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Waste Retrieval Enhancements to Achieve Preliminary Cease Waste Removal in Savannah River Site Liquid Waste Tanks 9H and 10H – 25348

The Liquid Waste (LW) contractor at the Savannah River Site (SRS) is Savannah River Mission Completion (SRMC). The LW Mission is tasked with processing legacy nuclear waste stored in underground waste tanks for final disposition. The Concentration, Storage, and Transfer Facilities (CSTF) contain 43 active waste tanks and 8 closed waste tanks between the two tank farms, F-Area Tank Farm (FTF) and H-Area Tank Farm (HTF). The first steps in the Waste Retrieval and Tank Closure (WRTC) process are the waste removal campaigns, consisting of either salt dissolution or sludge mobilization. Two tanks that are rapidly approaching the final closure determination and have demonstrated considerable success with salt dissolution are Tanks 9 and 10. The closure of these tanks is a high priority for the LW Mission due to the greater environmental risk they pose since both tanks reside within the water table and contain active leak sites from the primary tank to the annulus space. Tanks 9 and 10 have each recently completed their respective salt dissolution campaigns and achieved the Preliminary Cease Waste Removal (PCWR) milestone.

Stetson, Jacqueline G.↗

Advances in Glass Formulations for Hanford High-Aluminum, High-Iron and Enhanced Sulphate Management in HLW Streams - 13000

The current estimates and glass formulation efforts have been conservative in terms of achievable waste loadings. These formulations have been specified to ensure that the glasses are homogenous, contain essentially no crystalline phases, are processable in joule-heated, ceramic-lined melters and meet Hanford Tank Waste Treatment and Immobilization Plant (WTP) Contract terms. The WTP's overall mission will require the immobilization of tank waste compositions that are dominated by mixtures of aluminum (Al), chromium (Cr), bismuth (Bi), iron (Fe), phosphorous (P), zirconium (Zr), and sulphur (S) compounds as waste-limiting components. Glass compositions for these waste mixtures have been developed based upon previous experience and current glass property models. Recently, DOE has initiated a testing program to develop and characterize HLW glasses with higher waste loadings and higher throughput efficiencies. Results of this work have demonstrated the feasibility of increases in waste loading from about 25 wt% to 33-50 wt% (based on oxide loading) in the glass depending on the waste stream. In view of the importance of aluminum limited waste streams at Hanford (and also Savannah River), the ability to achieve high waste loadings without adversely impacting melt rates has the potential for enormous cost savings from reductions in canister count and the potential for schedule acceleration. Consequently, the potential return on the investment made in the development of these enhancements is extremely favorable. Glass composition development for one of the latest Hanford HLW projected compositions with sulphate concentrations high enough to limit waste loading have been successfully tested and show tolerance for previously unreported tolerance for sulphate. Though a significant increase in waste loading for high-iron wastes has been achieved, the magnitude of the increase is not as substantial as those achieved for high-aluminum, high-chromium, high-bismuth or sulphur. Waste processing rate increases for high-iron streams as a combined effect of higher waste loadings and higher melt rates resulting from new formulations have been achieved. (author)

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Analyze Scrap Rate for Waste Reduction

Manufacturing scrap is a term used for denoting in-process raw material waste. Many manufacturers accept scrap as an unavoidable part of the manufacturing. Scrap is created in all the phases of a manufacturing process and represents varying value of wasted materials along with other resources. The scrap is usually created in the final phases. Quality testing is the most expensive type of scrap and represents highest waste creation.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Characterization of U(VI)-Bearing Precipitates Produced by Ammonia Gas Injection Technology for Unsaturated Sediments - 16600

