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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Alternate Endpoints for Deep Vadose Zone Environments: Challenges, Opportunities, and Progress

Current requirements for site remediation and closure are standards-based and are often overly conservative, costly, and in some cases, technically impractical to achieve. Use of risk-informed alternate endpoints provide a means to achieve remediation goals that are permitted by regulations and are protective of human health and the environment. Alternate endpoints enable establishing a path for cleanup that may include intermediate remedial milestones and transition points and/or regulatory alternatives to standards-based remediation. A framework is presented that is centered around developing and refining conceptual models in conjunction with assessing risks and potential endpoints as part of a system-based assessment that integrates site data with scientific understanding of processes that control the distribution and transport of contaminants in the subsurface and pathways to receptors. This system based assessment and subsequent implementation of the remediation strategy with appropriate monitoring are targeted at providing a holistic approach to addressing risks to human health and the environment. This holistic approach also enables effective predictive analysis of contaminant behavior to provide defensible criteria and data for making long-term decisions. Developing and implementing an alternate endpoint-based approach for remediation and waste site closure presents a number of challenges and opportunities. Categories of these challenges include scientific and technical, regulatory, institutional, and budget and resource allocation issues. Opportunities exist for developing and implementing systems-based approaches with respect to supportive characterization, monitoring, predictive modeling, and remediation approaches.

endpoints↗
DOE OSTI2013

Alternate Endpoints for Deep Vadose Zone Environments: Challenges, Opportunities, and Progress - 13036

Current requirements for site remediation and closure are standards-based and are often overly conservative, costly, and in some cases, technically impractical to achieve. Use of risk-informed alternate endpoints provide a means to achieve remediation goals that are permitted by regulations and are protective of human health and the environment. Alternate endpoints enable establishing a path for cleanup that may include intermediate remedial milestones and transition points and/or regulatory alternatives to standards-based remediation. A framework is presented that is centered around developing and refining conceptual models in conjunction with assessing risks and potential endpoints as part of a system-based assessment that integrates site data with scientific understanding of processes that control the distribution and transport of contaminants in the subsurface and pathways to receptors. This system-based assessment and subsequent implementation of the remediation strategy with appropriate monitoring are targeted at providing a holistic approach to addressing risks to human health and the environment. This holistic approach also enables effective predictive analysis of contaminant behavior to provide defensible criteria and data for making long-term decisions. Developing and implementing an alternate endpoint-based approach for remediation and waste site closure presents a number of challenges and opportunities. Categories of these challenges include scientific and technical, regulatory, institutional, and budget and resource allocation issues. Opportunities exist for developing and implementing systems-based approaches with respect to supportive characterization, monitoring, predictive modeling, and remediation approaches. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2014

Ecological risk assessment of elemental pollution in sediment from Tunku Abdul Rahman National Park, Sabah

Eleven (11) surface sediment samples were collected from Tunku Abdul Rahman National Park, Sabah. The neutron activation analysis (NAA) and inductively coupled plasma-mass spectrometry (ICP-MS) techniques were applied for the determinations metal contents and their distributions in sediment samples. The results shown that Arsenic (As) concentrations are enriched at all sampling stations except for station TAR 09, with enrichment factor (EF) values ranged from 1.1 to 7.2. The elements such as Cd, Cr, Sb and U showed enrichment at a few stations and other elements (Cr, Cu, Pb, Th, Zn) shown as background levels in all stations. Degrees of contamination in this study were calculated base on concentrations of six elements (As, Cd, Cr, Cu, Pb, and Zn). TAR 11 station can be categorized as very high degree of contamination with degree of contamination value of 43.2. TAR 07 station can be categorized as a considerable degree of contamination (contamination value of 16.9). Six stations (TAR 01, 03, 04, 05, 06, 08, 10) showed moderate degree of contamination, with contamination values ranging from 8.0 to 16.0. TAR 02 and TAR 09 stations showed low degree of contaminations (< 8.0). TAR 11 showed very high ecological risk index (R{sub I}) with RI value is 916. TAR 07 and TAR 10 showed moderate ecological risk index with R{sub I} value 263 and 213, respectively. Other stations showed low ecological risk with RI values ranging from 42.3 to 117 (< 150). Very high ecological risk index could give an adverse effect to the benthic organism. The data obtained from the enrichment factor, degree of contamination and ecological risk index provided vital information, which can be used for future comparison. Information from the present study will be useful to the relevant government agencies and authorities in preparing preventive action to control direct discharge of heavy metals from industries, agro-base activities and domestic waste to the rivers and the sea.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗
DOE OSTI2021

