baseline CO 2 capture approaches by 2030. This project was divided into two phases. Phase 1 is the planning phase, and Phase 2 is the construction, operations, testing, and analysis phase. A down select occurred after Phase 1. Phase 1 activities were carried out during this reporting period, and therefore, Phase 1 activities are solely considered in this report. The project was not selected for Phase 2 funding.

01 COAL, LIGNITE, AND PEAT↗

Waste Water for Power Generation via Energy Efficient Selective Silica Separations

Silica is ubiquitous in produced and industrial waters, and plays a major disruptive role in water recycle. Herein we have investigated the use of mixed oxides for the removal of silica from these waters, and their incorporation into a low cost and low energy water purification process. High selectivity hydrotalcite (HTC, (Mg 6 Al 2 (OH) 16 (CO 3 )•4H 2 O)), is combined in series with high surface area active alumina (AA, (Al 2 O 3 )) as the dissolved silica removal media. Batch test results indicated that combined HTC/AA is a more effective method for removing silica from industrial cooling tower wasters (CTW) than using HTC or AA separately. The silica uptake via ion exchange on the mixed oxides was confirmed by Fourier transform infrared (FTIR), and Energy dispersive spectroscopy (EDS). Furthermore, HTC/AA effectively removes silica from CTW even in the presence of large concentrations of competing anions, such as Cl - , NO 3 - HCO 3 - , CO 3 2- and SO 4 2- . Similar to batch tests, Single Path Flow Through (SPFT) tests with sequential HTC/AA column filtration has very high silica removal too. Technoeconomic Analysis (TEA) was simultaneously performed for cost comparisons to existing silica removal technologies.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Radioactive aerosols training

An introduction to radioactive aerosols will be presented in this class. There will be a specific focus on transuranic materials, typical to those used in operations at Los Alamos. The uptake of radioactive aerosols is affected by the physical characteristics of the airborne material, the behavior of the aerosol in air (or gas), and the interaction of the material with the worker. Aerosol behavior in the radiological workplace will influence filtration, release control, and dose considerations. This course will review the basics of aerosol technology, distinguishing between the classical (Newtonian) and molecular (quantized) regimes. Particles from about 1 to 10 microns (diameter) are described by classical physics, but particles from about 0.01 to 0.3 microns must be understood through modern molecular theory (i.e. Einstein, 1905). The class will discuss relevant LANL accidents that involved aerosol releases from the years 1971, 1994, 2000, 2003 and 2005.

61 RADIATION PROTECTION AND DOSIMETRY↗

An Integrated Supercritical System for Efficient Produced Water Treatment and Power Generation