The processing of irradiated fuel to extract plutonium for the nuclear arsenal has resulted in a legacy of uranium contamination in the vadose zone (VZ) of the Hanford 200 Area. This contamination is a potential source for groundwater contamination, posing a risk to receptors through water uptake from contaminated wells or discharges to surface water. The injection of reactive gases is an innovative technology being evaluated for reducing the mobility of radionuclide contaminants in the Hanford vadose zone. Ammonia (NH{sub 3}) gas in particular has been used to reduce uranium mobility in laboratory scale studies and is being evaluated for field scale application. The sediment of the Hanford vadose zone is composed of a complex of mineral phases including quartz, feldspar, mica, and calcium carbonates. The silica content in the 200 Area subsurface markedly outweighs the majority of elements, with aluminum following closely. The injection of ammonia gas into the vadose zone is associated with an increase in pH conditions as the gas partitions into the pore water. The resulting alkaline conditions significantly increase the solubility of some aluminum and silicate-containing minerals within the system. As pH decreases to natural conditions, the aluminosilicate minerals will precipitate, potentially coating and sequestering the uranium contaminants. Although previous laboratory scale tests have shown decreased uranium mobility, there are many questions regarding the application of the remediation method to 200 Area vadose zone conditions. In particular, additional testing is required to understand the impact of various environmental factors on the formation of uranium mineral phases with the application of the NH{sub 3} injection method. In order to answer some of the unknowns regarding this remediation technology for the 200 Area vadose zone, an effort was made to characterize the uranium-bearing precipitates being formed with the injection of ammonia gas. Rather than a sediment-water system, a synthetic pore water solution was prepared using the ion concentrations relevant to the 200 Area vadose zone. These solutions were limited to select constituents believed to play a major role in the remediation process. The use of this carefully composed solution allows for the thorough evaluation of the contribution the variable components make to the formation of the solid analyte. The characterization of solid samples was attempted using a host of complementary analytical techniques including scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD). Though characterization of the samples is ongoing, the data produced thus far has allowed for the imaging and X-ray spectroscopy of the solid uranium phases produced as well as a tentative identification of cejkaite (Na{sub 4}(UO{sub 2})(CO{sub 3}){sub 3}) as the major uranium mineral phase. (authors)

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Emission factors of industrial boilers burning biomass-derived fuels

Boilers are combustion devices that provide process heat and are integral to many industrial facilities. Historically, outside of the pulp and paper industry, most boilers burned fossil fuels, although interest in decarbonization has been leading to an increased use of renewable fuels in boilers. These boilers, including those in the biorefineries, are often large sources of air pollutant emissions, and the characterization of these emissions is critical to obtaining air permits and ensuring protection of the surrounding air quality. Several industrial boilers and new biorefineries allow utilization of biomass-derived fuels (e.g. wastewater sludge, lignin, etc.) produced during their operation as a fuel for the boiler to meet process energy needs. However, there is limited empirical data on emission factors for the burning of unconventional fuels, such as solid-gas mixtures containing biomass residues. To fill this gap, we carry out a comprehensive data survey, collecting information on emission factors for boilers burning either a single or a mixture of solid and gaseous biomass-derived fuels. We review multiple hard-to-obtain and unconventional data sources, such as air permit applications, stack test data, and industry-sponsored data collection efforts, to compile emission factors for biomass-derived fuels. We then compare this data with wood residue emission factors from the U.S. Environmental Protection Agency’s AP-42 emission factor database. Our results indicate that the emission factors for boilers burning unconventional fuels vary widely depending on the fuel composition, boiler type, and fuel characteristics. Overall, we find that median emission factors of selected biomass-derived fuels are typically lower than those of wood residue boilers in AP-42. The information collected herein could be useful to permitting agencies and industries utilizing boilers who may want to reduce the carbon impact of their facilities by combusting biomass-derived wastes for process energy needs, for more accurate emission estimation for permitting.

