Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Contamination Control Engineering”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 145 records · Page 8

Radioactive Water Treatment at a United States Environmental Protection Agency Superfund Site - 12322

A water treatment system at a United States Environmental Protection Agency (USEPA) Superfund site impacted by radiological contaminants is used to treat water entering the site. The United States Army Corps of Engineers (USACE) is actively managing the remedial action for the USEPA using contracts to support the multiple activities on site. The site is where former gas mantle production facilities operated around the turn of the century. The manufacturing facilities used thorium ores to develop the mantles and disposed of off-specification mantles and ore residuals in the surrounding areas. During Site remedial actions, both groundwater and surface water comes into contact with contaminated soils and must be collected and treated at an on-site treatment facility. The radionuclides thorium and radium with associated progeny are the main concern for treatment. Suspended solids, volatile organic compounds, and select metals are also monitored during water treatment. The water treatment process begins were water is pumped to a collection tank where debris and grit settle out. Stored water is pumped to a coagulant tank containing poly-aluminum chloride to collect dissolved solids. The water passes into a reaction tube where aspirated air is added or reagent added to remove Volatile Organic Compounds (VOC'S) by mass transfer and convert dissolved iron to a solid. The water enters the flocculent polymer tank to drop solids out. The flocculated water overflows to a fluidized bed contact chamber to increase precipitation. Flocculation is where colloids of material drop out of suspension and settle. The settled solids are periodically removed and disposed of as radioactive waste. The water is passed through filters and an ion exchange process to extract the radionuclides. Several million liters of water are processed each year from two water treatment plants servicing different areas of the remediation site. Ion exchange resin and filter material are periodically replaced and disposed of as radioactive waste. A total of 0.85 m{sup 3} of waste sludge per year requires disposal on average, in addition to another 6.6 m{sup 3} of waste cartridge filters. All water discharges are regulated by a state of New Jersey Pollutant Discharge Elimination System Permit implemented by the Federal Water Pollution Control Act (Clean Water Act). Laboratory analyses are required to satisfy requirements of the state NPDES permit. Specific monitoring parameters and discharge rates will be provided. Use of the water treatment systems drastically reduces the amount of contaminated water requiring solidification and water disposal to near zero. Millions of liters of potentially contaminated water from excavation activities is treated and released within permit limits. A small volume of solid radioactive waste (21 cubic meters) is generated annually from water treatment process operations. Management of ground and surface water is effectively controlled in remediation areas by the use of sumps, erosion control measures and pumping of water to storage vessels. Continued excavations can be made as water impacting the site is effectively controlled. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Colonie, New York, FUSRAP Site: Pathway from Remediation to Redevelopment - 19465

The Colonie, New York, Formerly Utilized Sites Remedial Action Program (FUSRAP) Site consists of a 4.5-hectare (11.2-acre) US Department of Energy (DOE)-owned vacant property (Main Site) and 56 commercial and residential vicinity properties (VPs). The site was owned and operated by National Lead Industries (NL) from 1937 to 1984. The Main Site was used for manufacturing fuel and weapons components using uranium and thorium. Depleted uranium dust was emitted from exhaust stacks that contaminated the site and the VPs. NL also filled in portions of the site with industrial waste and released contaminants to groundwater. The state court shut the plant down in 1984. The site was acquired by DOE in 1985, which remediated the VPs and began to remediate the Main Site up to 1997. The US Army Corps of Engineers (USACE) undertook remedial actions beginning in 1997. The site has three Operable Units (Main Site, Groundwater, and VPs). The Main Site soil was remediated to residential standards except for three small easement areas. The soils in the easement areas are safe for exposure to workers. There is a groundwater plume beneath the site that will require the use of monitoring and temporary land use controls until cleanup standards are met. The VPs require no further action. A 2-year transition period from USACE to the DOE Office of Legacy Management (LM) began on June 18, 2018, with the receipt of the Site Closeout Report from USACE. LM has determined that the 4.5-hectare site is excess to its mission needs and intends to pursue sale of the property for redevelopment. There are several processes required before the disposal can occur. Organizations with similar sites that are federally owned and ready for private redevelopment may benefit from reviewing the Colonie site disposition processes. This paper will discuss (1) Determining disposal alternatives for the Colonie, New York, site. (2) Describing the federal requirements for the disposal of excess real property. (3) Communicating to stakeholders that the site is ready for disposal. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Ionic Strength-Controlled Mn (Hydr)oxide Nanoparticle Nucleation on Quartz: Effect of Aqueous Mn(OH) 2

