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At least 1,099 records · Page 61

Uranium Anodic Dissolution under Slightly Alkaline Conditions

Argonne National Laboratory is developing an alternative method for digesting irradiated low enriched uranium foil targets to produce 99 Mo in neutral/alkaline media. This method involves the electrolytic dissolution of irradiated uranium foil in sodium bicarbonate solution, followed by the precipitation of carbonate, base-insoluble fission and activation products, and uranyl species with CaO. The addition of CaO is vital for the effective anion exchange separation of 99 MoO 4 2- from the fission products, since most of the interfering anions (e.g., CO 3 2- ) are removed from the solution while the molybdate remains in it. An anion exchange is used to retain and purify the 99 Mo from the filtrate. The electrochemical dissolver has been designed and will be tested with low-burnup depleted uranium foil at Argonne and later with high-burnup targets at Oak Ridge National Laboratory.

Guelis, Artem V.↗

Final technical report for project titled Quantitative Characterization of Cell Aggregation/Adhesion as Predictor for Distribution and Transport of Microorganisms in Subsurface Environment

This project aims to explore and develop enabling methodology and techniques for nano-scale characterization of microbe cell surface contact mechanics, interactions and adhesion quantities that allow for identification and quantification of indicative properties related to microorganism migration and transport behavior in porous media and in subsurface environments. Microbe transport has wide impact and therefore is of great interest in various environmental applications such as in situ or enhanced subsurface bioremediation,filtration processes for water and wastewater treatments and protection of drinking water supplies. Although great progress has been made towards understanding the identities and activities of these microorganisms in the subsurface, to date, little is known of the mechanisms that govern the mobility and transport of microorganisms in DOE’s contaminated sites, making the outcomes of in situ natural attenuation or contaminant stability enhancement unpredictable. Conventionally, movement of microorganisms was believed to follows the rules governing solute (particle) transport. However, recent studies revealed that cell surface properties, especially those pertaining to cell attachment/adhesion and aggregation behavior, can cause the microbe behavior to deviate from non-viable particles and hence greatly influence the mobility and distribution of microorganisms in porous media.This complexity highlights the need to obtain detailed information of cell-cell and cell-surface interactions in order to improve and refine the conceptual and quantitative model development for fate and transport of microorganisms and contaminant in subsurface. Traditional cell surface characterization methods are not sufficient to fully predict the deposition rates and transport behaviors of microorganism observed. A breakthrough of methodology that would allow for quantitative and molecular-level description of intrinsic cell surface properties indicative for cell-surface interactions is essential for the field. To tackle this, we have developed a number of new Bio-nanomechanical techniques, including reflection interference contrast microscopy (RICM) and bio-AFM (Atomic Force Microscopy), for cell adhesion-detachment measurement of the long-range surface interactions, in combination with mathematical modeling, which would allow us to characterize the mechanical behavior from single cell to multi-cell aggregate, critical thresholds for large scale coaggregation and transportation of cells and aggregates in the presence of long range inter-surface forces etc. Although some technical and mathematical challenges remain, the preliminary results promise great breakthrough potential. In this study, we investigated the cellular surface characteristics of representative bio-remediating microorganisms relevant to DOE IFRC (Integrated Field-Scale Subsurface Research Challenges) sites and their transport behaviors in porous media, aiming to draw a groundbreaking correlation between the micro-scale genetic and biological origin-based cell surface properties, the consequent mechanical adhesion and aggregation behaviors, and the macro-scale microbial mobility and retention in porous media, which are unavailable in the literature. The long-term goal is to significantly improve the mechanistic and quantitative understanding of microbial mobility, sorption, and transport within reactive transport models as needed to manipulate subsurface contaminant fate and transport predictions.