The main goal of this project was to evaluate the feasibility of an integrated supercritical (SC) water desalination and power generation system for treatment of produced waters from CO 2 sequestration, oil production, and coal-bed methane recovery. This system may offer a transformative approach to generating power from coal or natural gas (NG) and purifying saline water or produced water with high total dissolved solids (TDS) in a zero-liquid discharge plant. The closed-loop steam cycle of conventional power plants was replaced with an open-loop steam cycle that heated the pretreated produced water above the SC point of water (374 °C and 221 bar) to precipitate and separate the salts dissolved in the water. After separation of the precipitated salt, the SC steam required further treatment to reduce the salt content from ~100 mg/L (ppm) to <1 ppm to make it suitable for use in turbines for power generation. A SC membrane distillation unit was used to polish the SC steam, which could be sent through a series of turbines for power generation, and the steam exiting the low-pressure turbine could be condensed by cooling water to produce pure water. Project tasks included a process simulation and a techno-economic evaluation of the integrated system; design and assembly of SC salt precipitation and membrane distillation systems; development and characterization of advanced carbon membranes for SC membrane distillation; and pretreatment, desalination, and purification of different produced water samples with salt concentrations of 30,000–200,000 ppm to a high-purity (<1 ppm) level. Process simulations were performed for 550 MW SC coal-fired or NG baseline cases and various scenarios for the proposed integrated SC system using produced water as the water source and coal or NG as the fuel source. Simulation results indicated that the net plant efficiency loss of the proposed SC cogeneration process would be in the range of <1% to ~4%, in which NG and lower TDS produced water cases would have higher efficiencies. The proposed process for coal-fired cases could provide all water needs for the power generation process and generate additional pure water for beneficial use. A techno-economic analysis was performed to estimate the cost of produced water treatment (dollars /kgal of treated water) by conventional treatment processes compared with the proposed cogeneration process. The cost estimation for the proposed cogeneration system included the cost of pretreatment, the cost of power loss to integrate the water desalination process into the power generation system, and the cost of plant modification or retrofitting. The cost of produced water treatment was calculated by assuming three different scenarios in which converting a baseline power plant to the proposed cogeneration plant would increase the cost of the boiler and feed water system by 10%, 50%, and 100%. Results indicated that the cost of produced water treatment, even with a 100% cost increase, was in the range of $8.6–11.6 dollars per kgal, which is about half of the treatment cost by conventional methods. The cost of produced water treatment by the proposed cogeneration system could be further reduced or a considerable income could be generated if the values of saltwater and freshwater products are considered. Overall, the techno-economic analysis results indicated that the proposed integrated SC system could potentially treat produced water at a cost significantly lower than the cost of produced water treatment by conventional technologies. To evaluate the feasibility of the proposed treatment system at a laboratory scale, a SC salt precipitation and membrane distillation system was designed and fabricated to treat a simulated brine or pretreated produced water by precipitating salts and further polishing the SC steam containing ~100 ppm salts to a high-purity steam. Through baseline tests with NaCl solutions, with concentrations ranging from 30,000 to 200,000 ppm, it was demonstrated that concentrated feed solutions could be treated by precipitating salt at SC conditions to a TDS level of 130 ppm. Produced water samples were collected from a potential CO 2 sequestration site, a coal-bed methane site, and an oilfield in Illinois. Representative samples were characterized for various water quality parameters, including pH; turbidity; conductivity; and concentrations of selected anions, cations, alkalinity, dissolved organic carbon, total suspended solids, TDS, and total petroleum hydrocarbons. The produced water samples were first treated by conventional pretreatment methods to remove residual oil, dissolved organic matter, and scale-forming species. Pretreatment methods included coagulation, sedimentation, filtration, activated carbon adsorption, and ion-exchange adsorption. Pretreated produced waters were treated at SC conditions in which salts were precipitated. Analysis of treated samples revealed that the concentration of Na (the main cation) in produced waters was reduced dramatically from 14,000–47,400 ppm in the feed to 21–80 ppm in treated waters. Concentrations of other main cations (Ca, Mg, Sr, K) also decreased significantly from initial values of ~1,000–22,000 ppm to ~1 ppm or less. However, a significant increase in the concentrations of Fe, Ni, Cu, and Co was observed, mainly caused by leaching of these elements from the system (vessels, filters, tubing), which is manufactured from alloys containing Fe, Ni, Cu, and Co. To polish the SC steam containing a salt content of ~100 ppm to a high-purity level of <1 ppm, a SC membrane distillation treatment using carbon membranes was employed. Different types of self-standing or supported carbon membranes were developed from graphite, graphene, carbon nanotubes, carbon nanofibers, and pyrolytic carbon. Screening tests revealed that only a limited number of developed carbon membranes were suitable for the purification of steam at SC conditions. Membranes that were either fragile and lacked mechanical strength or had large pores and showed limited salt rejection (<20%) were found to be unsuitable for the purification of SC steam. Promising carbon membranes that were successfully tested for purifying SC steam included two graphite membranes (i.e., AF-5, a porous graphite material, and FGS, a flexible graphite sheet) and a carbon nanotube membrane grown on a Hastelloy substrate and then further modified using a proprietary method (i.e., membrane C). The AF-5 membrane exhibited a stable water flux of ~50 kg/m 2 ∙h and ~40% salt rejection. The FGS membrane had a high salt rejection of 95%–98% but a lower water flux of ~15 kg/m 2 ∙h. Membrane C showed an extremely high flux of 200-800 kg/m 2 ∙h, which is one order of magnitude higher than the water flux of conventional membranes. Membrane C also exhibited 87%–93% salt rejection. Overall, a two-stage or multistage polishing treatment by these membranes could lower the salt content of the SC steam from initial values of ~100–200 ppm to the steam quality of <1 ppm or to parts per billion levels required for the power cycle.