09 BIOMASS FUELS↗

Distribution of Radioactive Materials in the Absheron Peninsula, Azerbaijan - 13567

The Absheron Peninsula forms the extreme Eastern part of Azerbaijan and juts into the Caspian Sea. The region has a long history of oil and gas exploration, transport, and processing and includes a number of abandoned chemical plants that were used in the separation of iodine from formation waters. As a result of lax environmental standards during the Soviet era, the industrial activity has led to serious contamination from oils residues, heavy metals and naturally occurring radioactive materials (NORM). Radiometric surveys performed over a wide range of the Absheron Peninsula showed generally low NORM concentrations. However, radiation levels two to three orders of magnitude above background levels were detected at two abandoned iodine separation plants near the capital city, Baku. These elevated radiation levels are mainly due to Ra-226 and U-238 with lower contributions from Ra-228 and U-235. (authors)

54 ENVIRONMENTAL SCIENCES↗

DETERMINATION OF STOKES SHAPE FACTOR FOR SINGLE PARTICLES AND AGGLOMERATES

The large octahedral crystals of spinel can precipitate from glass during the high-level waste vitrification process and potentially block the glass discharge riser of electrically heated ceramic melters. To help predict the settling behavior of spinel in the riser, the settling of single particles and agglomerates was studied in stagnant and transparent viscosity oils at room temperature with developed optical particle-dynamics-analyzer. Determined dimensions and terminal settling velocities of particles were used for calculation of their Stokes shape factors. Calculated shape factor for the glass beads was almost identical with the theoretical shape factor of 2/9 for a perfect sphere. The shape factor for single spinel crystal was about 7.6 % higher compare to the theoretically predicted value for octahedron. Stokes shape factor of irregularly shaped multi-particle agglomerates was lower than that of the glass beads and individual spinel crystals because of the higher surface drag caused by the larger surface area to volume ratio.

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Contribution of the numerical simulations in the development of the French HLLW vitrification Processes - 15126

For many years, the CEA (Commissariat a l'energie Atomique et aux energies Alternatives) Marcoule France has developed various processes dedicated to radioactive waste confinement, especially vitrification processes for HLLW. For 10 years now, the numerical simulation has become an important tool for research and development projects held in the CEA-AREVA Joint Vitrification Laboratory (LCV). Induction heating, fluid mechanics and thermal simulations take part of all new R and D projects. The contributions of such simulations are, first, the enhancement of the working knowledge of existing process. Those data are very useful to define optimisation choices, for example upgrades made on the hot metallic melter used since the 90's at La Hague facility. Second, the simulations are, of course, also used at the conception stage of new processes as a tool allowing wide ranges parametric tests. This has been extensively used in the design of the cold crucible inductive melter (CCIM) commissioned in 2010 at La Hague plant. Finally, it is a powerful and relatively cheap tool for prospective studies for processes of the future. Whatever the purpose, the potential benefits are gains on the reliability, the output capacity and the life time. (authors)

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Technical basis for the reduction of the maximum temperature TGA-MS analysis of oxide samples from the 3013 destructive examination program

Thermogravimetric analysis with mass spectroscopy of the evolved gas (TGA-MS) is used to quantify the moisture content of materials in the 3013 destructive examination (3013 DE) surveillance program. Salts frequently present in the 3013 DE materials volatilize in the TGA and condense in the gas lines just outside the TGA furnace. The buildup of condensate can restrict the flow of purge gas and affect both the TGA operations and the mass spectrometer calibration. Removal of the condensed salts requires frequent maintenance and subsequent calibration runs to keep the moisture measurements by mass spectroscopy within acceptable limits, creating delays in processing samples. In this report, the feasibility of determining the total moisture from TGA-MS measurements at a lower temperature is investigated. A temperature of the TGA-MS analysis which reduces the complications caused by the condensation of volatile materials is determined. Analysis shows that an excellent prediction of the presently measured total moisture value can be made using only the data generated up to 700 °C and there is a sound physical basis for this estimate. It is recommended that the maximum temperature of the TGA-MS determination of total moisture for the 3013 DE program be reduced from 1000 °C to 700 °C. It is also suggested that cumulative moisture measurements at 550 °C and 700°C be substituted for the measured value of total moisture in the 3013 DE database. Using these raw values, any of predictions of the total moisture discussed in this report can be made.