54 ENVIRONMENTAL SCIENCES↗

Healthy Zero Energy Buildings (HZEB) Program - Cross-Sectional Study of Contaminant Levels, Source, Strengths, and Ventilation Rates in Retail Stores

This field study measured ventilation rates and indoor air quality parameters in 21 visits to retail stores in California. The data was collected to guide the development of new, science-based commercial building ventilation rate standards that balance the dual objectives of increasing energy efficiency and maintaining acceptable indoor air quality. Data collection occurred between September 2011 and March 2013. Three types of stores participated in this study: grocery stores, furniture/hardware stores, and apparel stores. Ventilation rates and indoor air contaminant concentrations were measured on a weekday, typically between 9 am and 6 pm. Ventilation rates measured using a tracer gas decay method exceeded the minimum requirement of California’s Title 24 Standard in all but one store. Even though there was adequate ventilation according to Title 24, concentrations of formaldehyde, acetaldehyde, and acrolein exceeded the most stringent chronic health guidelines. Other indoor air contaminants measured included carbon dioxide (CO{sub 2}), carbon monoxide (CO), ozone (O{sub 3}), and particulate matter (PM). Concentrations of CO{sub 2} were kept low by adequate ventilation, and were assumed low also because the sampling occurred on a weekday when retail stores were less busy. CO concentrations were also low. The indoor-outdoor ratios of O{sub 3} showed that the first-order loss rate may vary by store trade types and also by ventilation mode (mechanical versus natural). Analysis of fine and ultrafine PM measurements showed that a substantial portion of the particle mass in grocery stores with cooking-related emissions was in particles less than 0.3 μm. Stores without cooking as an indoor source had PM size distributions that were more similar indoors and outdoors. The whole-building emission rates of volatile organic compounds (VOCs) and PM were estimated from the measured ventilation rates and indoor and outdoor contaminant concentrations. Mass balance models were then used to determine the ventilation rates, filtration strategies, or source reductions needed to maintain indoor contaminant concentrations below reference levels. Several scenarios of potential concern were considered: (i) formaldehyde levels in furniture/hardware stores, (ii) contaminants associated with cooking (e.g., PM, acrolein, and acetaldehyde) in grocery stores, and (iii) outdoor contaminants (e.g., PM and O{sub 3}) impacting stores that use natural ventilation. Estimated formaldehyde emission rates suggest that retail stores would need to ventilate at levels far exceeding the current Title 24 requirement to lower indoor concentrations below California’s stringent formaldehyde reference level. Given the high costs of providing ventilation but only modest chronic health benefit is expected, effective source control is an attractive alternative, as demonstrated by some retail stores in this study. Predictions showed that grocery stores need MERV 13 air filters, instead of MERV 8 filters that are more commonly used, to maintain indoor PM at levels that meet the chronic health standards for PM. Exposure to acrolein is a potential health concern in grocery stores, and should be addressed by increasing the use of kitchen range hoods or improving their contaminant removal efficiency. In stores that rely on natural ventilation, indoor PM can be a health concern if the stores are located in areas with high outdoor PM. This concern may be addressed by switching to mechanical ventilation when the outdoor air quality is poor, while continuing natural ventilation when outdoor air quality is good.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Effect Of Ventilation On Chronic Health Risks In Schools And Offices

This study provides a risk assessment for chronic health risks from inhalation exposure to indoor air pollutants in offices and schools with a focus how ventilation impacts exposures to, and risks from, volatile organic compounds (VOCs) and particulate matter (PM2.5). We estimate how much health risks could change with varying ventilation rates under two scenarios: (i) halving the measured ventilation rates and (ii) doubling the measured ventilation rates. For the hazard characterization we draw upon prior papers that identified pollutants potentially affecting health with indoor air concentrations responsive to changes in ventilation rates. For exposure assessment we determine representative concentrations of pollutants using data available in current literature and model changes in exposures with changes in ventilation rates. As a metric of disease burden, we use disability adjusted life years (DALYs) to address both cancer and non-cancer effects. We also compare exposures to guidelines published by regulatory agencies to assess chronic health risks. Chronic health risks are driven primarily by particulate matter exposure, with an estimated baseline disease burden of 150 DALYs per 100,000 people in offices and 140 DALYs per 100,000 people in schools. Study results show that PM2.5-related DALYs are not very sensitive to changes in ventilation rates. Filtration is more effective at controlling PM2.5 concentrations and health effects. Non-cancer health effects contribute only a small fraction of the overall chronic health burden of populations in offices and schools (<1 DALY per 100,000 people). Cancer health effects dominate the disease burden in schools (3 DALYs per 100,000) and offices (5 DALYs per 100,000), with formaldehyde being the primary risk driver. In spite of large uncertainties in toxicological data and dose-response modeling, our results support the finding that ventilation rate changes do not have significant impacts on estimated chronic disease burdens. Median estimates of DALYs are approximately doubled when the ventilation rates are halved and there is little reduction in health risks associated with doubling ventilation rates, but the very low baseline disease burden from the indoor exposures we considered makes this unremarkable. In exploring the full range of exposure concentrations, to find the fraction exceeding the Office of Environmental Health and Hazard Assessment’s (OEHHAs) chronic reference exposure levels (cRELs) and United States Environmental Protection Agency’s (USEPA) chronic reference dose (RfD) we found only minor shifts in exposure safety margins when ventilation was doubled or halved. We combined our exposure estimates with cancer potency factors published by OEHHA and USEPA to determine that the annual excess cancer risk per capita are below 1 in a million under all ventilation rate scenarios for individual pollutants. The results indicate that chronic health risks (cancer and non-cancer) associated with VOC and PM2.5 exposure in offices and schools are low and thus the chronic disease burden or health benefits of ventilation changes are likely to be well below both the level of detection by health surveillance studies and the level of regulatory thresholds.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Compilation of Published PM2.5 Emission Rates for Cooking, Candles and Incense for Use in Modeling of Exposures in Residences

