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At least 19 records

Photoautotrophic organic acid production: Glycolic acid production by microalgal cultivation

Although microalgae produce value-added products, such as lipids, pigments, and polysaccharides using light and carbon dioxide, these intracellular products require costly downstream processes such as extraction and purification. Thus, extracellular products are desirable for economic production. While reported before, the secretion of glycolic acid by microalgal photorespiration has not received attention for industrial applications. Here we developed a two-stage continuous cultivation system to increase glycolic acid production using a glycolate dehydrogenase (GYD1) deficient mutant of Chlamydomonas reinhardtii which produces high concentrations of glycolic acid. Specifically, 3% CO 2 was supplied in the first-stage culture for the production of biomass and ambient air (0.03% CO 2 ) was supplied to the second stage for the production of glycolic acid. As a result, overall glycolic acid productivity reached 82.0 mg L -1 d -1 at a dilution rate of 0.34 d -1 . However, as the pH of the second stage decreased to 4.7 due to the increased glycolic acid production, we controlled the pH of the second stage at pH 6.0, resulting in 122.6 mg L -1 d -1 of glycolic acid productivity. Flux balance analysis revealed that the experimental glycolic acid production rate was 69% of the theoretical glycolic acid production rate. The deviation might be due to the toxicity of glycolic acid. When a techno-economic analysis was conducted based on the experimental results, the minimum glycolic acid production cost was estimated to be $31 kg -1 , indicating a potential for industrial production. Our findings suggest that microalgae can be utilized for the cost-effective industrial production of glycolic acid.

42 ENGINEERING↗

Millimetre Wave Rotational Spectrum of Glycolic Acid

The pure rotational spectrum of glycolic acid, CH2OHCOOH, was studied in the region 115-318 GHz. For the most stable SSC conformer, transitions in all vibrational states up to 400 cm(exp -1) have been measured and their analysis is reported. The data sets for the ground state, v21 = 1, and v21 = 2 have been considerably extended. Immediately higher in vibrational energy are two triads of interacting vibrational states and their rotational transitions have been assigned and successfully fitted with coupled Hamiltonians accounting for Fermi and Coriolis resonances. The derived energy level spacings establish that the vibrational frequency of the v21 mode is close to 100 cm(exp -1). The existence of the less stable AAT conformer in the near 50 C sample used in our experiment was also confirmed and additional transitions have been measured.

Rotational Spectrum↗

Effect of osteoblastic culture conditions on the structure of poly(DL-lactic-co-glycolic acid) foam scaffolds

Poly(DL-lactic-co-glycolic acid) (PLGA) foams are an osteoconductive support that holds promise for the development of bone tissue in vitro and implantation into orthopedic defects. Because it is desirable that foams maintain their shape and size, we examined a variety of foams cultured in vitro with osteoblastic cells. Foams were prepared with different porosities and pore sizes by the method of solvent casting/porogen leaching using 80, 85, and 90 wt% NaCl sieved with particle sizes of 150-300 and 300-500 microm and characterized by mercury intrusion porosimetry. Foams seeded with cells were found to have volumes after 7 days in static culture that decreased with increasing porosity: the least porous exhibited no change in volume while the most porous foams decreased by 39 +/- 10%. In addition, a correlation was observed between decreasing foam volume after 7 days in culture and decreasing internal surface area of the foams prior to seeding. Furthermore, foams prepared with the 300-500 microm porogen had lower porosities, greater mean wall thicknesses between adjacent pores, and larger volumes after 7 days in culture than those prepared with the smaller porogen. Two culture conditions for maintaining cells, static and agitated (in a rotary vessel), were found to have similar influences on foam size, cell density, and osteoblastic function for 7 and 14 days in culture. Finally, we examined unseeded foams in aqueous solutions of pH 3.0, 5.0, and 7.4 and found no significant decrease in foam size with degradation. This study demonstrates that adherent osteoblastic cells may collapse very porous PLGA foams prepared by solvent casting/particulate leaching: a potentially undesirable property for repair of orthopedic defects.

