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At least 523 records · Page 29

Identification of 4-Hydroxycumyl Alcohol As the Major MnO 2 -Mediated Bisphenol A Transformation Product and Evaluation of Its Environmental Fate

Bisphenol A (BPA), an environmental contaminant with weak estrogenic activity, resists microbial degradation under anoxic conditions but is susceptible to abiotic transformation by manganese dioxide (MnO 2 ). BPA degradation followed pseudo-first-order kinetics with a rate constant of 0.96 (±0.03) min –1 in the presence of 2 mM MnO 2 (0.017% w/w) at pH 7.2. 4-hydroxycumyl alcohol (HCA) was the major transformation product, and, on a molar basis, up to 64% of the initial amount of BPA was recovered as HCA. MnO 2 was also reactive toward HCA, albeit at 5-fold lower rates, and CO 2 evolution (i.e., mineralization) occurred. In microcosms established with freshwater sediment, HCA was rapidly biodegraded under oxic, but not anoxic conditions. With a measured octanol–water partition coefficient (Log K ow ) of 0.76 and an aqueous solubility of 2.65 g L –1 , HCA is more mobile in saturated media than BPA (Log K ow = 2.76; aqueous solubility = 0.31 g L –1 ), and therefore more likely to encounter oxic zones and undergo aerobic biodegradation. In conclusion, these findings corroborate that BPA is not inert under anoxic conditions and suggest that MnO 2 -mediated coupled abiotic–biotic processes may be relevant for controlling the fate and longevity of BPA in sediments and aquifers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Benefits of less intrusive remediation alternatives; A review of case studies in Oak Ridge, Tennessee - 15482

Various alternative cleanup strategies have been utilized at Department of Energy facilities in Oak Ridge, Tennessee to avoid costly and potentially ineffective removal of contaminants in soil and sediments, transportation by truck, and long-term storage in landfills. One such example is a remedial decision in the 1990's to not conduct large-scale removal of PCB-contaminated sediments from a large downstream reservoir, and instead implement sediment disturbance controls and monitoring requirements. Monitoring results suggest the decision was a good one with PCB concentrations in fish decreasing substantially over the last 20 years, presumably due to recent cleaner sediments overlying historical sediment layers. At the East Tennessee Technology Park an innovative remediation strategy was developed to reduce human and ecological risks associated with a PCB-contaminated pond, while also enhancing the site's natural resources. Termed the 'Ecological Management and Enhancement' strategy, this remediation option provided an alternative approach to more conventional pond remediation options like sediment and soil removal, draining and capping, and point source/discharge actions. The basic premise of this option is that ecological management, including fish and wildlife management and vegetation management, can interrupt the contaminant exposure pathways that lead to ecological or human receptors. Recent monitoring results have demonstrated both risk reduction and increased natural resource value. Currently under investigation is the use of watershed management approaches that may help ameliorate mercury methylation and bioaccumulation in East Fork Poplar Creek. There is increased recognition that mercury source reduction alone will not achieve the human health risk target level in fish in the downstream environment, where water chemistry and ecological processes are conducive to mercury methylation. Additionally, significant losses in natural resource values are anticipated if major soil and sediment source removal activities are implemented. The Oak Ridge experience suggests that alternative approaches to the conventional 'muck and truck' options to sediment contamination are worth pursuing in some cases. Taking advantage of natural attenuation processes and/or implementing less intrusive water and ecological manipulations could be especially advantageous at contaminated sites where there are multiple or complex sources that are difficult to remediate, conventional source removal is costly, the contaminant of concern is highly bio-accumulative, or where natural resource values could be preserved or enhanced. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Experience in Remote Demolition of the Activated Biological Shielding of the Multi Purpose Research Reactor (MZFR) on the German Karlsruhe Site - 12208