recent analysis of health impacts from air pollutant inhalation in homes found that PM2.5 is the most damaging at the population level. Chronic exposure to elevated PM2.5 has the potential to damage human respiratory systems, and may result in premature death. PM2.5 exposures in homes can be mitigated through various approaches including kitchen exhaust ventilation, filtration, indoor pollutant source reduction and designing ventilation systems to reduce the entry of PM2.5 from outdoors. Analysis of the potential benefits and costs of various approaches can be accomplished using computer codes that simulate the key physical processes including emissions, dilution and ventilation. The largest sources of PM2.5 in residences broadly are entry from outdoors and emissions from indoor combustion. The largest indoor sources are tobacco combustion (smoking), cooking and the burning of candles and incense. Data on the magnitude of PM2.5 and other pollutant emissions from these events and processes are required to conduct simulations for analysis. The goal of this study was to produce a database of pollutant emission rates associated with cooking and the burning of candles and incense. The target use of these data is for indoor air quality modeling.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

C-14/I-29 Preservation and Hold Time Survey

Preservation and hold time of radionuclides must account for both nuclear half-lives and nonnuclear loss mechanisms, but variations in the latter are often neglected. Metals-based defaults are inappropriate for long-lived non-metals C-14 and I-129, which are vulnerable to chemical and biological volatilization. Non-acidification is already widely practiced for them. Recommended addition measures from radiological and chemical literature include glass containers where possible, water filtration where possible, headspace minimization, light shielding, cold (4°C) storage and unfiltered water hold time of 28 days. Soil hold time may need to be shortened when water-logged, excessively sandy, or still adjusting to significant new contamination.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

MST Filterability Tests

The Savannah River Site (SRS) is currently treating radioactive liquid waste with the Actinide Removal Process (ARP) and the Modular Caustic Side Solvent Extraction Unit (MCU). The low filter flux through the ARP has limited the rate at which radioactive liquid waste can be treated. Recent filter flux has averaged approximately 5 gallons per minute (gpm). Salt Batch 6 has had a lower processing rate and required frequent filter cleaning. Savannah River Remediation (SRR) has a desire to understand the causes of the low filter flux and to increase ARP/MCU throughput. In addition, at the time the testing started, SRR was assessing the impact of replacing the 0.1 micron filter with a 0.5 micron filter. This report describes testing of MST filterability to investigate the impact of filter pore size and MST particle size on filter flux and testing of filter enhancers to attempt to increase filter flux. The authors constructed a laboratory-scale crossflow filter apparatus with two crossflow filters operating in parallel. One filter was a 0.1 micron Mott sintered SS filter and the other was a 0.5 micron Mott sintered SS filter. The authors also constructed a dead-end filtration apparatus to conduct screening tests with potential filter aids and body feeds, referred to as filter enhancers. The original baseline for ARP was 5.6 M sodium salt solution with a free hydroxide concentration of approximately 1.7 M.3 ARP has been operating with a sodium concentration of approximately 6.4 M and a free hydroxide concentration of approximately 2.5 M. SRNL conducted tests varying the concentration of sodium and free hydroxide to determine whether those changes had a significant effect on filter flux. The feed slurries for the MST filterability tests were composed of simple salts (NaOH, NaNO 2 , and NaNO 3 ) and MST (0.2 – 4.8 g/L). The feed slurry for the filter enhancer tests contained simulated salt batch 6 supernate, MST, and filter enhancers.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Sample Results From Tank 48H Samples HTF-48-14-158, -159, -169, and -170