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

Foam, due to the high gas generation rates of boiling and chemical reaction offgasing, requires control measures to prevent the foam from contaminating the condensate and to facilitate efficient plant operation. Antifoam was utilized to minimize foam production during chemical processing in the DWPF and during High-Level Waste (HLW) evaporation at SRS and Hanford. However, the current antifoam used in the SRS DWPF increases flammability risk during chemical processing (generates three flammable degradation products) and while feeding the melter (can decompose to CO/hydrogen). It is also the likely source of methyl functional groups for the organo-mercury present in the tank farm and excessive mercury in Saltstone. Additionally, the planned startup of Salt Waste Processing Facility (SWPF), with much higher throughput, will challenge DWPF to process at higher gas generation rates. DWPF employs Antifoam 747, a superspreader produced by Momentive Performance Materials, as an antifoaming agent during waste processing. During DWPF chemical processing, antifoam must be effective up to boiling (i.e., up to 103°C) and between a pH of 3-13. Antifoam 747 is most effective at a pH range of 6-8 and degrades as pH deviates. In addition, SRNL identified three flammable antifoam degradation products using mass spectrometer (MS) and fourier transform infrared (FTIR) offgas analyzers during simulations. A new antifoam or a new method to control foam is needed to minimize DWPF processing time and reduce the risk of contamination. In addition, testing should be completed to ensure that other antifoams used in HLW processing do not have similar flammability hazards or cause unintended impacts in downstream processing.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

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↗
DOE OSTI2018

D and D of a Large Waste Treatment Plant in Germany - 18458

With its 40 years of nuclear experience, GNS, the world leading supplier of casks for spent fuel, ILW and HLW, also offers services for conditioning and management of all types of radioactive waste, especially for the German NPP. Since 1985, GNS treats and packages ILW and LLW from the operations and phase-out of German NPP in its Duisburg plant. To enable its permanent safe final disposal, solid wastes are compacted and dried before being shipped to an interim storage facility or - later - the Konrad repository. The total premises cover 20.000 m{sup 2} (215.000 sq ft), of which 9000 m{sup 2} (97.000 sq ft) is controlled area. The Duisburg Plant has three large industrial warehouses (each 25 m x 136 m or 82 ft x 446 ft) with a total capacity of 10.200 m{sup 2} or 110.000 sqft. For the treatment of open contaminated waste, six enclosures were built. These enclosures have a special ventilation system including a specific filtration plant. In one enclosure a high compaction plant was used, in another enclosures a drying facility for drums was in operation. During peak periods, more than 900 tonne of waste were treated annually. One enclosure was mainly used for maintenance, restoration and extension of mobile facilities, which were normally used for campaigns in NPP. Due to the decreasing amount of operational waste during the nuclear phase out in Germany, GNS has decided to close the Duisburg Plant. In the first half-year of 2017, the last waste packages were treated but around 80 20'-containers are still located on site. The D and D started in January 2017. The presentation will show the first experience of decommission processes of the first three enclosures. The following steps including the techniques used will be explained in detail: - Dismantling and removal of the high compaction facility; - Dismantling and removal of the drying facility; - Cleaning and wipe tests of the empty enclosures; - Removal of the stainless steel plates of the floor; - Investigations of the lower floor parts for contamination; - Removal of contaminated underground drainpipes; - Decontamination of the concrete floor; - Dismantling of the ventilation system in three enclosures; - Dismantling of the steel constructions. An important aim during the dismantling is to reduce the amount of nuclear waste and maximize the fraction material for free release. Next to the first three enclosures, in one of the enclosure IV - VI, a 150 tons scrap shear had been installed before the construction of the enclosure building. The scrap shear has to be dismantled and handled by heavy duty lifting equipment. Only afterwards is it possible to start the decommissioning of the last three enclosures. Our goal is to transfer this very large controlled area and the whole plant to the site owner, the Duisburg Port company, after 2 years and 5 months and doing so in a way so that the industrial warehouses can be used again for all possible types of industries. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