20 FOSSIL-FUELED POWER PLANTS↗

Advances in the Recovery of Uranium from Seawater: Studies Under Real Ocean Conditions

The objective of this project was to move the testing of uranium adsorbents from the laboratory to the field. We were successfully able to test fibers in both a flume and ocean environment under varying conditions to quantify the adsorptive properties and uranium uptake of adsorbents under coastal ocean conditions. Through this testing we have identified numerous challenges to be overcome prior to large-scale deployment of these fibers This project began in Phase I with laboratory experiments examining the effects of flow rates and water filtration on the absorption of uranium to fibers in flowthrough columns. In this experiment we found that fibers adsorb most efficiently at a flow rate of 250 ml/min, on a per liter basis. However faster flow rates increase exposure volume and allowed for slightly greater total U absorption. Therefore a balance between current speeds that are too fast and potentially break down fibers and those that are slower will be important to consider, alongside bio-fouling and exposure time, when deciding which current regimes are best to place fibers in the ocean. Phase II examined biofouling, comparing exposure of fibers in filtered flume water to that in a coastal ocean environment. Results from the dock and flume parallel experiment indicate a strong effect of biofouling on the capacity of the adsorbent fibers to adsorb uranium towards the very end of the experiment. Dock and flume samples showed comparable adsorption rates with the flume maximum achieved at day 49 with an adsorbance of 3.4 g U/kg-ads while the dock maximum was reached at day 42 with an adsorbance of 2.7 g U/kg-ads. Biofouling mitigation techniques were also examined. A comparison of 5 m and 12 m samples showed less growth at 12 meters where there is less light as well as less growth on the copper cages, which are toxic to many marine organisms. Overall despite biofouling, particles and other elements present, the fibers adsorbed uranium up to 2.7 g U/kg-ads in our open water dock experiments. This is lower than the maximum achieved in the flume of 3.4 g U/kg-ads and much lower than rates observed with synthetic seawater in laboratory experiments. Phase III involved two parts: working at Woods Hole Oceanographic Institution (WHOI) we examined the feasibility of reusing fibers after ocean deployment. Fiber reuse is an important consideration for operational costs associated with deployment. At present our data implies that reuse after open ocean exposure may not be significantly more effective than a single long deployment of fibers. The second part of Phase III involved collaboration with A. Slocum and M. Haji at MIT to examine the effects of various enclosures for fibers. This also involved testing a rotating system, designed to be deployed as part of an offshore wind turbine.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Liquefaction of Forest Biomass to "Drop-in" Hydrocarbon Biofuels

The overall goal of the project was to demonstrate solvent liquefaction as a viable path to stable intermediates for subsequent upgrading to fuel blendstocks. Iowa State University (ISU) utilized technology developed by Chevron to produce “green crude” via continuous biomass liquefaction to bio-oil without catalyst or reducing gas, then upgraded the crude to drop-in hydrocarbon liquid transportation fuels. Original benchmarks for the project included conversion of biomass to bio-oil at a yield of 50% or more, produce bio-oil with oxygen content below 20 wt%, and recycle a portion of the bio-oil product for use as solvent, displacing initial hydrocarbon solvent. Initial testing and technology development was completed by Chevron using a custom Small Continuous Liquefaction Unit (SCLU) operated in “once-through” mode. In this system, liquid product and solid residual/char was collected together and required both off-line solids removal and product separation. This unit was disassembled and major components incorporated into a redesigned solvent liquefaction system at ISU capable of processing biomass at rates up to 1 kg/h. Online, continuous solids separation and bio-oil recovery/separation systems were successfully implemented. Online solids removal using an acetone injection to aid in separation achieved over 99% solids removal efficiency, and acetone recovery of greater than 97% was achieved. The gas stripping system developed for the separation of medium wood oil (MWO) for the recycle stream from the heavy wood oil (HWO) product stream was also successful in recovering approximately 93 wt% of the initial solvent from the biomass-derived products. Due to the generation of fine particulate and the high molecular weight of the HWO which both negatively affect the ability to separate the product oil, solvent recycle was not fully implemented in the system. The biomass used in this project is loblolly pine forest residue. The solvent was a blend of two hydrocarbon liquids. The majority of the solvent was comprised of commercially available naphthalene-depleted heavy aromatic solvent. The hydrogen donor solvent was a proprietary cut of light cycle oil (LCO) that was hydrotreated. As much as 25 wt% of the solvent mixture was comprised of the hydrotreated LCO. Higher blend ratios were limited by the economics of providing hydrogen to the process in this manner. Two cases were evaluated for technical feasibility on the SCLU. These are 1. Simulated phenolic solvent recycle and 2. Hydrocarbon-rich solvent processing. The simulated phenolic solvent recycle case was based on an idealistic solvent mixture where only 5% makeup or hydrogen donor solvent entered the system. The resulting solvent mixture at steady state was estimated to be 75 wt% depleted hydrogen donor, 20 wt% biomass derived phenolic monomers, and 5 wt% HLCO. This case resulted in the highest bio-oil organic yield observed in the project of 66.7 wt% on a solvent-less, dry biomass basis and relatively low oxygen content of 12%. Additionally, these conditions deconstructed the biomass so well, that extremely fine particulate was generated such that 5 micron barrier filters were unable to remove the material. Offline addition of acetone, centrifugation and acetone removal were required in order to remove the particulate prior to fractionation with the stripping column. The resulting HWO had a high molecular weight and was therefore very viscous in nature, remaining solid at room temperature. Additionally, the column was unable to sustainably strip enough MWO to close the recycle loop balance while maintaining flowability of product oil exiting the column. It was determined that additional HLCO would be required at the front of the process to decrease product viscosity both by dilution and additional hydrogen transfer into the HWO product oil. The hydrocarbon rich mixture was the preferred mixture for a majority of the project and featured a 25% donor or HLCO content and 75% depleted hydrogen donor mix. A series of three tests were conducted using this mixture and serve as the basis for a paper detailing the system. While the online acetone injection system for high pressure solids removal was demonstrated early on using this mixture, difficulty controlling process flows led to the use of an atmospheric stirred tank filtration system. At these high donor solvent levels, the product stream easily partitioned with sufficient MWO to close the recycle loop balance. Additionally, this mixture produced HWO product oil at just over 55% yield, <5% oxygen content, and a reasonable viscosity at room temperature. A 56 hour campaign was conducted with the ISU pilot to produce a large enough batch of HWO product oil to conduct upgrading experiments at Chevron’s Richmond, CA facility. Benchtop hydrotreating units were used to conduct long-duration hydrogenation/hydrogenolysis reactions in order to provide yield data and help validate assumptions made in the TEA model. Resulting products featured an oxygen content of <1%, near the detectability limit. Hydrocracking simulations were also performed, and a distribution of heavy wood oil to refinery products was determined. These distributions are based on a database of commercial and pilot plant operation used by Chevron to estimate product yield from novel inputs based on the input physical and chemical characteristics. While multi-week benchtop hydrotreating tests were successfully conducted without fouling, analysis and testing of the heavy wood oil suggest it may be better suited for hydrocracking. Metals content in the heavy wood oil would likely create catalyst fouling over time and reduce lifetime of hydrotreating catalysts. Yields and product partitioning were also more favorable from hydrocracking compared to those from hydrotreating.