In 2009, WAK Decommissioning and Waste Management GmbH (WAK) became owner and operator of the waste treatment facilities of Karlsruhe Institute of Technology (KIT) as well as of the prototype reactors, the Compact Sodium-Cooled Fast Reactor (KNK) and Multi-Purpose Reactor (MZFR), both being in an advanced stage of dismantling. Together with the dismantling and decontamination activities of the former WAK reprocessing facility since 1990, the envisaged demolishing of the R and D reactor FR2 and a hot cell facility, all governmentally funded nuclear decommissioning projects on the Karlsruhe site are concentrated under the WAK management. The small space typical of prototype research reactors represented a challenge also during the last phase of activated dismantling, dismantling of the activated biological shield of the MZFR. Successful demolition of the biological shield required detailed planning and extensive testing in the years before. In view of the limited space and the ambient dose rate that was too high for manual work, it was required to find a tool carrier system to take up and control various demolition and dismantling tools in a remote manner. The strategy formulated in the concept of dismantling the biological shield by means of a modified electro-hydraulic demolition excavator in an adaptable working scaffolding turned out to be feasible. The following boundary conditions were essential: - Remote exchange of the dismantling and removal tools in smallest space. - Positioning of various supply facilities on the working platform. - Avoiding of interfering edges. - Optimization of mass flow (removal of the dismantled mass from the working area). - Maintenance in the surroundings of the dismantling area (in the controlled area). - Testing and qualification of the facilities and training of the staff. Both the dismantling technique chosen and the proceeding selected proved to be successful. Using various designs of universal cutters developed on the basis of wall saws, both the activated steel liner and the inner reinforcing layer were cut remotely in one process. This allowed for the efficient execution of the following remote concrete removal steps using mining techniques. The electro-hydraulic demolition excavator that was purchased and then modified turned out to be an ideal tool carrier system with rapid-exchange coupling. Due to the high availability, no major delays occurred. This also was a result of the consistently implemented maintenance and repair concept. With the excavator installed in a modifiable scaffolding suspended from a rotating carrier ring, all dismantling areas could be reached and treated in spite of the small space. Thanks to an optimum organization of work-flows, routine change of dismantling work, and maintenance or repair, the iterative radiological measurement campaigns could be integrated in the whole activity without the dismantling work being disturbed significantly. The ventilation system with pressure grading and pre-filtration units ensured a low contamination level in the dismantling area. It was also possible to manage the dust formed by the milling of concrete surfaces. As it was possible to further cut metal parts and crushed concrete later on, residue flows were optimized. The planned overall period for testing, dismantling the bio-shield and removing the equipment was 36 months. The final duration was 39 months. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Letter Report: LAW Simulant Development for Cast Stone Screening Test

More than 56 million gallons of radioactive and hazardous waste are stored in 177 underground storage tanks at the U.S. Department of Energy’s (DOE’s) Hanford Site in southeastern Washington State. The Hanford Tank Waste Treatment and Immobilization Plant (WTP) is being constructed to treat the wastes and immobilize them in a glass waste form. The WTP includes a pretreatment facility to separate the wastes into a small volume of high-level waste (HLW) containing most of the radioactivity and a larger volume of low-activity waste (LAW) containing most of the nonradioactive chemicals. The HLW will be converted to glass in the HLW vitrification facility for ultimate disposal at an offsite federal repository. At least a portion (~35%) of the LAW will be converted to glass in the LAW vitrification facility and will be disposed of onsite at the Integrated Disposal Facility (IDF). The pretreatment and HLW vitrification facilities will have the capacity to treat and immobilize the wastes destined for each facility. However, a second facility will be needed for the expected volume of additional LAW requiring immobilization. A cementitious waste form known as Cast Stone is being considered to provide the required additional LAW immobilization capacity. The Cast Stone waste form must be acceptable for disposal in the IDF. The Cast Stone waste form and immobilization process must be tested to demonstrate that the final Cast Stone waste form can comply with waste acceptance criteria for the IDF disposal facility and that the immobilization processes can be controlled to consistently provide an acceptable waste form product. Further, the waste form must be tested to provide the technical basis for understanding the long term performance of the waste form in the IDF disposal environment. These waste form performance data are needed to support risk assessment and performance assessment (PA) analyses of the long-term environmental impact of the waste disposal in the IDF. A testing program was developed in fiscal year (FY) 2012 describing in some detail the work needed to develop and qualify Cast Stone as a waste form for the solidification of Hanford LAW (Westsik et al. 2012). Included within Westsik et al. (2012) is a section on the near-term needs to address Tri-Party Agreement Milestone M-062-40ZZ. The objectives of the testing program to be conducted in FY 2013 and FY 2014 are to: • Determine an acceptable formulation for the LAW Cast Stone waste form. • Evaluate sources of dry materials for preparing the LAW Cast Stone. • Demonstrate the robustness of the Cast Stone waste form for a range of LAW compositions. • Demonstrate the robustness of the formulation for variability in the Cast Stone process. • Provide Cast Stone contaminant release data for PA and risk assessment evaluations. The first step in determining an acceptable formulation for the LAW Cast Stone waste form is to conduct screening tests to examine expected ranges in pretreated LAW composition, waste stream concentrations, dry-materials sources, and mix ratios of waste feed to dry blend. A statistically designed test matrix will be used to evaluate the effects of these key parameters on the properties of the Cast Stone as it is initially prepared and after curing. The second phase of testing will focus on selection of a baseline Cast Stone formulation for LAW and demonstrating that Cast Stone can meet expected waste form requirements for disposal in the IDF. It is expected that this testing will use the results of the screening tests to define a smaller suite of tests to refine the composition of the baseline Cast Stone formulation (e.g. waste concentration, water to dry mix ratio, waste loading).