Savannah River National Laboratory (SRNL) analyzed samples from Tank 48H in support of determining the cause for the unusually high dose rates at the sampling points for this tank. A set of two samples was taken from the quiescent tank, and two additional samples were taken after the contents of the tank were mixed. The results of the analyses of all the samples show that the contents of the tank have changed very little since the analysis of the previous sample in 2012. The solids are almost exclusively composed of tetraphenylborate (TPB) salts, and there is no indication of acceleration in the TPB decomposition. The filtrate composition shows a moderate increase in salt concentration and density, which is attributable to the addition of NaOH for the purposes of corrosion control. An older modeling simulation of the TPB degradation was updated, and the supernate results from a 2012 sample were run in the model. This result was compared to the results from the 2014 recent sample results reported in this document. The model indicates there is no change in the TPB degradation from 2012 to 2014. SRNL measured the buoyancy of the TPB solids in Tank 48H simulant solutions. It was determined that a solution of density 1.279 g/mL (~6.5M sodium) was capable of indefinitely suspending the TPB solids evenly throughout the solution. A solution of density 1.296 g/mL (~7M sodium) caused a significant fraction of the solids to float on the solution surface. As the experiments could not include the effect of additional buoyancy elements such as benzene or hydrogen generation, the buoyancy measurements provide an upper bound estimate of the density in Tank 48H required to float the solids.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Analysis of Tank 35H Samples in Support of Salt Batch Planning

Savannah River Remediation obtained three samples from different heights within Tank 35H. The samples were analyzed by Savannah River National Laboratory to support Salt Batch planning. The results from the analysis indicate the compositions of the three samples show increasing concentrations for most analytes going from HTF-35-15-17 through HTF-35-15-19 corresponding to successively deeper sampling locations. The data indicate some stratification within the tank. The plutonium and Sr-90 concentrations measured in the filtered samples were slightly lower than in the decanted (unfiltered) samples. The difference in the results for the filtered and unfiltered samples likely lies within the expected uncertainty for the measurement, but may indicate that filtration removed a small amount of suspended material from the samples.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Sustainable Management of Flowback Water during Hydraulic Fracturing of Marcellus Shale for Natural Gas Production

This study evaluated the feasibility of using abandoned mine drainage (AMD) as make- up water for the reuse of produced water for hydraulic fracturing. There is an abundance of AMD sources near permitted gas wells as documented in this study that can not only serve as makeup water and reduce the demand on high quality water resources but can also as a source of chemicals to treat produced water prior to reuse. The assessment of AMD availability for this purpose based on proximity and relevant regulations was accompanied by bench- and pilot-scale studies to determine optimal treatment to achieve desired water quality for use in hydraulic fracturing. Sulfate ions that are often present in AMD at elevated levels will react with Ba²⁺ and Sr²⁺ in produced water to form insoluble sulfate compounds. Both membrane microfiltration and gravity separation were evaluated for the removal of solids formed as a result of mixing these two impaired waters. Laboratory studies revealed that neither AMD nor barite formed in solution had significant impact on membrane filtration but that some produced waters contained submicron particles that can cause severe fouling of microfiltration membrane. Coagulation/flocculation was found to be an effective process for the removal of suspended solids and both bench- and pilot-scale studies revealed that optimal process conditions can consistently achieve the turbidity of the finished water below 5 NTU. Adjusting the blending ratio of AMD and produced water can achieve the desired effluent sulfate concentration that can be accurately predicted by chemical thermodynamics. Co-treatment of produced water and AMD will result in elevated levels of naturally occurring radioactive materials (NORM) in the solid waste generated in this process due to radium co-precipitation with barium sulfate. Laboratory studies revealed that the mobility of barite that may form in the subsurface due to the presence of sulfate in the fracturing fluid can be controlled by the addition of appropriate antiscalants.