Divertor detachment and heat exhaust mitigation control in KSTAR with tungsten divertor

KSTAR has recently undergone an upgrade to use a new tungsten divertor to run experiments in ITER-relevant scenarios. Even with a high melting point of tungsten, it is important to control the heat flux impinging on tungsten divertor targets to minimize sputtering and contamination of the core plasma. Heat flux on the divertor is often controlled by increasing the degree of detachment of scrape-off layer plasma from the target plates. In this work, we have demonstrated successful divertor detachment and heat exhaust dissipation control experiments using two different methods. The first method uses attachment fraction as a control variable which is estimated using ion saturation current measurements from embedded Langmuir probes in the divertor. The second method uses a novel machine-learning-based surrogate model of 2D UEDGE simulation database, DivControlNN. We demonstrated running inference operation of DivControlNN in realtime to estimate heat flux at the divertor and use it as the control variable in a feedback loop with impurity gas flow. We present interesting insights from these experiments including a systematic approach to tuning controllers and discuss future improvements in the control infrastructure and control variables for future burning plasma experiments.

KSTAR tungsten divertor operations↗
DOE OSTI2020

Contaminant Migration Modeling to Support the In Situ Decommissioning of Hardened Nuclear Facilities - 20215

The decommissioning of hardened nuclear facilities provides a unique challenge in balancing current worker dose with exposure to future receptors and media. In situ decommissioning (ISD) is a cost-effective and safe option for the closure of such facilities but requires a detailed understanding of the threat that radioactive and hazardous constituents remaining in the facilities pose to groundwater and surrounding surface water. The Savannah River Site (SRS) extensively employs contaminant migration models within the decommissioning process to develop site-specific removal, grouting, and monitoring strategies in support of safe and effective final end states of nuclear facilities. This work discusses the use of contaminant migration modeling in the ISD process at SRS, including specific examples from the closure of P-Reactor and R-Reactor, Building 235-F, F-Canyon and F/H Laboratory Complex. Migration models developed during the closure of P-Reactor and R-Reactor were divided into four source areas: the reactor vessel, the process area, the disassembly basin, and the purification wing. Each source area was assigned a specific inventory and migration pathway and was then subject to varying hypothetical removal, capping, and grouting schemes. Modeling indicated that groundwater Maximum Concentration Limits (MCLs) might be exceeded if no action was taken for eleven and ten constituents of concern (COCs) at P-Reactor and R-Reactor, respectively. These exceedances could occur in as few as 200 to 500 years. Alternatively, the migration modeling demonstrated that the selected ISD actions reduced contaminant mobility which allowed for significant radioactive decay and resulted in fewer predicted exceedances of groundwater MCLs (five COCs for P-Reactor; eight COCs for R-Reactor). In response to the modeling results for P-Reactor and R-Reactor, effectiveness monitoring programs were developed to target contaminants, specific to each reactor, that may migrate to groundwater. Contaminant migration modeling also revealed that roof collapse was a large factor in the release of COCs to the environment, giving rise to roof improvements, and an inspection and vegetation control program to ensure roof stability over time. Contaminant migration modeling is also aiding in the closure planning for hardened facilities in F Area. Building 235-F housed the Actinide Billet Line, which produced Np-237 billets for irradiation in SRS reactors, and the Plutonium Fuel Form (PuFF) facility that produced Pu-238 heat sources for the space program. As a result of these missions, areas within Building 235-F contain considerable residual amounts of both Pu-238 and Np-237. Contaminant migration modeling of Building 235-F was originally performed in 2012 to identify the feasibility of ISD and the amount of radioactive material removal required to prevent the exceedance of groundwater MCLs. The original model indicated that a 60% reduction in the PuFF facility Pu-238 inventory could keep groundwater concentrations below standards, while Np-237 did not pose a threat to groundwater. However, updates to the model with an emphasis on source impact pathways revealed that, due to the orientation of the source areas relative to groundwater flow, no amount of reasonable removal of Pu-238 would keep groundwater concentrations below MCLs and that Np-237 could be a large contributor to localized MCL exceedances. With this insight, the refined 2019 model is being used to assist in the development of grouting plans specific to each facility source area, where bentonite may be utilized to slow the migration of Pu-238 and its daughter products from the PuFF facility and a reducing grout may decrease Np-237 transport by ensuring the nuclide remains in the less mobile +IV oxidation state. The beginning phases of contaminant migration modeling are underway for F-Canyon and associated facilities using lessons learned from the Reactors and Building 235-F. A contaminant migration pathway, similar to the pathway used for the reactor vessels, is being developed for the hot and warm canyons. The F-Canyon inventories are being spatially refined to identify specific and localized source zones, comparable to Building 235-F, that may impact groundwater. Contaminant migration modeling provides vital input within the ISD process, from facility investigation to post closure effectiveness monitoring, making it a valuable tool in the development of safe and effective end states for hardened nuclear facilities at SRS. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Detailed analysis of excited-state systematics in a lattice QCD calculation of 𝑔 𝐴