Russell, Renee L.↗

Multi‐Material Gradient Printing Using Meniscus‐enabled Projection Stereolithography (MAPS)

Light‐based additive manufacturing methods are widely used to print high‐resolution 3D structures for applications in tissue engineering, soft robotics, photonics, and microfluidics, among others. Despite this progress, multi‐material printing with these methods remains challenging due to constraints associated with hardware modifications, control systems, cross‐contamination, waste, and resin properties. Here, a new printing platform coined Meniscus‐enabled Projection Stereolithography (MAPS) is reported, a vat‐free method that relies on generating and maintaining a resin meniscus between a crosslinked structure and bottom window to print lateral, vertical, discrete, or gradient multi‐material 3D structures with no waste and user‐defined mixing between layers. MAPS is compatible with a wide range of resins shown and can print complex multi‐material 3D structures without requiring specialized hardware, software, or complex washing protocols. MAPS's ability to print structures with microscale variations in mechanical stiffness, opacity, surface energy, cell densities, and magnetic properties provides a generic method to make advanced materials for a broad range of applications.

bioprinting↗

Total metals & anion concentration data; Slate River floodplain, Crested Butte, CO; May 2020-September 2020

This data package includes processed and undiluted measurements for metal and anion concentrations from pore water (groundwater) samples from the Slate River floodplain of Crested Butte, CO, a focus field site for the SLAC Floodplain Hydro-Biogeochemistry SFA. The data was generated as part of the work targeting the overarching research question for the SLAC SFA: How do ubiquitous subsurface interfaces mediate molecular-scale biogeochemical processes and groundwater quality in floodplains and watersheds? Samples were collected between May and September of 2020. These measurements were all recorded at the Arizona Laboratory for Emerging Contaminants (ALEC) at the University of Arizona located in Tucson, AZ. Groundwater samples were extracted from a network of installed rhizon (Rhizosphere Research Products, part no. 19.60.21F, 0.6 micrometer mesh size) and piezometer wells within the river floodplain. All water samples were shaded from sun exposure during extraction from the subsurface and preserved at 4C until measured at ALEC.Analysis by ICP-MS:Measurements for total metals were made on the Agilent 7700x ICP-MS (for total metals) – Agilent Technologies, Santa Clara, CA.The analytical QA/QC protocol was adapted from US EPA Method 200.8 for analysis by ICP-MS. Calibration standards were prepared from multi-element stock solution (Sigma-Aldrich Multielement standard solution for ICP, St. Louis, MO) using matrix matched to sample solutions (either 2% HCl or HNO3 from AriStar Plus,grade acids from VWR Scientific). Calibration curves include at least 7 points with correlation coefficients > 0.995. The QC protocol includes a continuing calibration blank (CCB), a continuing calibration verification (CCV) solution and at least one quality control sample (QCS) to be analyzed just after calibration and again after every 12 samples and at the completion of the run. The QCS solutions are from an independent source, such as NIST SRM 1643e - Trace Elements in Water, or QCS solutions from High Purity Standards (Charleston, SC). Acceptable QC responses must be between 90 and 110% of the certified value. An internal standard (Rh) is added via on-line addition into the sample line using a mixing tee.Analysis by Ion Chromatography (Anions):The protocol follows Method 4110 in Standard Methods for Examination of Water and Wastewater.The instrument used is the Thermo Scientific Dionex ICS-6000 using AS+AG22 column set for anion analysis with isocratic method using sodium carbonate eluent. Detection is by chemical suppression of eluent conductivity. Quality control solutions and mixed analyte standards purchased from Inorganic Ventures, Christiansburg, VA.All files are in csv format.