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Radioactive Demonstration Of Mineralized Waste Forms Made From Hanford Low Activity Waste (Tank Farm Blend) By Fluidized Bed Steam Reformation (FBSR)

The U.S. Department of Energy’s Office of River Protection (ORP) is responsible for the retrieval, treatment, immobilization, and disposal of Hanford’s tank waste. A key aspect of the River Protection Project (RPP) cleanup mission is to construct and operate the Hanford Tank Waste Treatment and Immobilization Plant (WTP). The WTP will separate the tank waste into high-level and low-activity waste (LAW) fractions, both of which will subsequently be vitrified. The projected throughput capacity of the WTP LAW Vitrification Facility is insufficient to complete the RPP mission in the time frame required by the Hanford Federal Facility Agreement and Consent Order, also known as the Tri-Party Agreement (TPA), i.e. December 31, 2047. Supplemental Treatment is likely to be required both to meet the TPA treatment requirements as well as to more cost effectively complete the tank waste treatment mission. The Supplemental Treatment chosen will immobilize that portion of the retrieved LAW that is not sent to the WTP’s LAW Vitrification facility into a solidified waste form. The solidified waste will then be disposed on the Hanford site in the Integrated Disposal Facility (IDF). Fluidized Bed Steam Reforming (FBSR) offers a moderate temperature (700-750°C) continuous method by which LAW can be processed irrespective of whether the waste contain organics, nitrates, sulfates/sulfides, chlorides, fluorides, volatile radionuclides or other aqueous components. The FBSR technology can process these wastes into a crystalline ceramic (mineral) waste form. The mineral waste form that is produced by co-processing waste with kaolin clay in an FBSR process has been shown to be comparable to LAW glass, i.e. leaches Tc-99, Re and Na at <2g/m 2 during ASTM C1285 (Product Consistency) durability testing. Monolithing of the granular FBSR product was investigated to prevent dispersion during transport or burial/storage. Monolithing in an inorganic geopolymer binder, which is amorphous, macro-encapsulates the granules, and the monoliths pass ANSI/ANS 16.1 and ASTM C1308 durability testing with Re achieving a Leach Index (LI) of 9 (the Hanford Integrated Disposal Facility, IDF, criteria for Tc-99) after a few days and Na achieving an LI of >6 (the Hanford IDF criteria for Na) in the first few hours. The granular and monolithic waste forms also pass the EPA Toxicity Characteristic Leaching Procedure (TCLP) for all Resource Conservation and Recovery Act (RCRA) components at the Universal Treatment Standards (UTS). Two identical Benchscale Steam Reformers (BSR) were designed and constructed at SRNL, one to treat non-radioactive simulants and the other to treat actual radioactive wastes. The results from the non-radioactive BSR were used to determine the parameters needed to operate the radioactive BSR in order to confirm the findings of non-radioactive FBSR pilot scale and engineering scale tests and to qualify an FBSR LAW waste form for applications at Hanford. Radioactive testing commenced using SRS LAW from Tank 50 chemically trimmed to look like Hanford’s blended LAW known as the Rassat simulant as this simulant composition had been tested in the non-radioactive BSR, the non-radioactive pilot scale FBSR at the Science Applications International Corporation-Science and Technology Applications Research (SAIC-STAR) facility in Idaho Falls, ID and in the TTT Engineering Scale Technology Demonstration (ESTD) at Hazen Research Inc. (HRI) in Denver, CO. This provided a “tie back” between radioactive BSR testing and non-radioactive BSR, pilot scale, and engineering scale testing. Approximately six hundred grams of non-radioactive and radioactive BSR product were made for extensive testing and comparison to the non-radioactive pilot scale tests performed in 2004 at SAIC-STAR and the engineering scale test performed in 2008 at HRI with the Rassat simulant. The same mineral phases and off-gas species were found in the radioactive and non-radioactive testing. The granular ESTD and BSR products (radioactive and non-radioactive) were analyzed for total constituents and durability tested as a granular waste form. A subset of the granular material was stabilized in a clay based geopolymer matrix at 42% and 65% FBSR loadings and durability tested as a monolith waste form. The 65 wt% FBSR loaded monolith made with clay (radioactive) was more durable than the 67-68 wt% FBSR loaded monoliths made from fly ash (non-radioactive) based on short term PCT testing. Long term, 90 to 107 day, ASTM C1308 testing (similar to ANSI/ANS 16.1 testing) was only performed on two fly ash geopolymer monoliths at 67-68 wt% FBSR loading and three clay geopolymer monoliths at 42 wt% FBSR loading. More clay geopolymers need to be made and tested at longer times at higher FBSR loadings for comparison to the fly ash monoliths. Monoliths made with metakaolin (heat treated) clay are of a more constant composition and are very reactive as the heat treated clay is amorphous and alkali activated. The monoliths made with fly ash are subject to the inherent compositional variation found in fly ash as it is a waste product from burning coal and it contains unreactive components such as mullite. However, both the fly ash and the clay based monoliths perform well in long term ASTM C1308 testing.