Excited state contamination remains one of the most challenging sources of systematic uncertainty to control in lattice QCD calculations of nucleon matrix elements and form factors: early time separations are contaminated by excited states and late times suffer from an exponentially bad signal-to-noise problem. High-statistics calculations at large time separations ≳ 1 fm are commonly used to combat these issues. In this work, focusing on g A , we explore the alternative strategy of utilizing a large number of relatively low-statistics calculations at short to medium time separations (0.2–1 fm), combined with a multistate analysis. On an ensemble with a pion mass of approximately 310 MeV and a lattice spacing of approximately 0.09 fm, we find this provides a more robust and economical method of quantifying and controlling the excited state systematic uncertainty. A quantitative separation of various types of excited states enables the identification of the transition matrix elements as the dominant contamination. The excited state contamination of the Feynman-Hellmann correlation function is found to reduce to the 1% level at approximately 1 fm while, for the more standard three-point functions, this does not occur until after 2 fm. Critical to our findings is the use of a global minimization, rather than fixing the spectrum from the two-point functions and using them as input to the three-point analysis. We find that the ground state parameters determined in such a global analysis are stable against variations in the excited state model, the number of excited states, and the truncation of early-time or late-time numerical data.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2019

Mercury Remediation in Oak Ridge, Tennessee; Successes and Remaining Challenges

Mercury remediation is a high priority for the US Department of Energy’s (DOE’s) Environmental Management program in Oak Ridge, Tennessee because of large historical losses of mercury to the environment, and the potential health risks to humans and wildlife primarily through fish consumption. Remedial solutions for mercury contaminated aquatic systems are limited – many aquatic systems have diffuse sources of mercury (Hg) and depending on the environmental conditions, these low concentrations of inorganic Hg can result in fish consumption advisories due to the production of the more toxic methylmercury (MeHg) and its bioaccumulation and biomagnification. From the 1980s to the present, long-term monitoring of mercury concentrations in water and fish downstream of DOE facilities in Oak Ridge have provided an opportunity to assess the performance and effectiveness of various remedial and abatement actions to address mercury. Early actions in the mid-1980s focused on pollution control that positively affected mercury discharges to one local stream, including consolidation and elimination of untreated discharges, sanitary sewer relining, the construction of a pollution control facility, and the replacement of a contaminated settling basin. The 1990s were an intensive period of facility remedial actions designed to improve stream water quality and reduce mercury discharges. Actions included dechlorinating cooling water discharges, an additional phase of storm sewer relining, the addition of flow from a nearby reservoir, the addition of two small-scale mercury treatment systems, the bypass of stream flow around the settling basin, and the removal of high mercury-contaminated floodplain soils. Because of these multiple remedial actions total mercury concentrations in receiving streams decreased significantly; however, mercury concentrations in fish did not respond commensurately and remain a challenge to the present day. Although the mercury remedial strategy in Oak Ridge will continue to focus in the near-term on upstream facility source reduction, recent research suggests that understanding