NASA Program Fundamental Space Biology↗

Radioactive Waste Sludge Washing and Demonstration of the Nitric-Glycolic Acid Flowsheet for Sludge Batch 10 Qualification

For each sludge batch that is processed in the Defense Waste Processing Facility (DWPF), the Savannah River National Laboratory (SRNL) performs qualification testing to demonstrate that the sludge batch (SB) is processible. During processing of SB9, DWPF will be transitioning from the Nitric-Formic Acid (NFA) flowsheet to the Nitric-Glycolic Acid (NGA) flowsheet. Thus, the qualification of SB10 was requested to only be performed using the NGA flowsheet. In order to qualify the batch for the NGA flowsheet, Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) cycles, designated SC-19, were performed using SB10 Tank 51 sample material. SRNL received Tank 51 material in the midst of Tank Farm washing. SRNL continued the washing in the SRNL Shielded Cells. The SRNL process included the addition of Sodium Reactor Experiment (SRE) material from H Canyon, simulating the transfer of SRE from H Canyon to Tank 51 during Tank Farm washing. The washed SB10 Tank 51 material, with SRE, was characterized prior to flowsheet qualification testing.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Oxidation of glucose to glycolic acid using oxygen and pyrolyzed spent Li-ion battery electrode material as catalyst

A search for non-noble catalysts for biomass processing led to the discovery that pyrolyzed electrode coating of spent Li-ion batteries can be used as an excellent catalyst for oxidation of D-glucose to glycolic acid. New no/low-cost catalyst was prepared by pyrolyzing black electrode coatings of 18,650 Li-ion cells from a spent DELL 1525 laptop battery at 600 ºC. Catalyst was characterized using SEM, EDX and X-ray and was shown to contain lithium nickel manganese cobalt oxide (Li a Ni b Mn c Co d O e ) on carbon with Ni: Mn: Co 4.12: 2.10: 1.50. Here, the catalytic activity of this material was evaluated for oxidation of D-glucose in aq. NaOH and water; glycolic, tartaric, malic, succinic and 2-hydroxybutaric acid were identified as key degradation products. The highest glycolic acid yield of 94% was obtained for oxidation of D-glucose under 3.4 Atm. oxygen, 120 °C, 2.0 h in 0.5 M aq. NaOH using 10 g catalyst/mol glucose.

25 ENERGY STORAGE↗

Poly(lactic- co -glycolic acid) Nanoparticles as Delivery Systems for the Improved Administration of Radiotherapeutic Anticancer Agents

This letter reports the development of poly(lactic- co -glycolic acid) (PLGA) nanoparticles (NPs) as delivery systems that could potentially encapsulate and improve the administration of radiotherapeutic anticancer agents. Different metal ions (Ba, Gd, and Ce) were used as surrogates of α-emitting radionuclides ( 223 Ra, 225 Ac, and 227 Th), and their encapsulation within the PLGA NPs ( D h < 300 nm) was evaluated. The initial concentration of metal ions, the metal salt (nitrate vs chloride), and the presence of chelators influenced the concentration of surrogate ions within the PLGA NPs. This letter shows the potential of PLGA NPs to encapsulate radionuclides, particularly α-emitters, for their application in nuclear medicine.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Lignin-Graft-Poly(lactic- co -glycolic) Acid Biopolymers for Polymeric Nanoparticle Synthesis

A lignin-graft-poly(lactic- co -glycolic) acid (PLGA) biopolymer was synthesized with two types of lignin (LGN), alkaline lignin (ALGN) and sodium lignosulfonate (SLGN), at different (A/S)LGN/PLGA ratios (1:2, 1:4, and 1:6 w/w). 1 H NMR and Fourier-transform infrared spectroscopy (FT-IR) confirmed the conjugation of PLGA to LGN. The (A/S)LGN-graft-PLGA biopolymers were used to form nanodelivery systems suitable for entrapment and delivery of drugs for disease treatment. The LGN-graft-PLGA NPs were generally small (100–200 nm), increased in size with the amount of PLGA added, monodisperse, and negatively charged (-48 to -60 mV). Small-angle scattering data showed that particles feature a relatively smooth surface and a compact spherical structure with a distinct core and a shell. The core size and shell thickness varied with the LGN/PLGA ratio, and at a 1:6 ratio, the particles deviated from the core–shell structure to a complex internal structure. The newly developed (A/S)LGN-graft-PLGA NPs are proposed as a potential delivery system for applications in biopharmaceutical, food, and agricultural sectors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of the Sludge Batch 9 (Macrobatch 11) DWPF Pour Stream Glass Sample Collected During the Nitric-Glycolic Acid Flowsheet Transition