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A Model from the Mind to the Operating Facility - 16448

The reprocessing of Spent Magnox fuel has been undertaken at the Sellafield site in the United Kingdom (UK) for more than 50 years and is now entering the final few years of its operating programme. The age of this facility has resulted in additional operational challenges which have led to the need for a sustained programme of continuous improvement. It has therefore been necessary to assess what potential plant improvements are key to delivering a successful end to the operating programme. In 2003 the UK National Nuclear Laboratory (NNL) (then Nexia Solutions) worked with Sellafield Ltd to produce a visual discrete event simulation (DES) model. The DES approach models plant equipment (such as a storage pond crane or fuel element processing equipment), and the key processes that these items undertake. Process times, availability and process logic are all combined to provide a prediction of the plant performance. Through the use of 'what-if' scenarios, changes to any model parameter can be undertaken. The benefits of such an approach have been in the ability for Sellafield Ltd to understand which changes to make and which do not add value. This then allows the operating facility to focus the improvement programme on quantitatively underpinned benefits, thus increasing the potential to complete the reprocessing programme ahead of schedule, which is a key aim for Sellafield Ltd. Maximising the benefit of this model has required a close working relationship between NNL, Sellafield Ltd Technical and the Sellafield Ltd Operations teams to ensure that the model is using the correct information and is addressing the real issues at hand. Over the past 12 years many ideas have been assessed and three examples have been selected to demonstrate the range of use of the model, and the different approaches used to identify issues and opportunities, agree an approach and provide solutions. (authors)

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Radioisotope Analysis of Wastewater from Livermore Site Retention Tanks by Gel Laboratory Gross Alpha, Gross Beta and Tritium Sampling Method

Lawrence Livermore National Laboratory discharged approximately 4.4% of the City of Livermore’s total wastewater in 2022 (LLNL’s Annual Site Environmental Report, Chapter 5, 2022). This volume includes wastewater from Sandia National Laboratories (SNL) and some process wastewater from Site 300. Due to the high volume and constituents of the discharge, LLNL works alongside the City of Livermore under permit #1250, requiring wastewater generated to be monitored and sampled in accordance with permit limits. Process wastewater, from buildings with the highest risk to sewer, is collected by wastewater retention tanks throughout the Livermore Site and sampled prior to discharge. Domestic wastewater directly discharges to sanitary sewer. To maintain permit requirements and ensure proper wastewater discharge practices, an internal wastewater audit was conducted during the summer of 2023. Current wastewater practices, regulatory knowledge and risk management across various Livermore Site buildings were evaluated. Workspaces connected to a wastewater retention tank and sanitary sewer drains were major focus areas. Data collected from walk-throughs prompted further evaluation as many practices were reported to be done based on historical usage. A table of concerns was created to showcase reasons for auditing and proceeding action. An analysis of current and historical retention tank usage throughout LLNL Livermore Site buildings with radioisotope results over a 5-year period from 2019 to 2024, was done to assess building trends and any significant changes throughout the 5-year period. Analytes evaluated were Gross Alpha, Gross Beta and Tritium (GABT) of eleven buildings at the Livermore Site, posing the highest risk to sanitary sewer for radioisotopes.