The early formation of manganese (hydr)oxide nanoparticles at mineral–water interfaces is crucial in understanding how Mn oxides control the fate and transport of heavy metals and the cycling of nutrients. Using atomic force microscopy, we investigated the heterogeneous nucleation and growth of Mn (hydr)oxide under varied ionic strengths (IS; 1–100 mM NaNO 3 ). Experimental conditions (i.e., 0.1 mM Mn 2+ (aq) concentration and pH 10.1) were chosen to be relevant to Mn remediation sites. We found that IS controls Mn(OH) 2 (aq) formation, and that the controlled Mn(OH) 2 (aq) formation can affect the system’s saturation and subsequent Mn(OH) 2 (s) and further Mn 3 O 4 (s) nanoparticle formation. In 100 mM IS system, nucleated Mn (hydr)oxide particles had more coverage on the quartz substrate than those in 1 mM and 10 mM IS systems. This high IS also resulted in low supersaturation ratio and thus favor heterogeneous nucleation, having better structural matching between nucleating Mn (hydr)oxides and quartz. Here, the unique information obtained in this work improves our understanding of Mn (hydr)oxide formation in natural as well as engineered aqueous environments, such as groundwater contaminated by natural leachate and acid mine drainage remediation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cryogenic target system for hydrogen layering

Here, a cryogenic target positioning system was designed and installed on the National Ignition Facility (NIF) target chamber. This instrument incorporates the ability to fill, form, and characterize the NIF targets with hydrogen isotopes needed for ignition experiments inside the NIF target bay then transport and position them in the target chamber. This effort brought to fruition years of research in growing and metrologizing high-quality hydrogen fuel layers and landed it in an especially demanding operations environment in the NIF facility. D-T (deuterium-tritium) layers for NIF ignition experiments have extremely tight specifications and must be grown in a very highly constrained environment: a NIF ignition target inside a cryogenic target positioner inside the NIF target bay. Exquisite control of temperature, pressure, contaminant level, and thermal uniformity are necessary throughout seed formation and layer growth to create an essentially-groove-free single crystal layer.

42 ENGINEERING↗

The impact of contamination and aging effects on the long-term laser-damage resistance of SiO 2 /HfO 2 /TiO 2 high-reflection coatings for 1054nm

The laser damage thresholds of optical coatings can degrade over time due to a variety of factors, including contamination and aging. Optical coatings deposited using electron beam evaporation are particularly susceptible to degradation due to their porous structure. In a previous study, the laser damage thresholds of optical coatings were reduced by roughly a factor of two from 2013 to 2017. The coatings in question were high reflectors for 1054 nm that contained SiO 2 and HfO 2 and/or TiO 2 layers, and they were stored in sealed PETG containers in a class 100 cleanroom with temperature control. At the time, it was not certain whether contamination or thin film aging effects were responsible for the reduced laser damage thresholds. Therefore, to better understand the role of contamination, the coatings were recleaned and the laser damage thresholds were measured again in 2018. Here, the results indicate that contamination played the most dominant role in reducing the laser damage thresholds of these optical coatings, even though they were stored in an environment that was presumed to be clean.