03 NATURAL GAS↗

Advancement of Systems Designs and Key Engineering Technologies for Materials Based Hydrogen Storage

UTRC lead the development of the Simulink Framework model that enables a comparison of different hydrogen storage systems on a common basis. The Simulink Framework model was disseminated on the www.HSECoE.org website that is hosted by NREL. UTRC contributed to a better understanding of the safety aspects of the proposed hydrogen storage systems. UTRC also participated in the Failure Mode and Effect Analysis of both the chemical- and the adsorbent-based hydrogen storage system during Phase 2 of the Hydrogen Storage Engineering Center of Excellence. UTRC designed a hydrogen storage system with a reversible metal hydride material in a compacted form for light-duty vehicles with a 5.6 kg H2 storage capacity, giving it a 300 miles range. It contains a heat exchanger that enables efficient cooling of the metal hydride material during hydrogen absorption in order to meet the 3.3 minute refueling time target. It has been shown through computation that the kinetics of hydrogen absorption of Ti-catalyzed NaAlH4 was ultimately limiting the rate of hydrogen absorption to 85% of the material capacity in 3.3 minutes. An inverse analysis was performed in order to determine the material property requirements in order for a metal hydride based hydrogen storage system to meet the DOE targets. Work on metal hydride storage systems was halted after the Phase 1 to Phase 2 review due to the lack of metal hydride materials with the required material properties. UTRC contributed to the design of a chemical hydrogen storage system by developing an adsorbent for removing the impurity ammonia from the hydrogen gas, by developing a system to meter the transport of Ammonia Borane (AB) powder to a thermolysis reactor, and by developing a gas-liquid-separator (GLS) for the separation of hydrogen gas from AB slurry in silicone oil. Stripping impurities from hydrogen gas is essential for a long life of the fuel cell system on board of a vehicle. Work on solid transport of AB was halted after the Phase 1 to Phase 2 review in favor of studying the slurry-form of AB as it appeared to be difficult to transport a solid form of AB through the thermolysis reactor. UTRC demonstrated the operation of a compact GLS in the laboratory at a scale that would be required for the actual automotive application. The GLS met the targets for weight and volume. UTRC also reported about the unresolved issue associated with the high vapor pressure of fluids that could be used for making a slurry-form of AB. Work on the GLS was halted after the Phase 2 to Phase 3 review as the off-board regeneration efficiency of the spent AB was below the DOE target of 60%. UTRC contributed to the design of an adsorbent-based hydrogen storage system through measurements of the thermal conductivity of a compacted form of Metal Organic Framework (MOF) number 5 and through the development and sizing of a particulate filter. Thermal conductivity is important for the design of the modular adsorbent tank insert (MATI), as developed by Oregon State University (OSU), in order to enable a rapid refueling process. Stringent hydrogen quality requirements can only be met with an efficient particulate filtration system. UTRC developed a method to size the particulate filter by taking into account the effect of the pressure drop on the hydrogen adsorption process in the tank. UTRC raised awareness about the potential use of materials-based H2 storage systems in applications outside the traditional light-duty vehicle market segment by presenting at several conferences about niche application opportunities in Unmanned Aerial Vehicles (UAV), Autonomous Underwater Vehicles (AUV), portable power and others.

08 HYDROGEN↗

Summary of recent Raman Spectroscopy testing of SRS processes

This report describes several scoping projects conducted at SRNL using Raman spectroscopic methods for monitoring different aspects of nuclear waste and materials processing. One project examined the suitability of a Raman telescope for in situ measurement of solid residues in waste tanks. Characteristics evaluated for this equipment included radiation resistance, ease of use, and sensitivity. A second project monitored the nitrate content in liquid filtrate from the testing of a rotary microfilter using a fiber-based insertion probe. The third project made Raman measurements of various gases, including H 2 and NO x , in the headspace of a vessel while dissolving aluminum coupons in nitric acid. Measurements followed the evolution of these species in real time. Although the majority of these projects occurred in the laboratory environment, SRNL has substantial experience with implementing other optical techniques into nuclear materials processing environments. The work described in this report shows the potential of the Raman technology to provide real time measurements of species such as nitrate or hydroxide during sludge washing or evolved gases such as hydrogen or NO x during waste processing.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Treatment of Oil & Gas Produced Water.