54 ENVIRONMENTAL SCIENCES↗

Adsorption of Iodine and Tritium from UNF Reprocessing Off-Gas Streams

The need to control emissions of the gaseous radionuclides to the air during nuclear fuel recycling is widely recognized. Gaseous radionuclides can partition to off-gas streams emanating from the various individual processes used in the recycle plant, such as from the mechanical head end (shear), tritium pretreatment, fuel dissolver, vessel vents, cell ventilation, and conversion operations. In traditional recycle plants, the bulk of the four primary volatile fission products (i.e., {sup 3}H, {sup 14}C, {sup 85}Kr, and {sup 129}I) is released in the head-end processes, for example, the dissolution process. The usual off-gas treatment sequence of operations targets removal of tritium (as {sup 3}HHO), iodine, carbon (as {sup 14}CO{sub 2}), and the noble gases, in that order. Water and iodine are captured first because the other species are relatively unimpeded by the sorbents used for water and iodine, so they flow downstream to additional treatment processes. Water and iodine do react with one another, and many techniques used to collect one of these species also collect some fraction of the other. It is quite desirable to sequester the iodine and water separately because the tritiated water may be disposed of as a low level waste. If not cleanly separated, contamination of the low-level waste by iodine may elevate its classification to high-level waste and result in greater costs for disposal. The proposed sorption sequence was tested in the laboratory. Use of a second column of AgZ permits the detection of breakthrough from the primary AgZ column while protecting the downstream 3AMS column from collecting iodine. (This arrangement is equivalent to enabling intra-column sampling of the primary column.) Neutron activation analysis of the 3AMS revealed that iodine was below, or at, the level of detection. The results successfully demonstrated that iodine can be sequestered in the AgZ while the water is collected free of iodine in the 3AMS column. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Conventional and Next Generation Treatment Technologies for PFAS - 20067

In 2016, the United States Environmental Protection Agency (USEPA) established a Health Advisory Limit (HAL) for perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) (individually and the summation) of 70 nanograms per liter (ng/L) based on developing toxicological information. These two compounds are among several thousand per- and polyfluoroalkyl substances (PFAS). Due to a multitude of commercially beneficial physical and chemical properties, the availability of PFAS-relevant and practical water treatment technologies is limited. The use of conventional adsorbents, such as activated carbon (AC) and anion exchange (AIX) resins, have become a 'de facto' interim measure to immediately address drinking water above this criterion. However, these adsorbents can have marginal long-term efficiency and are relatively unproven against the diversity of polyfluorinated compounds. Additionally, geochemical and/or co-contaminant competition can significantly impede adsorption based PFAS removal. These challenges may be addressed using engineered filtration, such as reverse osmosis or nanofiltration (RO/NF); however, for larger flow systems RO/NF may have unacceptable reject ratios as high as 35% and the capital cost may preclude these technologies. Extending these technologies to natural waters, which have various degrees of geochemical and co-contaminant competition, often requires a treatment train, combining conventional adsorbents or engineered filtration with pretreatment and more innovative and emerging remediation solutions for PFAS. Conventional and Next Generation water treatment technologies for PFAS generally employ one of three mechanisms (adsorption, separation, or destruction). These mechanisms include many types of technologies for both municipal drinking water and extracted natural water applications. The previously mentioned AC, AIX, and RO/NF are commercially available technologies that are actively being deployed for PFAS treatment. Research and development around these technologies is focused on optimization, and ultimate destruction of PFAS is achieved through incineration. Next Generation water treatment technologies include PFAS-specific flocculants, foam fractionation, novel AIX resins, new engineered adsorptive media, electrochemical treatment, sonolysis, and photolysis, radiation, and plasma (forms of advanced reductive processes [ARP]). Research and development around these technologies is focused on proof of concept and assimilation to real world applications. As the PFAS-relevant destructive technologies (such as incineration, electrochemical treatment, sonolysis, and ARP) are energy intensive, the state of the practice for PFAS water treatment is to focus adsorption/separation based technologies on reducing and concentrating the volume of water requiring destructive treatment. This enables more flexibility with respect to circulation frequency, residence time, and more control over energy usage. Water treatment for PFAS presently requires multiple technologies (i.e. a treatment train) to protect human health in a cost-conscious manner. An investment in research and development to explore new technologies is part of a key initiative for efficient protection of human health. This presentation attempts to review PFAS-relevant water treatment technologies and provide perspective as to their status with respect to applicability and commercial relevance. (authors)

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Reassessment of Resuspension Factor Following Radionuclide Dispersal: Toward a General-purpose Rate Constant

A recent analysis of historical radionuclide resuspension datasets confirmed the general applicability of the Anspaugh and modified Anspaugh models of resuspension factors following both controlled and disastrous releases. While observations appear to have larger variance earlier in time, previous studies equally weighted the data for statistical fit calculations; this could induce a positive skewing of resuspension coefficients in the early time-period. A refitting is performed using a relative instrumental weighting of the observations. Measurements within a 3-d window are grouped into singular sample sets to construct standard deviations. The resulting best-fit equations produce tamer exponentials, which give decreased integrated resuspension factor values relative to those reported by Anspaugh. As expected, the fits attenuate greater error among the data at earlier time. In conclusion, the reevaluation provides a sharper contrast between the empirical models and reaffirms their deficiencies in the short-lived timeframe wherein the dynamics of particulate dispersion dominate the resuspension process.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