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Antarctica Radiological Source Removals (Final Report)

On 18 May 2015, the research vessel Akademik Fedorov of the Russian Antarctic Expedition (RAE) delivered four radioisotope thermoelectric generators (RTGs) from Antarctica to the port of St. Petersburg, Russia. The RTGs had been previously used in the work program of the former Soviet Antarctic Expedition (SAE). From the mid-1970s, RTGs have been used to provide autonomous power at geophysical and meteorological stations located in remote regions of Antarctica. The research was completed in the early 1990s, but not all the generators had been removed when the stations were decommissioned. The remaining four unsecured RTGs, with their strontium-90 ( 90 Sr) radiological material and a combined total activity of 80,000 curies (Ci), still posed a potential risk as they could be used for nefarious purposes. Therefore, a plan of action for the removal of the RTGs from Antarctica was developed. This was done within the framework of the international program for the disposal of Russian RTGs. Financial support and technical oversight was provided by the U.S. Department of Energy (DOE), while logistical support was provided by the Russian Antarctic Expedition (RAE) of the Arctic and Antarctic Research Institute (AARI) and by subsidiaries of the Russian Federation’s Rosatom State Corporation. Recovering and repatriating the RTGs from the continent of Antarctica to the Russian Federation proved to be a very difficult task, including satisfying all the legal aspects within a very tight timeframe. This involved indemnification issues, adhering to new laws enacted after the Soviet Union era, and obtaining all the necessary permits and certifications for transport of the RTGs by air, sea, and land. It was an international, collaborative effort involving the cooperation of multiple organizations to complete the legal work and preparation of necessary documents. In addition, AARI needed to create a separate structure within its organization to manage the process, including the provision of special medical screenings, training, and certifications of its institute personnel. This was done so AARI could fulfill its obligation for the safe handling of radioactive materials while in the field. Recovery of the RTGs required overcoming several logistical hurdles. The Akademik Fedorov, which transported the RTGs back to the Russian Federation, required retrofits to accommodate the RTGs for safe and secure transport of radioactive material. The United States Project Team (USPT) inspected the vessel while it was in dry dock in Turku, Finland, being retrofitted with their design. Special sleds had to be designed to transport RTGs, as well as equipment for identifying crevasses in the glaciers, over the Antarctic packed snow and ice. Provision of adequate fuel supplies for the long trek to the interior of Antarctica to recover one of the RTGs also had to be addressed. With the successful recovery, repatriation, and disassembly of the RTGs, the Radioactive Heat Sources (RHSs) were extracted and dispositioned, thus eliminating any risk of these radioactive sources being used for terrorist purposes. Successful completion of the project also fulfilled the requirements of the Protocol on Environmental Protection to the Antarctic Treaty concerning the need to remove unused radioactive materials.

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Performance evaluation of a hybrid-passive landfill leachate treatment system using multivariate statistical techniques

Highlights: • Performance of a hybrid passive landfill leachate treatment system was evaluated. • 33 Water chemistry parameters were sampled for 21 months and statistically analyzed. • Parameters were strongly linked and explained most (>40%) of the variation in data. • Alkalinity, ammonia, COD, heavy metals, and iron were criteria for performance. • Eight other parameters were key in modeling system dynamics and criteria. - Abstract: A pilot-scale hybrid-passive treatment system operated at the Merrick Landfill in North Bay, Ontario, Canada, treats municipal landfill leachate and provides for subsequent natural attenuation. Collected leachate is directed to a hybrid-passive treatment system, followed by controlled release to a natural attenuation zone before entering the nearby Little Sturgeon River. The study presents a comprehensive evaluation of the performance of the system using multivariate statistical techniques to determine the interactions between parameters, major pollutants in the leachate, and the biological and chemical processes occurring in the system. Five parameters (ammonia, alkalinity, chemical oxygen demand (COD), “heavy” metals of interest, with atomic weights above calcium, and iron) were set as criteria for the evaluation of system performance based on their toxicity to aquatic ecosystems and importance in treatment with respect to discharge regulations. System data for a full range of water quality parameters over a 21-month period were analyzed using principal components analysis (PCA), as well as principal components (PC) and partial least squares (PLS) regressions. PCA indicated a high degree of association for most parameters with the first PC, which explained a high percentage (>40%) of the variation in the data, suggesting strong statistical relationships among most of the parameters in the system. Regression analyses identified 8 parameters (set as independent variables) that were most frequently retained for modeling the five criteria parameters (set as dependent variables), on a statistically significant level: conductivity, dissolved oxygen (DO), nitrite (NO{sub 2}{sup −}), organic nitrogen (N), oxidation reduction potential (ORP), pH, sulfate and total volatile solids (TVS). The criteria parameters and the significant explanatory parameters were most important in modeling the dynamics of the passive treatment system during the study period. Such techniques and procedures were found to be highly valuable and could be applied to other sites to determine parameters of interest in similar naturalized engineered systems.