Production of oil and gas reserves in the New Mexico Four Corners Region results in large volumes of "produced water". The common method for handling the produced water from well production is re-injection in regulatory permitted salt water disposal wells. This is expensive (%7E $5/bbl.) and does not recycle water, an ever increasingly valuable commodity. Previously, Sandia National Laboratories and several NM small business tested pressure driven membrane-filtration techniques to remove the high TDS (total dissolved solids) from a Four Corners Coal Bed Methane produced water. Treatment effectiveness was less than optimal due to problems with pre-treatment. Inadequate pre-treatment allowed hydrocarbons, wax and biological growth to foul the membranes. Recently, an innovative pre-treatment scheme using ozone and hydrogen peroxide was pilot tested. Results showed complete removal of hydrocarbons and the majority of organic constituents from a gas well production water. ACKNOWLEDGEMENTS This report was made possible through funding from the New Mexico Small Business Administration (NMSBA) Program at Sandia National Laboratories. Special thanks to Juan Martinez and Genaro Montoya for guidance and support from project inception to completion. Also, special thanks to Frank McDonald, the small businesses team POC, for laying the ground work for the entire project; Teresa McCown, the gas well owner and very knowledgeable- fantastic site host; Lea and Tim Phillips for their tremendous knowledge and passion in the oil & gas industry.; and Frank Miller and Steve Addleman for providing a pilot scale version of their proprietary process to facilitate the pilot testing.

54 ENVIRONMENTAL SCIENCES↗

Analytical Results from Routine DSSHT and SEHT Monthly Samples

Strip Effluent Hold Tank (SEHT) and Decontaminated Salt Solution Hold Tank (DSSHT) samples from several of the “microbatches” of Integrated Salt Disposition Project (ISDP) Salt Batch (“Macrobatch”) 8B have been analyzed for 238 Pu, 90 Sr, 137 Cs, cations (Inductively Coupled Plasma Emission Spectroscopy - ICPES), and anions (Ion Chromatography Anions - IC-A). The analytical results from the current microbatch samples are similar to those from previous macrobatch samples. The Actinide Removal Process (ARP) and the Modular Caustic-Side Solvent Extraction Unit (MCU) continue to show more than adequate Pu and Sr removal for times when monosodium titanate (MST) is used. Even with no MST strike being performed there exists some small Pu and Sr removal, likely from filtration of fines containing these elements. The Cs removal continues to be excellent, with decontamination factors (DF) averaging 16,400. The bulk chemistry of the DSSHT and SEHT samples do not show any signs of unusual behavior. SRNL recommends that a sample of the strip feed be analyzed for cation and anion content if a further decline in boron concentration is noted in future SEHT samples.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development of Ultrafiltration Membrane-Separation Technology for Energy-Efficient Water Treatment and Desalination Process

The growing scarcity of fresh water is a major political and economic challenge in the 21st century. Compared to thermal-based distillation technique of water production, pressure driven membrane-based water purification process, such as ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO), can offer more energy-efficient and environmentally friendly solution to clean water production. Potential applications also include removal of hazardous chemicals (i.e., arsenic, pesticides, organics) from water. Although those membrane-separation technologies have been used to produce drinking water from seawater (desalination) and non-traditional water (i.e., municipal wastewater and brackish groundwater) over the last decades, they still have problems in order to be applied in large-scale operations. Currently, a major huddle of membrane-based water purification technology for large-scale commercialization is membrane fouling and its resulting increases in pressure and energy cost of filtration process. Membrane cleaning methods, which can restore the membrane properties to some degree, usually cause irreversible damage to the membranes. Considering that electricity for creating of pressure constitutes a majority of cost (~50%) in membrane-based water purification process, the development of new nano-porous membranes that are more resistant to degradation and less subject to fouling is highly desired. Styrene-ethylene/butylene-styrene (SEBS) block copolymer is one of the best known block copolymers that induces well defined morphologies. Due to the polarity difference of aromatic styrene unit and saturated ethylene/butylene unit, these two polymer chains self-assemble each other and form different phase-separated morphologies depending on the ratios of two polymer chain lengths. Because the surface of SEBS is hydrophobic which easily causes fouling of membrane, incorporation of ionic group (e,g, sulfonate) to the polymer is necessary to reduces fouling. Recently, sulfonated SEBS became commercially available and has been extensively explored for membrane-mediated water purification technology. The sulfonated block copolymer creates a well developed nano-sale phase-separated morphologies composed of hydrophilic domains (sulfonated polystyrene) and hydrophobic domains (polyethylene/polybutylene). The hydrophilic domains determines transport properties (water transport, salt and/or ion rejection, etc) and the hydrophobic domains provides mechanical stability of the membrane. Unfortunately, a high degree of sulfonation of SEBS induces excessive swelling and deterioration of mechanical stability of the membrane. In an effort to develop robust polymeric membrane materials for water purification technology, phosphonic acid-functionalized SEBS membranes are investigated during this report period. In compare to sulfonated polymers, the corresponding phosphonated polymers are known to swell less because of the formation of extensive hydrogen bonding networks between phosphonates. In addition to the expected better mechanical stability, phosphonated polymers has another advantage over sulfonated polymers for the use water purification membrane; each phosphonate can accommodate two ions while each sulfonate accommodates only one ion. Membrane properties (ion type, ionic density, etc) of new membranes will be studied and their separation performance will be evaluated in water purification and desalination process. Through systematic study of the relationship of chemical structure–surface property–membrane performance, we aim to better understand the nature of membrane fouling and develop more fouling-resistant water purification membranes. The basic understanding of this relationship will lead to the development of advanced membrane materials which can offer a solution to environmentally sustainable production of fresh water.