Impact of sedimentary provenance and weathering on arsenic distribution in aquifers of the Datong basin, China: Constraints from elemental geochemistry

Arsenic (As)-contaminated aquifer sediments from Datong basin, China have been analyzed to infer the provenance and depositional environment related to As distribution in the aquifer sediments. The As content in the sediments ranged from 2.45 to 27.38 mg/kg with an average value of 9.54 mg/kg, which is comparable to the average value in modern unconsolidated sediments. However, minor variation in As concentration with depth has been observed in the core. There was a significant correlation between Fe, and Al and As, which was attributed to the adsorption or co-precipitation of As onto/with Fe oxides/hydroxides and/or Fe-coated clay minerals. Post-Archean Australian Shale (PAAS)-normalized REEs patterns of sediment samples along the borehole were constant, and the sediments had a notably restricted range of La-N/Yb-N ratios from 0.7 to 1.0. These results suggested that the provenance of the Datong basin remained similar throughout the whole depositional period. The analysis of major geochemical compositions confirmed that all core sediments were from the same sedimentary source and experienced significant sedimentary recycling. The co-variation of As, V/Al, Ni/Al and chemical index of alteration (CIA) values in the sediments along the borehole suggested that As distribution in the sediments was primarily controlled by weathering processes. The calculated CIA values of the sediments along the borehole indicate that a relative strong chemical weathering occurred during the deposition of sediments at depths of similar to 35 to 88 m, which was corresponding to the depth at which high As groundwater was observed at the site. Strong chemical weathering favored the deposition of Fe-bearing minerals including poorly crystalline and crystalline Fe oxide mineral phases and concomitant co-precipitation of As with these minerals in the sediments. Subsequent reductive dissolution of As-bearing poorly crystalline and crystalline Fe oxides would result in the enrichment of As in groundwater. In general, the chemical weathering during the deposition of the sediments governed the co-accumulation of Fe oxides and As in the aquifer sediments. And then, the reductive dissolution of Fe oxides/hydroxides is the mechanism of As enrichment in the groundwater in the Datong basin

Xie, Xianjun↗

Pore-Scale Characterization of Biogeochemical Controls on Iron and Uranium Speciation under Flow Conditions

Etched silicon microfluidic pore network models (micromodels) with controlled chemical and redox gradients, mineralogy, and microbiology under continuous flow conditions are used for the incremental development of complex microenvironments that simulate subsurface conditions. We demonstrate the colonization of micromodel pore spaces by an anaerobic Fe(III)-reducing bacterial species (Geobacter sulfurreducens) and the enzymatic reduction of a bioavailable Fe(III) phase within this environment. Using both X-ray Microprobe and X-ray Absorption Spectroscopy, we investigate the combined effects of the precipitated Fe(III) phases and the microbial population on uranium biogeochemistry under flow conditions. Precipitated Fe(III) phases within the micromodel were most effectively reduced in the presence of an electron shuttle (AQDS), and Fe(II) ions adsorbed onto the precipitated mineral surface without inducing any structural change. In the absence of Fe(III), U(VI) was effectively reduced by the microbial population to insoluble U(IV), which was precipitated in discrete regions associated with biomass. In the presence of Fe(III) phases, however, both U(IV) and U(VI) could be detected associated with biomass, suggesting re-oxidation of U(IV) by localized Fe(III) phases. These results demonstrate the importance of the spatial localization of biomass and redox active metals, and illustrate the key effects of pore-scale processes on contaminant fate and reactive transport.

Environmental Molecular Sciences Laboratory↗

Field-Scale Lysimeter Studies of Glass and Cementitious Waste Forms at the Hanford Site - 20392