42 ENGINEERING↗

Pilot-Scale Silicone Process for Low-Cost Carbon Dioxide Capture

GE Global Research is developing technology to remove carbon dioxide (CO 2) from the flue gas of coal-fired powerplants. A mixture of 3-aminopropyl end-capped polydimethylsiloxane (GAP-1m) and triethylene glycol (TEG) is the preferred CO2-capture solvent. GE Global Research was contracted by the Department of Energy to test a pilot-scale continuous CO2 absorption/desorption system using a GAP-1m/TEG mixture as the solvent. As part of that effort, an Environmental, Health, and Safety (EH&S) assessment for a CO2-capture system for a 550 MW coal-fired powerplant was conducted. Five components of the solvent, CAS#2469-55-8 (GAP-0), CAS#106214-84-0 (GAP-1-4), TEG, and methanol and xylene (minor contaminants from the aminosilicone) are included in this assessment. One by-product, GAP- 1m/SOX salt, and dodecylbenzenesulfonicacid (DDBSA) were also identified foranalysis. An EH&S assessment was also completed for the manufacturing process for the GAP-1m solvent. The chemicals associated with the manufacturing process include methanol, xylene, allyl chloride, potassium cyanate, sodium hydroxide (NaOH), tetramethyldisiloxane (TMDSO), tetramethyl ammonium hydroxide, Karstedt catalyst, octamethylcyclotetrasiloxane (D4), Aliquat 336, methyl carbamate, potassium chloride, trimethylamine, and (3-aminopropyl) dimethyl silanol. The toxicological effects of each component of both the CO2 capture system and the manufacturing process were defined, and control mechanisms necessary to comply with U.S. EH&S regulations are summarized. Engineering and control systems, including environmental abatement, are described for minimizing exposure and release of the chemical components. Proper handling and storage recommendations are made for each chemical to minimize risk to workers and the surrounding community.

01 COAL, LIGNITE, AND PEAT↗

Targeted Health Assessment for Wastes Contained at the Niagara Falls Storage Site to Guide Planning for Remedial Action Alternatives - 13428

The U.S. Army Corps of Engineers (USACE) is evaluating potential remedial alternatives at the 191-acre Niagara Falls Storage Site (NFSS) in Lewiston, New York, under the Formerly Utilized Sites Remedial Action Program (FUSRAP). The Manhattan Engineer District (MED) and Atomic Energy Commission (AEC) brought radioactive wastes to the site during the 1940's and 1950's, and the U.S. Department of Energy (US DOE) consolidated these wastes into a 10-acre interim waste containment structure (IWCS) in the southwest portion of the site during the 1980's. The USACE is evaluating remedial alternatives for radioactive waste contained within the IWCS at the NFSS under the Feasibility Study phase of the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) process. A preliminary evaluation of the IWCS has been conducted to assess potential airborne releases associated with uncovered wastes, particularly during waste excavation, as well as direct exposures to uncovered wastes. Key technical issues for this assessment include: (1) limitations in waste characterization data; (2) representative receptors and exposure routes; (3) estimates of contaminant emissions at an early stage of the evaluation process; (4) consideration of candidate meteorological data and air dispersion modeling approaches; and (5) estimates of health effects from potential exposures to both radionuclides and chemicals that account for recent updates of exposure and toxicity factors. Results of this preliminary health risk assessment indicate if the wastes were uncovered and someone stayed at the IWCS for a number of days to weeks, substantial doses and serious health effects could be incurred. Current controls prevent such exposures, and the controls that would be applied to protect onsite workers during remedial action at the IWCS would also effectively protect the public nearby. This evaluation provides framing context for the upcoming development and detailed evaluation of remedial alternatives for the IWCS. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Microbial Activity and Precipitation at Solution-Solution Mixing Zones in Porous Media (Final Report)