36 MATERIALS SCIENCE↗

BER-Myriant Succinic Acid Biorefinery

Myriant Corporation (Myriant) has successfully produced the bioproduct succinic acid by the fermentation of glucose at a commercial scale operation in Lake Providence, Louisiana. The MySAB facility (Myriant Succinic Acid Biorefinery) came on stream in May 2013 and has been producing product since then. The MySAB facility is a demonstration-scale plant, capable of utilizing sorghum grits and commercially available dextrose, to ferment glucose into succinic acid. A downstream processing train has demonstrated the ability to produce an industrial, a standard and a polymer grade product. It consists of cell separation, membrane filtration, continuous chromatography, polishing to remove ionic and color bodies impurities, and final evaporation and crystallization. A by-product of the process is ammonium sulfate which is sold as a liquid fertilizer product. Since 2007 when development work began in the Woburn, Massachusetts R&D laboratories, the succinic acid bio-process has evolved through: Process development (microbiology, fermentation, and downstream) – R&D development laboratories; Piloting efforts at Fermic S.A. de C.V., Mexico City, Mexico – upstream and downstream processes; Design, construction, commissioning, and commercial production operations at the MySAB facility Additionally, Myriant became a wholly-owned subsidiary of the PTT Global Chemical Plc., Thailand, in late 2015, their investment into and support of Myriant goes back to 2011. The support of PTT Global Chemical Plc. helped to improve the upstream and downstream processes, and produce significant metric ton quantities of high quality bio-based succinic acid. The product has gone into a number of commercial markets worldwide for customer applications, development and production. The experience base gained via operations at the MySAB facility since May 2013, along with continued R&D development efforts involving Microbiology, Fermentation, and Downstream processes, at both the Woburn, Massachusetts and PTT Global Chemical Plc. Thailand laboratories, positions the company well for future production at the plant and commercialization of new bio-based products. This will be especially important and valuable as the green chemistry business climate continues to take root and flourish.

09 BIOMASS FUELS↗

Characterization of the Tribological Behavior of Graphene-Based Additives

XG-supplied nanocrystalline additives were extensively tested for friction and wear behavior. A technique for investigating the stability of additives was developed, and a report covered filtration and centrifugation methods for settling and filterable content. Friction and wear trends in partially and fully formulated oils were reported. Particle size analysis was performed and reported.

36 MATERIALS SCIENCE↗

Water Availability Indices – A Literature Review

Fresh water is a critical resource for humanity and the ecosystem. In general, water resources can be partitioned into two major categories: blue water and green water (Falkenmark and Rockström 2006). Precipitation that runs off or percolates into the deep aquifer is defined as blue water, and precipitation that filtrates into soil, which eventually returns to the atmosphere as evaporation, is called green water (Hoekstra et al. 2011). For human purposes, green water is almost exclusively used for agricultural production, but blue water can be used for multiple competing sectors, such as irrigation and municipal water.

54 ENVIRONMENTAL SCIENCES↗