09 BIOMASS FUELS↗

On The Management Of Radiographic Noise Sources

The numerous types of noise in a typical radiograph include: quantum noise, read noise, thermal noise, scatter, etc. The character of these noise sources can be non-stationary, non-linear, Gaussian, Poisson, white, pink, additive, multiplicative, point, random and/or systematic. Furthermore these noise sources impact radiographic factors including: conjugates, exposure duration, filtration, detector type, Swank & Fano factors, Bucky grids, energy, collection optics, charge leakage, digitizer type, dynamic range, detector temperature, pixel size, calibration technique, system stability etc. In short, the “noise” in a radiograph is a very complex subject with many real-world tradeoffs. We delineate the noise sources in a typical silicon detector (e.g. CCD, CMOS, or AmSi, TFT) to illustrate the character of those sources and statistics behind some of the choices required to readout and calibrate those detectors.

47 OTHER INSTRUMENTATION↗

Innovative Gasification to Produce Fischer-Tropsch Jet and Diesel Fuel

The primary objective of this project and the U.S. DOE’s integrated biorefinery (“IBR”) program was to demonstrate conversion of biomass and waste-derived feedstocks into military spec liquid fuels. Frontline’s proposed integrated process was to incorporate several novel technologies and innovative applications of existing technologies that would serve both to increase plant efficiency and also to lower the cost of the produced biofuels. The project was intended to demonstrate Frontline Bioenergy’s technologies for gasification and synthesis gas clean-up configuration to produce a syngas stream suitable for a proven Fischer-Tropsch (“F-T”) unit that would produce F-T intermediate products. These F-T intermediate products were to be upgraded to military spec diesel and jet fuel, including F76, JP5, and JP8. Specifically, these technologies consisted of: 1. Frontline’s PMFreeGas® ultra low particulate matter (PM) hot gas filtration technology 2. Application of Frontline’s TarFreeGas® ultra low-tar gasification technology 3. Frontline’s novel approach to syngas conditioning The proposed gasifier system was to operate at 10 tpd capacity while the F-T plant was capable of approximately one barrel per day. Although the gasifier output would have been roughly ten times the F-T plant’s required input, the 10 tpd capacity was chosen to enable scaling to commercial capacity. Project partners included i) SGC Energia, owner of the F-T technology and owner of the proposed demonstration site in Pasadena, Texas; ii) Stanley Consultants, a reputable engineering company that provided detailed electrical engineering services; and iii) Delphi Engineering & Construction LLC, a consulting company that provided project management advisory services. The integrated plant was never constructed due to lack of cost share funds. However, the commercialization plan and associated financial model suggested such a plant could be economically viable when the price of oil exceeds $70 per barrel. The price of feedstock plays a significant role in the profitability of the plant for a given value of oil. An integrated biorefinery capable of producing liquid transportation fuels and other chemical feedstocks would benefit the public by providing a sustainable pathway to convert domestically available feedstocks into fuels that might otherwise be imported from countries or regions of the world that are typically hostile to the United States.