The use of biological and chemical processes that degrade or immobilize contaminants in subsurface environments is a cornerstone of remediation technology. The enhancement of biological and chemical processes in situ, involves the transport, displacement, distribution and mixing of one or more reactive agents. Biological and chemical reactions all require diffusive transport of solutes to reaction sites at the molecular scale and accordingly, the success of processes at the meter-scale and larger is dictated by the success of phenomena that occur at the micron-scale. However, current understanding of scaling effects on the mixing and delivery of nutrients in biogeochemically dynamic porous media systems is limited, despite the limitations this imposes on the efficiency and effectiveness of the remediation challenges at hand. We therefore proposed to experimentally characterize and computationally describe the growth, evolution, and distribution of microbial activity and mineral formation as well as changes in transport processes in porous media that receive two or more reactive amendments. The model system chosen for this project was based on a method for immobilizing 90 Sr, which involves stimulating microbial urea hydrolysis with ensuing mineral precipitation (CaCO 3 ), and co-precipitation of Sr. Studies at different laboratory scales were used to visualize and quantitatively describe the spatial relationships between amendment transport and consumption that stimulate the production of biomass and mineral phases that subsequently modify the permeability and heterogeneity of porous media. Biomass growth, activity, and mass deposition in mixing zones was investigated using two-dimensional micro-model flow cells as well as flow cells that could be analyzed using synchrotron-based x-ray tomography. Larger-scale flow-cell experiments were conducted where the spatial distribution of media properties, flow, segregation of biological activity and impact on ancillary constituents (i.e., Sr) was determined. Model simulations accompanied the experimental efforts. The research contributed towards defining the key physical, chemical, and biological processes influencing the form and mobility of DOE priority contaminants (e.g., 60 Co, 90 Sr, U) in the subsurface. The work conducted and reported herein, will in the future (i) contribute to controlling the juxtaposition of microbial activity, contaminants and amendments, (ii) promote new strategies for delivering amendments, and (iii) allow new approaches for modifying permeability and flow in porous media. We feel that the work has already translated directly to improving the efficiency of amendment based remediation strategies. The results of the project have been published in a number of peer reviewed journal articles. The abstracts and citations to those articles, given in section 2.0 below, make up the bulk of this final report.

42 ENGINEERING↗

H-Canyon Tunnel Inspection System

Cable Analysis: The crawlers is controlled remotely via a long coax cable. In order to make sure we do not damage the cable which could cut our contact (data/power/control), we had to determine the bend radius of it at certain locations. This was done with dimensional analysis in Creo and inputting the information into a MATLAB program. Engineering Drawings: Since many of the crawlers parts, such as the main body, needed to be machined, part drawings were needed to communicate the details necessary for manufacture. Project Overview: The H-Canyon Ventilation Exhaust Tunnel due both to its long service history and exposure to aggressive process offgas chemistry has experienced degradation. In order to allow visual inspection of the condition of the radioactively-contaminated tunnel, a remote crawler was designed to deliver cameras as needed to return high definition video. My involvement included Vendor Searches, Cable Analysis, Thermal Analysis, and Engineering Drawings. Thermal Analysis: In order to see if internal active cooling is needed for the crawler, simplified thermal models were designed to approximate the internal temperatures: Conduction (assumes all heat sources are thermally-coupled to the crawler body); Convection (assumes no heat sources are thermally-bonded to crawler). Going Forward: Continue refining the cable analysis as the crawler model is updated and refined. Use my knowledge gained here to further my skills in engineering.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Requirements Document for the Redesign of the DIM-based Diagnostics Transport and Handling System at the National Ignition Facility (NIF)