The Hanford site Integrated Disposal Facility (IDF) will receive waste forms from vitrification activities at the Hanford Waste Treatment and Immobilization Plant (WTP). The waste form inventory to be disposed of at the IDF will consist of vitrified low-activity waste (LAW) in glass forms and solidified (or encapsulated) secondary wastes in cementitious forms. The IDF is a near-surface burial facility located near Hanford's Waste Treatment and Immobilization Plant in the 200 East Area of the site's Central Plateau. An extensive set of laboratory experimental data has been collected to support IDF performance assessment calculations of the eventual degradation of waste forms and mobility of contaminants. This paper describes the start of a field experiment to generate waste-form performance data on a larger scale (tens of centimeters), over a longer duration (five years or more), and under field conditions representative of the IDF. Results from this study are expected to improve model descriptions of contaminant mobility, reduce uncertainties about the representativeness of laboratory results in the IDF performance assessment, improve stakeholder confidence in the safe disposal of treated waste at the IDF, and facilitate the adoption of informed facility designs with the potential to reduce operational costs. A lysimeter test facility near Hanford's 200 West Area has been repurposed to carry out long-term assessments of waste forms buried in sediments excavated from the IDF. The waste forms are buried in large drainage lysimeters, open caissons that are two meters in diameter and three meters deep. Waste forms are buried in up to six locations in each lysimeter. Samplers collect pore water and drainage water beneath the waste forms and air from the pore space adjacent to waste forms. Sensors measure temperature, soil water content, soil water tension, and drainage flux. One lysimeter containing cementitious waste forms and one containing glass waste forms have been completed, along with a control lysimeter (without waste forms). The cementitious waste forms are Cast Stone grout formulations using a liquid secondary waste simulant and a generic Hanford high-salt simulant, as well as a hydrated lime-based grout formulation using a liquid secondary waste simulant. Technetium-99 and iodine-127 were added as tracers to monitor contaminant mobility. Glass waste forms were fabricated in two formulations (LAWA44 and ORLEC28), with rhenium and molybdenum tracers to monitor waste form degradation. The predicted performance of the waste forms in the lysimeters was modeled prior to installation to determine waste form size, tracer concentration/activity, and locations of sensors and samplers. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The Complexation Properties of Self-Defensive Microgel-Modified Antimicrobial Surfaces

The complexation of cationic antimicrobials with polyanionic microgels on a biomaterial surface can render that surface self-defensive against bacteria by killing those bacteria which physically contact the antimicrobial-loaded microgels. This killing has been attributed to the contact-driven transfer of antimicrobial from a microgel to a challenging bacterium, though much remains unknown about this process. Here, in this study, we use a combination of experiments and computational modeling to identify key aspects of the complexation phenomena which influence the self-defensive properties. We synthesize poly(acrylic acid) (PAA) microgels (∼2–5 μm diameter) via membrane emulsification and electrostatically deposit them onto polycaprolactone (PCL) coupons or onto glass to form a discontinuous submonolayer. Subsequent microgel loading with colistin or with Sub5 antimicrobial peptide (AMP) causes microgel deswelling. Under physiological conditions Sub5 remains stably sequestered whereas colistin is quickly released. Coarse-grained molecular dynamics (CGMD) simulations confirm stronger Sub5/PAA complexation. CGMD calculations also indicate that Sub5 forms dimers and higher-order structures, a prediction confirmed experimentally by Small-Angle X-ray Scattering (SAXS). Supramolecular structure entropically enhances the complexation strength because of enhanced counterion release per complexation event, and this finding can help identify other antimicrobials well suited for such a nonelutive yet self-defensive strategy. CGMD simulations also show that Sub5 has a higher complexation strength with the Staphylococcus aureus membrane than it does with PAA, confirming that there is a thermodynamic driving force for antimicrobial transfer. Such self-defensive surfaces significantly reduce S. aureus colonization (over 90% reduction relative to unmodified controls) in an in vitro hematogenous contamination model and remain cyto-compatible as evidenced by mesenchymal stem cell spreading and proliferation.

36 MATERIALS SCIENCE↗

Motion Tracking Of A Handheld Scanner With An Infrared Vision System

Handheld scanners are used in a large number of applications to inspect walls, floors, tanks, and other large structures. Measurements are made to characterize physical properties, uncover defects, detect evidence of tampering, quantify surface contamination, and so forth. Handheld scanning suffers from a number of drawbacks. The relationship between the data collected and scanned location is difficult or impossible to track. Humans using handheld scanners can unintentionally scan the same area multiple times or entirely overlook an area of interest. An automated scanner tracking system could improve upon current inspection practices with a handheld scanner in terms of efficiency, accuracy, and quality. The authors have developed a handheld scanner tracking system that will allow users to visualize previously scanned areas, highlight areas where important or unusual data are acquired, and store scanning location with acquired data. The scanned regions are saved in real time and projected back on the scanned area using a projector. The system currently utilizes the Smoothboard software, which has already been designed to interpret the location of a captured infrared source from a Wii Remote controller to create an interactive whiteboard. This software takes advantage of the Wii Remote’s ability to track the location of an infrared source, and when proper calibration of the Wii Remote orientation is complete, any surface can become a virtual whiteboard. In addition to recording and projecting scan pathways, the system developed by the authors can be used to make notes on the scanning process and project acquired data on top of the scanned area. This latter capability can be used to guide sample acquisition or demolition activities. This paper discusses development of the system and potential benefits to wall scanning with handheld scanners.