A pour stream (PS) sample taken near the end of processing of Sludge Batch 9 (SB9, Macrobatch 11) during the transition to the nitric-glycolic acid (NGA) flowsheet was analyzed by the Savannah River National Laboratory (SRNL). The SB9 NGA PS sample was taken on 12/18/2022 during Melter Feed Batch 823 associated with glass canister S04773 and was transferred to SRNL in Primary Container PC0139 in February 2023.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Ectopic bone formation by marrow stromal osteoblast transplantation using poly(DL-lactic-co-glycolic acid) foams implanted into the rat mesentery

Porous biodegradable poly(DL-lactic-co-glycolic acid) foams were seeded with rat marrow stromal cells and implanted into the rat mesentery to investigate in vivo bone formation at an ectopic site. Cells were seeded at a density of 6.83 x 10(5) cells/cm2 onto polymer foams having pore sizes ranging from either 150 to 300 to 710 microns and cultured for 7 days in vitro prior to implantation. The polymer/cell constructs were harvested after 1, 7, 28, or 49 days in vivo and processed for histology and gel permeation chromatography. Visual observation of hematoxylin and eosin-stained sections and von Kossa-stained sections revealed the formation of mineralized bonelike tissue in the constructs within 7 days postimplantation. Ingrowth of vascular tissue was also found adjacent to the islands of bone, supplying the necessary metabolic requirements to the newly formed tissue. Mineralization and bone tissue formation were investigated by histomorphometry. The average penetration depth of mineralized tissue in the construct ranged from 190 +/- 50 microns for foams with 500-710-microns pores to 370 +/- 160 microns for foams with 150-300-microns pores after 49 days in vivo. The mineralized bone volume per surface area and total bone volume per surface area had maximal values of 0.28 +/- 0.21 mm (500-710-microns pore size, day 28) and 0.038 +/- 0.024 mm (150-300-microns, day 28), respectively. As much as 11% of the foam volume penetrated by bone tissue was filled with mineralized tissue. No significant trends over time were observed for any of the measured values (penetration depth, bone volume/surface area, or percent mineralized bone volume). These results suggest the feasibility of bone formation by osteoblast transplantation in an orthotopic site where not only bone formation from transplanted cells but also ingrowth from adjacent bone may occur.

NASA Discipline Developmental Biology↗

Electrospraying and Electrospinning of Polymers for Biomedical Applications. Poly(Lactic-Co-Glycolic Acid) and Poly(Ethylene-Co-Vinylacetate)

Significant opportunities exist for the processing of polymers (homopolymers and blends) using electric fields. Specific attention is given here to electrospinning, but we note that electroaerosol formation and field-modulated film casting represent additional processing options. Of particular interest is the ability to generate polymer fibers of sub-micron dimensions using electrospinning, down to about 0.05 microns (50 nm), a size range that has been traditionally difficult to access. In our work, poly(lactic-co-glycolic acid), PLA/PGA, poly(lactic acid) PLA, and poly(ethylene-co-vinylacetate) (PEVA) have been deposited from solutions in methylene chloride or chloroform by electrospraying or electrospinning to afford morphologically tailored materials for tissue engineering and related applications. Low solution concentrations tend to favor electrostatic spraying ('electro-aerosolization') while higher concentrations lead to spinning on fibrous mats. Preliminary observations of muscle cell growth on PLA electrospun mats are reported.