The National Ignition Facility (NIF, Figure 1) is the world’s leading user research facility for inertial confinement fusion. Diagnostic instruments that collect data from the experiment shots are transported around the facility using a series of disjointed, suboptimal transport and handling (T&H) subsystems that compromise user efficiency and ergonomics. Significant time savings and improvements to the diagnostic exchange process could be realized by designing a new transport and handling system that minimizes the hand-offs between T&H subsystems, reduces operator hassle and ergonomic strain, and improves the long-term maintainability of the system. In contrast to the current system – which employs several manually-operated carts and containers to transport the diagnostic, dock it to its destination, and install it – the new diagnostic transporter integrates the contamination container with the transport cart and provides a dynamic range of adjustability to interface with its destination. This single transporter has the requisite maneuverability, height adjustability, and fine adjustment capabilities without any rigging transactions to support contaminated diagnostic transport and handling at the alignment station and Equatorial and Polar DIMs. A remote-controlled user interface device allows operators a more hands-off experience that reduces ergonomic strain and improves safety. Assuming the cost is not prohibitive, diagnostic storage will be accomplished by simply stowing the transporter in its lowest position in the designated area of NIF. This concept for a new diagnostic transport and handling system would be better aligned with the core values of NIF: safety, quality, and reliability.

42 ENGINEERING↗

FX2 advanced fogging technology - 15711

Problem statement: The need for an advanced technology that can better address potential airborne contaminants at DOE Savannah River Site 235-F. Current methods of knocking down or fixing this contamination are labor intensive, costly, and sometimes ineffective. Thus, to make exposure ALARA, the advanced fogging effort is being tested using Idaho National Laboratory's FX2 fixative agent. The FX2 fogging agent is a proprietary mixture of water, latex paint (LTX), glycerin (GLY) and sodium lauryl sulfate (SLS). Initial development began in 2006 when a DOE Small Business Innovative Research (SBIR) grant resulted in the development of a conceptual advanced capture coating fog system. This coating is shown to be excellent at reducing airborne contamination and 'fixing' particulates in place as demonstrated by Idaho National Lab. Controlling Potential Airborne Particulates: Testing capacity to knockdown airborne particulates. Evaluating ability to fix to different surfaces (e.g., glass, wood, steel, concrete, brick). Line of sight as well as non-line of sight (shadowed) locations will be tested for coverage. Adhesiveness and Coverage of Surface Area: Contact area will be placed under air pressure to attempt dislodging of dried mixture. Particle analysis utilizing ImageJ will be conducted to determine quantifiable coverage. Ignitability: Observation of the FX2's reactivity to flame and heat sources as it is being applied. Results will provide useful information for the prevention of potential hazards. Determine Shielding Properties Against Alpha Sources: Determine the shielding abilities of the FX2. Fogging agent against an alpha particle emitting point source. Evaluating Critical Properties: These properties will be evaluated to better characterize the FX2 and allow for optimal understanding of results: ASTM E1354 - Burn Rate; NFPA 296-Flashover; ASTM D2196 - Viscosity; ASTM D1331 - Surface Tension; ASTM D792 - Density. Testing Innovations: Developed by the National Institutes of Health, ImageJ is a public domain image processing program that allows for the analysis that this effort requires. Coverage: Through contrast analysis, ImageJ can be used to determine the coverage of the agent upon any of the testing surfaces. Correlations: With the feature of coverage evaluation, a relationship, and thus a graphical representation, can be made between surface coverage and radiation shielding. Future work: Engineering and manufacturing of mobile robotic fogging device. ASTM WK5394: establishing performance specifications for stabilizers to minimize migration of dispersible radioactive contamination.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Can Common Pool Resource Theory Catalyze Stakeholder-Driven Solutions to the Freshwater Salinization Syndrome?

Freshwater salinity is rising across many regions of the United States as well as globally, a phenomenon called the freshwater salinization syndrome (FSS). The FSS mobilizes organic carbon, nutrients, heavy metals, and other contaminants sequestered in soils and freshwater sediments, alters the structures and functions of soils, streams, and riparian ecosystems, threatens drinking water supplies, and undermines progress toward many of the United Nations Sustainable Development Goals. There is an urgent need to leverage the current understanding of salinization’s causes and consequences–in partnership with engineers, social scientists, policymakers, and other stakeholders–into locally tailored approaches for balancing our nation’s salt budget. In this feature, we propose that the FSS can be understood as a common pool resource problem and explore Nobel Laureate Elinor Ostrom’s social-ecological systems framework as an approach for identifying the conditions under which local actors may work collectively to manage the FSS in the absence of top-down regulatory controls. We adopt as a case study rising sodium concentrations in the Occoquan Reservoir, a critical water supply for up to one million residents in Northern Virginia (USA), to illustrate emerging impacts, underlying causes, possible solutions, and critical research needs.