Wii Remote, Wall scanner, IR tracking, Motion Trac↗

Risk to ecological resources following remediation can be due mainly to increased resource value of successful restoration: A case study from the Department of Energy's Hanford Site

Several nations are faced with the need to remediate large contaminated sites following World War II, the Cold War, and abandoned industrial sites, and to return them to productive land uses. In the United States, the Department of Energy (DOE) has the largest cleanup challenge, and its Hanford Site in the state of Washington has the most extensive and most expensive cleanup task. Ideally, the risk to ecological resources on remediation sites is evaluated before, during, and after remediation, and the risk from, or damage to, ecological resources from contaminants should be lower following remediation. In this paper, we report the risk to ecological resources before, during, and as a consequence of remediation on contaminated units requiring cleanup, and then examine the causes for changes in risk by evaluating 56 cleanup evaluation units (EUs) at the Hanford Site. In this case, remediation includes a restoration phase. In general, the risk to ecological and eco-cultural resources is currently not discernible or low at most contaminated units, increases during remediation, and decreases thereafter. Remediation often causes physical disruption to ecosystems as it reduces the risk from exposure to contaminants. Most new remediation projects at the Hanford Site include ecological restoration. Ecological restoration results in the potential for the presence of higher quality resources after remediation than currently exists on these contaminated lands and facilities. Although counter-intuitive, our evaluation of the risk to ecological resources following remediation indicated that a significant percentage of units (61%) will be at increased risk in the post-remediation period. This increased risk is due to DOE's successful remediation and restoration that results in a higher percent of native vegetation and higher ecological value on the sites in the post-remediation period than before. These newly-created resources can then be at risk from post-remediation activities. Risks to these new higher quality resources include the potential for spread of invasive species and of noxious grasses used in previous cleanup actions, disruption of ecosystems (including those with state or federally listed species and unique ecosystems), compaction of soil, use of pesticides to control invasive species, and the eventual need for continued monitoring activities. Thus, by greatly improving the existing habitat and health of eco-receptors, and maintaining habitat corridors between high quality habitats, the ecological resources in the post-remediated units are at risk unless care is taken to protect them. Many of the negative effects of both remediation and future monitoring (or other future land uses) can be avoided by planning and management early in the remediation process. We suggest DOE and other agencies convene a panel of managers, remediation scientists, regulators, environmental and ecological scientists, Native Americans, economists, and the public to develop a generic list of performance metrics for the restoration phase of remediation, including evaluation of success, which could be applied across the DOE complex.

54 ENVIRONMENTAL SCIENCES↗

Formation of zinc carbonate phases on dissolving calcite, aragonite, and vaterite in acidic aqueous solutions

Calcium carbonate (CaCO 3 ) minerals serve as a major sink to retain metal ions through mineral-water interfacial reactions in which the capacity and long-term stability of contaminant uptake are influenced by coupled dissolution and precipitation reactions of both primary and secondary carbonate minerals (i.e., mineral replacement). Notably, recent studies of calcite reactivity in acidic solutions containing high levels of metal ions demonstrated complex behavior under conditions of sustained disequilibrium. Here, we explored the reactivity of three CaCO 3 polymorphs (calcite, aragonite, and vaterite) with acidic Zn 2+ -containing aqueous solutions using a suite of imaging techniques including optical and scanning electron microscopies, synchrotron-based micro X-ray fluorescence, and transmission X-ray microscopy. Zn uptake by calcite occurred through a two-step process: the formation of a thin layer of the zinc precipitate on the substrate surface followed by the growth of fibrous and radiating hydrozincite particles from the layer. In contrast, Zn uptake by aragonite occurred by mineral replacement where the secondary Zn carbonate phase preserved the external morphology of the original crystal (i.e., a pseudomorph). The replacement of vaterite by hydrozincite occurred within the confined space beneath the porous shell of vaterite, signifying that the primary mechanism driving Zn carbonate precipitation was chemical exchange through the pores. When multiple CaCO 3 polymorphs coexisted, the replacement of aragonite and vaterite occurred preferentially over that of calcite. These results demonstrate the distinct morphological and mineralogical controls over the reactivities of calcium carbonate minerals with Zn 2+ under acidic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrometallurgical Recycling of Black Mass of Spent Lithium-Ion Batteries Using Methanesulfonic Acid: Leaching, Kinetic Studies, and Potential for Total Recovery of Valuable Components