Stitzel, Joel D.↗

Photolysis products of CO, NH3 aND H2O and their significance to reactions on interstellar grains

With the increase in evidence that interstellar grains are the basic building blocks of comets and with the realization that comet collisions with the earth have probably occured at a much higher frequency than earlier assumed it may be presumed that interstellar dust chemistry played an important role in the early chemistry of the earth. As a part of the study of the photochemical processes taking place on interstellar grains the photolysis of mixtures of CO, NH3 and H2O was performed at 10 K, 77K and 298K. The reaction products were determined by GC/MS and HPLC analysis to be lactic acid, glycolic acid, hydroxyacetamide, urea, biuret, oxamic acid, oxamide, glyceric acid and glyceramide. Ethylene glycol and glycerol were also detected but is is not clear at present whether these are true photoproducts or contaminants. The mechanism of formation of these molecules are discussed as well as their possible significance to the origins of life.

Ferris, J. P.↗

Impacts of the Addition of Sodium Reactor Experiment (SRE) and DR-3 Fuel from H-Canyon to Tank 40 on Acid Stoichiometry and Hydrogen Production

H-Canyon plans to discard Sodium Reactor Experiment (SRE) material that is currently stored in Tanks 16.3 and 16.4. Savannah River Remediation (SRR) determined that a portion of the SRE material can be added to Sludge Batch 9 (SB9) in Tank 40 and the remainder will be added to Sludge Batch 10 (SB10) that is currently being prepared in Tank 51. A processing flowsheet for both the nitric-formic acid flowsheet and the nitric-glycolic acid flowsheet were previously developed for SB9 sludge-only and coupled operation with the Actinide Removal Process – Modular Caustic Side Solvent Extraction Unit (ARP-MCU) and the Salt Waste Processing Facility (SWPF). Due to the compositional change in Tank 40 after the addition of SRE material, it is necessary to determine the influence on the acid stoichiometry operating window and hydrogen production for SB9 processing. An assessment was completed to address the influence of an addition of SRE and DR-3 Fuel from H-Canyon on the chemistry of Tank 40, the defined acid stoichiometry window (with and without SWPF streams) for the nitric-formic and nitric-glycolic acid flowsheets, and the resulting influence of the hydrogen production. Hydrogen production during the SRAT/SME cycles consists of thermolytic, radiolytic, and catalytic hydrogen. For the nitric-formic acid flowsheet, catalytic hydrogen dominates the hydrogen production during DWPF operation mode for the SRAT and SME vessels. This report was written to summarize that assessment. No SRNL testing is needed prior to adding up to 7,100 additional gallons of SRE and DR-3 Fuel from H-Canyon to Tank 40. Also, the addition of SRE will not exceed the Shielded Cells reported values for catalytic hydrogen for either the nitric-formic acid flowsheet (Technical Safety Requirement (TSR) limit of 0.15 lb/h) or the nitric-glycolic acid flowsheet (TSR limit 0.024 lb/h). The addition of the ARP stream from SWPF and the use of the nitric-glycolic acid flowsheet are both expected to decrease hydrogen generation, leading to a larger safety margin in the CPC.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Influence of Glycolate Anion on Aqueous Corrosion in DWPF and Downstream Facilities – SCC Testing

Glycolic acid is being evaluated as an alternate reductant in the preparation of High Level Waste for the Defense Waste Processing Facility (DWPF) at the Savannah River Site (SRS). During processing, the glycolic acid may not be completely consumed with small quantities of the glycolate anion being carried forward to waste facilities. The SRS liquid waste contractor requested an assessment of the influence of the glycolate anion on the corrosion of the materials of construction (MoC) throughout the waste processing system since this concern had not been previously evaluated. The influence of glycolic acid on the occurrence of stress corrosion cracking (SCC) had not been evaluated specifically in the previous testing. The present testing used electrochemical and coupon immersion testing to assess this influence. Additionally, the primary guidance on corrosion for operating DWPF with a formate-based flowsheet is based on testing that utilized test solutions with a small number of constituents. Recent testing used more complex solutions based on flowsheet development for DWPF. Additional electrochemical tests were also conducted to assess the influence of this difference on test results.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Antifoam Development for Eliminating Flammability Hazards and Decreasing Cycle Time in the Defense Waste Processing Facility