54 ENVIRONMENTAL SCIENCES↗

Smart Ventilation for Advanced California Homes – Single Zone Technology Task

This study is intended to demonstrate the potential for energy savings while providing acceptable Indoor Air Quality (IAQ) for ZNE homes. It uses the concept of Smart Ventilation where ventilation systems are designed and controlled to produce the same, or better, IAQ compared to simple, continuously operated ventilation systems. The key energy saving principle for smart ventilation is that ventilation is shifted in time to when the energy required to condition the air is lower. A variety of smart ventilation controls based on outdoor temperature, occupancy and auxiliary fan sensing were developed and assessed across homes built to the 2016 Title 24 Prescriptive standards in California climate regions. Simulations used a co-simulation strategy that combines EnergyPlus with CONTAM. The IAQ calculations were based on the equivalent ventilation principle outlined in the ASHRAE 62.2-2016 ventilation standard, Appendix C. Two prototype homes were simulated (1-story 2,100 ft2 and 2-story 2,700 ft2). Their envelope airtightness was varied between 1, 3 and 5 ACH50. Climate zones were chosen to reflect the variety of heating and cooling demand throughout California. A weighted average analysis was used to generalize the energy predictions across the projected new housing stock in the state. Temperature-based controls were found to be effective, with the most successful smart controls reducing weighted average site ventilation energy use by about 40%, while TDV weighted average ventilation energy reductions were higher, up to roughly 60%. Results were also normalized to ensure identical IAQ in all cases, and the weighted average site and TDV ventilation savings increased, up to 55% and 72% ventilation savings, respectively, for the top-performing temperature-based controls. Peak demand during the 2-6pm period on the hottest days of the year was reduced by up to 400 watts. More than 90% of site energy savings were for heating end-uses, while TDV energy savings were split fairly evenly between heating and cooling. On average, the smart controls reduced occupant pollutant exposure by 0-10%, and they increased ventilation rates by roughly 20%. Occupancy-based controls that accounted for contaminants released by building materials and furnishings during unoccupied times were generally ineffective, with very low energy savings. Performance was improved somewhat through use of a 1-hour pre-occupancy flush out period, though savings were still marginal compared to temperature-based controls. All temperature and occupancy controls were also tested with auxiliary fan sensing capability (i.e., accounting for the use of other exhaust devices in the home, like bathroom or kitchen fans). Auxiliary fan sensing increased energy savings in all cases, from roughly 5 to 15%.

42 ENGINEERING↗

Implementation and evaluation of permeability-porosity and tortuosity-porosity relationships linked to mineral dissolution-precipitation

Changes of porosity, permeability, and tortuosity due to physical and geochemical processes are of vital importance for a variety of hydrogeological systems, including passive treatment facilities for contaminated groundwater, engineered barrier systems (EBS), and host rocks for high-level nuclear waste (HLW) repositories. Due to the nonlinear nature and chemical complexity of the problem, in most cases, it is impossible to verify reactive transport codes analytically, and code intercomparisons are the most suitable method to assess code capabilities and model performance. This paper summarizes model intercomparisons for six hypothetical scenarios with generally increasing geochemical or physical complexity using the reactive transport codes CrunchFlow, HP1, MIN 3 P, PFlotran, and TOUGHREACT. Benchmark problems include the enhancement of porosity and permeability through mineral dissolution, as well as near complete clogging due to localized mineral precipitation, leading to reduction of permeability and tortuosity. Processes considered in the benchmark simulations are advective-dispersive transport in saturated media, kinetically controlled mineral dissolution-precipitation, and aqueous complexation. Porosity changes are induced by mineral dissolution-precipitation reactions, and the Carman-Kozeny relationship is used to describe changes in permeability as a function of porosity. Archie’s law is used to update the tortuosity and the pore diffusion coefficient as a function of porosity. Results demonstrate that, generally, good agreement is reached amongst the computer models despite significant differences in model formulations. As a result, some differences are observed, in particular for the more complex scenarios involving clogging; however, these differences do not affect the interpretation of system behavior and evolution.