Methanesulfonic acid (MSA) exhibits several advantageous properties rendering it a promising candidate for circular hydrometallurgical processes. These properties include a high acidity (pKa = - 1.9) comparable to that of classical mineral acids as well as biodegradability, high stability, and high solubility of metal-MSA complexes in aqueous solutions. In this study, MSA was employed as a lixiviant for the leaching of metals (lithium, nickel, cobalt, and manganese) from the black mass of spent lithium-ion batteries (LIBs). The effect of various parameters, including MSA concentration, H 2 O 2 concentration, temperature, and pulp density, was systematically investigated. Under the optimized conditions (1.5 M MSA, 0.2 M H 2 O 2 , 60 °C, and 50 g/L pulp density), quantitative leaching of lithium was achieved within 30 min, while for nickel and cobalt it was after 2 h, and 4 h for manganese leaching. The leaching kinetics of Li, Ni, Co, and Mn were studies using the shrinking particle models (SPM) and the Avrami model. The results indicated that the Avrami model provided the best fit to the kinetic data, with apparent activation energies of 46.81 kJ/mol for Li, 58.61 kJ/mol for Ni, 59.69 kJ/mol for Co, and 58.86 kJ/mol for Mn, within the temperature range of 25-70 °C (except for Li, which was analyzed in the range of 25-60 °C), consistent with chemical reaction control. Subsequently, residual contaminants in the leaching residue were eliminated through pyrolysis. The quantitative leaching of metals in MSA solution (a green lixiviant), combined with the pyrolytic treatment of leaching residues, represents a circular strategy for the total recovery of valuable components from the black mass of spent LIBs.

25 ENERGY STORAGE↗

Innovative Strategies for Long-Term Monitoring of Complex Groundwater Plumes at DOE’s Legacy Sites (Workshop Report)

Most remaining Department of Energy (DOE) sites will require extended periods of institutional control, especially at complex groundwater sites where attenuation-based strategies have been implemented to facilitate closure. The current practice of monitoring—obtaining and analyzing contaminant concentration in groundwater samples at numerous wells—will account for a large portion of the projected life-cycle at these DOE sites unless a new approach is adopted. State-of-the-art technologies are being developed, including in situ sensors, geophysics, radiation mapping, numerical modeling and AI/ML. These technologies can optimize monitoring strategies in space and time, provide spatially extensive information at vulnerable regions and/or provide more continuous monitoring at lower cost. As part of DOE’s Office of Environmental Management (DOE-EM’s) efforts to advance long-term monitoring systems, an in-person/virtual hybrid workshop was hosted by Savannah River National Laboratory (SRNL) on January 24 and 25, 2023, in Augusta, Georgia. Because DOE-EM’s complex sites will eventually be transferred to DOE’s Office of Legacy Management (DOE-LM), representatives of DOE-LM were important participants in the workshop. The purpose of the workshop was to identify challenges and opportunities for deploying advanced technologies for long-term monitoring at DOE sites. The key questions during the workshop were: 1) the regulatory acceptance of replacing a process that traditionally has used laboratory sampling and analysis of groundwater samples, and 2) the application of this strategy to the southwestern arid sites that include many of the remaining DOE-EM and DOE-LM complex groundwater plumes. Characteristics common to most arid sites present both limitations and opportunities for advanced technologies. DOE-EM has funded a National Laboratory team from SRNL, Lawrence Berkeley National Laboratory (LBNL), and Pacific Northwest National Laboratory (PNNL) to establish the overarching framework of long-term monitoring by systematically combining advanced hardware and software technologies. This project is titled “Advanced Long-Term Environmental Monitoring Systems (ALTEMIS)” and is sponsored by the DOE-EM Technology Development Program. The multi-laboratory team is currently developing and testing innovative monitoring strategies, including the use of in situ groundwater sensors, geophysics, drone/satellite-based remote sensing, reactive transport modeling, and artificial intelligence/machine learning (AI/ML). The project’s demonstration testbed is at the Savannah River Site (SRS) F-Area Seepage Basins, where a well-characterized complex groundwater plume composed of uranium and other radionuclides is in the latter stages of remediation. The workshop included more than 70 participants, presentations, a field visit to F-Area, breakout working groups, and large group discussion. Participants developed recommendations on five topics: in situ sensors, spatially integrative tools, challenges to regulatory acceptance, AI/ML strategies, and transitioning sites to DOE-LM.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