The Savannah River National Laboratory (SRNL) was requested to develop a new antifoam control method for the Defense Waste Processing Facility’s (DWPF) Chemical Process Cell (CPC). SRNL completed testing of both chemical and nonchemical foam controls. The nonchemical foam controls were either ineffective (or worse, created more foam) or impractical (a water spray can control foam, but excessive water is needed). As a result, the focus of this study was on finding a superwetter or commercial antifoam for controlling foam. Thirty potential antifoams were tested as part of this study. A series of tests were developed to help screen out ineffective alternatives including: 1. Spreading testing of superspreaders, 2. Foam column testing with physical simulants, 3. Boiling testing with physical and chemical simulants, 4. Days-only Sludge Receipt and Adjustment Tank (SRAT) process simulations with sludge (containing noble metals and mercury), Precipitate Reactor Feed Tank (PRFT), and Slurry Mix Evaporator Feed Tank (SEFT) simulants in the RC1 Reaction Calorimeter (purchased for antifoam testing), and 5. Around-the-clock SRAT and Slurry Mix Evaporator (SME) process simulations with sludge(containing noble metals and mercury), PRFT, and SEFT simulants in the RC1 Reaction Calorimeter. Evonik Surfynol® MD20, a commercially available defoamer, was relatively effective in controlling foam, while remaining chemically stable in SRAT and SME processing across the pH range of 4 to 13. No degradation products were detected in the offgas, in the condensate or in the SRAT and SME products. In nitric-glycolic acid flowsheet testing, 250 mg/kg Evonik Surfynol® MD20 was needed for foam control compared to 1,625 mg/kg for Antifoam 747, DWPF’s current antifoam. In nitric-formic acid flowsheet testing, 1,125 mg/kg of Evonik Surfynol® MD20 was needed to control foam throughout the SRAT and SME cycles. The commercially available superspreader Momentive™ Y-17112 was even more effective than Evonik Surfynol® MD20 as both a defoamer and an antifoam. Not only was the foam destroyed upon addition but also was less persistent between additions. It was the most effective antifoam in testing using both the nitric-glycolic acid flowsheet and the nitric-formic acid flowsheet. In nitric-glycolic acid flowsheet testing, only 100 mg/kg Momentive™ Y-17112 was needed to control foam throughout the SRAT and SME cycles. In nitric-formic acid flowsheet testing, 300 mg/kg Momentive™ Y-17112 was needed to control foam throughout the SRAT and SME cycles. Momentive™ Y-17112 is also resistant to hydrolysis as demonstrated by its chemical stability in SRAT and SME processing across the pH range of 4 to 13 and lack of degradation products in offgas or condensate. Both candidates were effective as potential replacements for Antifoam 747, with Y-17112 demonstrating superior foam control. During nitric-glycolic flowsheet testing 50% less antifoam was needed when using Momentive™ Y-17112 compared to MD20. During nitric-formic flowsheet testing 75% less antifoam was needed when using Momentive™ Y-17112 compared to MD20. Foam remediated with Momentive™ Y-17112 was less persistent throughout testing. In addition, no degradation products were detected in the offgas, in the condensate or in the SRAT and SME products. Based on this testing, Momentive™ Y-17112 is clearly superior to Evonik Surfynol® MD20 and Antifoam 747, especially for the nitric-formic acid flowsheet processing; it is recommended that Momentive™ Y-17112 replace Antifoam 747 in DWPF. An antifoam addition strategy is recommended for both the nitric-glycolic acid flowsheet and the nitric-formic acid flowsheet. Implementation of Momentive™ Y-17112 is expected to decrease SRAT and SME boiling times by up to 50%, eliminate the issues resulting from Antifoam 747 degradation products, and minimize foamovers. To validate the effectiveness of these defoaming agents, SRNL recommends irradiation of a SRAT or SME product simulant containing fresh antifoam. The goal of this testing is to determine whether the irradiation causes decomposition of the antifoam that would make it less effective or produce new species in the offgas or slurry. This testing began in April 2020. An evaluation should be completed to determine the thermolytic hydrogen and methane generation rate in downstream equipment, including the High-Level Waste evaporators.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