09 BIOMASS FUELS↗

Functions and Requirements of the Radioactive Waste Test Platform

The purpose of this document is to provide the function and requirements for the Radioactive Waste Test Platform (hereafter called “test platform”). Historically, testing has been performed at the bench scale with actual waste samples (Fiskum et al. 2006a, b, 2008, 2009; Lumetta et al. 2009; Edwards et al. 2009; Smith et al. 2000, 2001). These tests form the basis for waste treatment operations at the Hanford Site. However, since 2008, there has been limited capability to perform bench-scale tests with actual waste samples. Prior work has shown that simulants can provide useful information about the performance of unit operations; however, there have been examples in the past where simulants did not adequately capture the expected performance of the tank waste materials. Therefore, as the Hanford Site moves towards initiating treatment of tank waste, it is important to have a platform available that can evaluate process options utilizing tank waste samples. This platform can be utilized to evaluate processing options and to address troubleshooting for unexpected system performance. The initial operations for the test platform will be to contribute towards maturing the Direct Feed Low-Activity Waste (DFLAW) feed qualification program and to demonstrate an option for disposition of the melter offgas stream. This equipment will be the ideal platform to evaluate additional process options including filtration operating conditions associated with precipitation, methods to extend resin lifetime associated with multi-cycle degradation, and evaluation of other approaches to minimize the impact of recycle streams from the effluent management system (including Tc) on melter performance.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Colloid-Facilitated Transport: Studies Related to CFM Project at GTS

Presentation Summary: Insights have been gained as to how to obtain defensible answers to predict radionuclide transport in fractured granites. However, site specific studies still need to be performed to to gain confidence in the prediction; The CFT ladder should be applied to evaluate the potential for enhanced transport with colloids, but most indications are that only very small fractions of strongly-sorbing radionuclides will be capable of CFT over repository time and distance scales; CFT requires very slow desorption from colloids AND very slow filtration of the RN-bearing colloids (relative to time scales of interest); Interrogating such slow processes is a challenge, especially if they are associated with a very small fraction of colloids or very small fraction of sorption sites on colloids (or both); Intuitively, one might expect that stable colloids generated from wasteform degradation that have radionuclides incorporated into their structure (as opposed to asorption association) might pose the biggest risk; Experiments have informed generic modeling approach, including GDSA; Experiments have provided insights into how experimental designs can be tailored and improved to address site-specific and scenario-specific issues; Different host rocks, EBS vs. natural system, and DPC concept can all, in principle, be addressed via different parameterizations of the generic model, with the understanding that parameterizations must be developed through site- and scenario-specific experimental testing

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Exploratory Research: Transport and Transformation of Particulate Organic Matter in Permeable River Sediments

The hyporheic zone (HZ) is the volume of streambed sediments where surface water and groundwater mix. The mixing of ground and surface water geochemical constituents including organic matter and the presence of large microbial populations create an important location for biogeochemical activity. Large and periodic fluctuations in river stage such as those associated with operation of hydroelectric dams, may enhance downstream hyporheic exchange by reversing the direction of flow to/from the stream on a regular basis. Solute transport in hyporheic zones is affected by river regulation; however, little is known about the transport of particulate organic matter (POM) under these conditions. We performed a laboratory experiment to simulate the transport and retention of POM under conditions simulating flow reversal in the hyporheic zone. Here, POM is created by inoculating artificial river water with algae obtained from the Hanford Reach of the Columbia River. POM transport experiments are then conducted in columns packed with sandy sediments; these data are then used to calibrate a model describing fundamental processes controlling its transport in saturated sediments. Models results reveal that filtration, sorption to sediment, and sorption to previously retained POM are important mechanisms of POM retention in sandy, saturated sediments. Additionally, upon flow direction reversal, POM is readily mobilized leading to effluents concentrations above the initial input concentrations. These findings indicate that river stage changes may change POM storage in the hyporheic zone depending on the type and magnitude of flow variation.