54 ENVIRONMENTAL SCIENCES↗

Processing of combined domestic bath and laundry waste waters for reuse as commode flushing water

An experimental investigation of processes and system configurations for reclaiming combined bath and laundry waste waters for reuse as commode flush water was conducted. A 90-min recycle flow was effective in removing particulates and in improving other physical characteristics to the extent that the filtered water was subjectively acceptable for reuse. The addition of a charcoal filter resulted in noticeable improvements in color, turbidity, and suds elimination. Heating and chlorination of the waste waters were investigated for reducing total organism counts and eliminating coliform organisms. A temperature of 335.9 K (145 F) for 30 min and chlorine concentrations of 20 mg/l in the collection tank followed by 10 mg/l in the storage tank were determined to be adequate for this purpose. Water volume relationships and energy-use rates for the waste water reuse systems are also discussed.

Hypes, W. D.↗

Non–solvent Fractionation of Lignin Enhances Carbon Fiber Performance

Even though lignin carbon fiber has been sought after for several decades, the poor mechanical performance remains to be a major barrier for commercial applications. The low mechanical performance is attributed to the heterogeneity of lignin polymer. Recent advances in fractionation technologies showed the great potential to reduce lignin heterogeneity, but current fractionation methods often depend on costly chemicals and materials such as enzymes, organic solvents, membranes, and dialysis tubes. Here, a new non–solvent strategy was developed to fractionate lignin by autohydrolysis. By using only water, lignin was efficiently fractionated into water–soluble and –insoluble fractions. The latter fraction had increased molecular weight and uniformity and resulted in more β–O–4 interunitary linkages as analyzed by size–exclusion chromatography and 2D heteronuclear single quantum coherence NMR spectroscopy, respectively. In particular, the water–insoluble fraction significantly enhanced the mechanical performances of the resultant carbon fibers. Mechanistic study by differential scanning calorimetry (DSC) revealed that the miscibility of lignin with guest polyacrylonitrile molecules was improved with the reduced lignin heterogeneity. Crystallite analyses by XRD and Raman spectroscopy revealed that the crystallite size and content of the pre–graphitic turbostratic carbon structure were increased. The fundamental understanding revealed how lignin fractionation could modify lignin chemical features to enhance the mechanical performance of resultant carbon fibers. As a result, the autohydrolysis fractionation thus represents a green, economic, and efficient methodology to process lignin waste and boost lignin carbon fiber quality, which could open new horizons for lignin valorization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Incorporation of trace metals in Hanford waste boehmite mineral phases and dissolution rate impacts

Abstract Data from radioactive Hanford tank waste samples was analyzed to assess whether trace metals present were incorporated into the bulk boehmite matrix or were simply intermingled with the bulk material and subsequent impacts to the boehmite dissolution rate. Results suggest that chromium is primarily blended into the bulk boehmite, with a small fraction present on the surface of the solids. However, increasing the level of chromium incorporation 30‐fold decreased the dissolution rate of boehmite by only 8%, suggesting incorporation of chromium into these samples had a minimal impact on the dissolution rate. Iron was also found to be incorporated in the boehmite solids. Silicon appears to be simply intermingled and not blended into the boehmite crystals.

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