58 GEOSCIENCES↗

Roles of surface Mn(III) and MgOH + /CaOH + complexation in photochemically assisted Mn 2+ oxidation and Todorokite formation

Todorokite, a Mn oxide phase commonly found in seafloor Mn nodules, is one of the most abundant Mn oxides in nature and has wide applications in environmental engineering, including heavy metal remediation, contaminant adsorption for water purification, and catalysis for organic pollutant degradation. However, traditional abiotic formation of todorokite reported to date typically requires high temperature, pressure, and pH outside circumneutral conditions, or involves several days of phase transformations from precursor phases. In this study, we demonstrate rapid todorokite formation within 6 h via photochemically assisted oxidation of Mn 2+ (aq) in the presence of Mg 2+ or Ca 2+ , notably at ambient temperature and pressure. The concentrations of aqueous MgOH + and CaOH + , as well as the pH (initial 9 or 6), had significant collective influences on the crystalline phases of the formed Mn oxide solids. The proportions of the Mn oxidation states (IV, III, and II) and the extent of Mn(III) surface complexation with MgOH + or CaOH + controlled the crystalline phases (todorokite, feitknechtite, and birnessite) and the extent of cation incorporation into the resulting Mn oxide solids. Specifically, the oxidation state of Mn influenced the crystallization of different Mn oxide phases, and the formed Mn(III) complexed with MgOH + or CaOH + facilitated the formation of todorokite, along with cation incorporation. X-ray pair distribution function analysis revealed that incorporated Mg species were located at the inside corner sites of the 5 × 3 MnO 6 octahedral tunnel structure of todorokite, suggesting complexation between MgOH + and Mn(III) at the corners of the tunnel. Furthermore, this study provides novel insights into the elusive formation of todorokite and its potential for applications in advanced water treatment and environmental remediation.

Abiotic Mn2+ oxidation↗

Redox potential control in molten salt systems for corrosion mitigation

In a molten salt nuclear reactor system, the redox potential must be controlled for mitigating corrosion of structural materials. The paper presented a critical review on the available knowledge of redox potential control in molten fluoride salt systems. The major potential contaminants that affect the redox potential and material corrosion are TF, oxides, hydroxides, and various metal fluorides. Redox potential control methodologies include gas sparging, contacting the salt with a reducing metal, and adding soluble salt redox buffers to the salt. Redox potential measurement technologies include electrochemical sensors and optical spectroscopy. This work also analyzed the current technology issues and recommended near future studies.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Groundwater flowpath characteristics drive variability in per- and polyfluoroalkyl substances (PFAS) loading across a stream-wetland system