54 ENVIRONMENTAL SCIENCES↗

AP-105 Melter Offgas Condensate and EMF Evaporator Concentrate Raman and LIBS Qualitative Evaluation for the use of In-Line Monitoring (Rev. 0)

The Pacific Northwest National Laboratory (PNNL) was tasked to perform Raman spectroscopy and laser induced breakdown spectroscopy (LIBS) testing on the melter off-gas condensate generated during low-activity waste process testing of a sample from Hanford Site tank AP-105 and/or evaporate from evaporation of the condensate. This was a proof-of-principle demonstration that Raman spectroscopy and LIBS have the potential to be used as analytical tools for in-line process analysis of key aqueous phase analytes in radioactive process streams associated with the Hanford Waste Treatment and Immobilization Plant. The work completed under this project complements work completed for WRPS with the development of in-line monitoring systems to characterize and quantify constituents of tank waste following Cs removal and filtration. The WRPS work is currently limited to Raman sensors and utilizes chemometric models for quantification of several anionic species in the sample system. It should be noted that while this approach can be applied to off-gas condensate streams, new chemometric models are needed to accurately quantify analytes under off-gas condensate conditions. The work completed under this project makes timely use of available samples and equipment at PNNL. The project utilized the opportunity to collect off-gas samples from planned AP-105 processing work and included the direct condensate and the evaporate from the DFLAW Radioactive Waste Test Platform. Samples were characterized by instruments already in place at PNNL including a Raman spectrometer optimized for in-line monitoring of flowing and stationary samples as well as a LIBS instrument, which was optimized for static liquid droplet analysis. The ultimate objective was to determine if these techniques could be used to qualitatively characterize analytes present within the off-gas samples. The testing confirmed the use of the Raman as an in-line monitoring system was able to qualitatively observe NO 3 - , NO 2 - , aluminum (as aluminate, Al(OH) 4 - ), SO 4 2- , CrO 4 2- , CO 3 2- , and PO 4 3- in the AP-105 melter feed evaporator condensate samples. The testing also confirmed LIBS as a potential useful technique for in-line monitoring, able to qualitatively detect Na, N, Al, and tentatively Cr and Cl in a simulant stock evaporate solution.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Techno-Economic Analysis for the Production of Algal Biomass via Closed Photobioreactors: Future Cost Potential Evaluated Across a Range of Cultivation System Designs

In this assessment, we have evaluated target minimum biomass selling prices (MBSPs) of algae biomass production for four photobioreactor (PBR) designs compared to a previous open pond target case. We utilized techno-economic assessment modeling to determine if the target PBR cases can compete with open ponds for low-cost commodity fuels in an 'n th -plant' scenario. In the process, algal biomass is produced in one of the five cultivation options, including: open ponds, horizontal tubes, helical tubes, and two vertical bag/panel designs termed 'GWP-II flat panels' and 'Leidos hanging bags.' The projected target cultivation productivity for each PBR design was estimated based on the most credible literature data presenting PBR and pond cultivation on a directly comparable basis, and then extrapolating out to the future. Resulting productivities on an aerial basis were estimated to range from 25 g/m 2 /day to 52.5 g/m 2 /day (cultivation area). CO 2 , nutrients, and algae inoculum are supplied to the production area. After cultivation, the biomass is dewatered to 20 wt% solids in three stages including in-ground gravity settling, membrane filtration, and centrifugation. CO 2 piping, water piping, and storage are also included in the analysis. Based on our recently published 'algae farm' design report, the open pond cultivation benchmark was set at an MBSP of $494/ton ash-free dry weight (AFDW). The horizontal tubes are large volume reactors with productivity similar to that of open ponds, but result in an MBSP of $708/ton AFDW. The helical tubes are made from glass and have a high capital investment resulting in a MBSP of $1,737/ton AFDW. The GWP-II PBR is a vertical flexible plastic flat-panel system with an estimated MBSP of $1,793/ton AFDW. Finally, the Leidos hanging bag system, which derives cultivation cost values based on inputs furnished by Algenol, results in an estimated MBSP of $639/ton AFDW.

09 BIOMASS FUELS↗