Groundwater dependent ecosystems in areas with industrial and military land use are at risk of direct exposure to a wide range of contaminants, including PFAS chemicals. Glaciated terrain often has mixed high and low permeability sediments coupled with groundwater flow-through lake features. These hydrogeologic attributes create highly complex ‘source to seep’ dynamics that make spatiotemporal contaminant transport patterns difficult to predict. We investigated one such system in detail using a suite of heat-tracing and chemical methods. Numerous (n=57) preferential groundwater discharge zones (vertical flux rates ranging 0.2 to 3.2 m/d) were identified across the upper Quashnet River stream-wetland system in Mashpee, MA, USA, adjacent to an Air Force Base with several known PFAS source areas. Surface-water and groundwater samples were collected and analyzed (n=145) for precursors and terminal PFAS compounds between March and September 2022. Samples were collected at identified seeps along the Quashnet River (n=59), from wells upgradient from the stream-wetland system (n= 44), from contributing flow-through kettle lakes (n=8), and at multiple locations along the Quashnet River (n=34). Samples from seeps and wells had measured PFAS concentrations ranging from non-detect to approximate 3,500 ng/L (mean= 1,650 ng/L), and a range of deuterium excess values (3.2 to 15.9 per mil) indicative of varying degrees of groundwater-lake interaction prior to emergence at the discharge zones. Groundwater-lake interaction along flowpaths that sourced the sampled seeps was farther supported by significant correlations (p < 0.01) between deuterium excess and %PFAS precursors, and between %PFAS precursors and multiple terminal PFAS compounds (e.g., PFPeS, PFBS, PFHxS). However, some sampled seeps contributing groundwater to the stream-wetland system had much higher total PFAS concentrations (>1000 ng/L) than the upgradient kettle lakes, despite showing lake (evaporative) isotopic signatures, indicating the potential for groundwater flowpath convergence at wetland discharge zones and the influence of lakebed PFAS precursor reactions. PFAS compounds and water isotopic composition at sampled multilevel groundwater wells, rivers, lakes, and seeps suggest that a complex mixture of source groundwater and flowpath characteristics are responsible for diverse observed PFAS mixtures at preferential discharge zones across the stream-wetland system. Further, total PFAS loading patterns to the Quashnet River via groundwater discharge remained remarkably similar from winter to summer to fall conditions, despite a regional dry period in late summer 2022 with the upper river channel completely drying. This work addresses gaps in the existing PFAS literature by demonstrating the importance of subsurface fate and transport on PFAS compound concentrations in controlling contaminant mass loading in preferential groundwater discharge zones and presents a transferrable field toolkit for efficient characterization of spatially preferential PFAS transport dynamics.

Contaminant transport↗

Inducing Mineral Precipitation in Groundwater by Addition of Phosphate

Induced precipitation of phosphate minerals to scavenge trace metals and radionuclides from groundwater is a potential remediation approach for contaminated aquifers. Phosphate minerals can sequester trace elements by primary mineral formation, solid solution formation and/or adsorption, and they are poorly soluble under many environmental conditions, making them attractive for long-term sustainable remediation. The success of such engineered schemes will depend on the particular mineral phases generated, their rates of formation, and their long term stability. The purpose of this study was to examine the precipitation of calcium phosphate minerals under conditions representative of a natural groundwater. Because microorganisms are present in groundwater, and because some proposed schemes for induced phosphate mineral precipitation rely on the stimulation of native groundwater populations, we also tested the effect of bacterial cells (initial densities of 105 and 107 ml-1) within the precipitation medium. We also tested the effect of a trace mixture of propionic, isovaleric, formic and butyric acids (total concentration 0.035 mM). The experiments showed that the general progression of mineral precipitation was similar under all of the conditions, with initial formation of amorphous calcium carbonate, and transformation to poorly crystalline hydroxyapatite (HAP) by the end of the week-long experiments. The presence of the bacterial cells appeared to delay precipitation, although by the end of 7 days the overall extent of precipitation was similar for all of the treatments. The stoichiometry of the final precipitates as well as results of Rietveld refinement of x-ray diffraction data indicated that the treatments including organic acids and bacterial cells resulted in increased distortion of the HAP crystal lattice, with the higher concentration of cells resulting in the greatest distortion. Uptake of Sr into the phosphate minerals was decreased in the treatments with cells and organic acids, compared to the control. The results of the experiments enable a greater understanding of the challenges associated with phosphate-based remediation schemes for contaminated environments.

54 ENVIRONMENTAL SCIENCES↗