mercury transport, methylation, and bioaccumulation processes in the downstream environment is essential to reducing mercury fish concentrations. Since 2014, mercury remediation research and technology development activities have been underway to develop potential remedial solutions for the downstream environment, including use of sorbents to control soil leaching and the potential use of chemical or biological manipulations. The Oak Ridge mercury remediation story is a valuable case study for flowing systems that can inform our national-level understanding of potential mercury cleanup actions and their likely environmental response.

Peterson, Mark J.↗
DOE OSTI2019

Mercury Remediation in Oak Ridge, Tennessee; Successes and Remaining Challenges - 19390

Mercury remediation is a high priority for the US Department of Energy's (DoE's) Environmental Management program in Oak Ridge, Tennessee because of large historical losses of mercury to the environment, and the potential health risks to humans and wildlife primarily through fish consumption. Remedial solutions for mercury contaminated aquatic systems are limited - many aquatic systems have diffuse sources of mercury (Hg) and depending on the environmental conditions, these low concentrations of inorganic Hg can result in fish consumption advisories due to the production of the more toxic methylmercury (MeHg) and its bioaccumulation and biomagnification. From the 1980's to the present, long-term monitoring of mercury concentrations in water and fish downstream of DOE facilities in Oak Ridge have provided an opportunity to assess the performance and effectiveness of various remedial and abatement actions to address mercury. Early actions in the mid-1980's focused on pollution control that positively affected mercury discharges to one local stream, including consolidation and elimination of untreated discharges, sanitary sewer relining, the construction of a pollution control facility, and the replacement of a contaminated settling basin. The 1990's were an intensive period of facility remedial actions designed to improve stream water quality and reduce mercury discharges. Actions included dechlorinating cooling water discharges, an additional phase of storm sewer relining, the addition of flow from a nearby reservoir, the addition of two small-scale mercury treatment systems, the bypass of stream flow around the settling basin, and the removal of high mercury-contaminated floodplain soils. Because of these multiple remedial actions total mercury concentrations in receiving streams decreased significantly; however, mercury concentrations in fish did not respond commensurately and remain a challenge to the present day. Although the mercury remedial strategy in Oak Ridge will continue to focus in the near-term on upstream facility source reduction, recent research suggests that understanding mercury transport, methylation, and bioaccumulation processes in the downstream environment is essential to reducing mercury fish concentrations. Since 2014, mercury remediation research and technology development activities have been underway to develop potential remedial solutions for the downstream environment, including use of sorbents to control soil leaching and the potential use of chemical or biological manipulations. The Oak Ridge mercury remediation story is a valuable case study for flowing systems that can inform our national-level understanding of potential mercury cleanup actions and their likely environmental response. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Novel Remediation of Mercury-Contaminated Sediments Using Manganese Oxide and Activated Carbon Amendments - 20394

Mercury contamination in sediments poses a challenging remediation problem because of its ability to biogeochemically cycle and biomagnify in the food chain as methylmercury from low resident sediment and porewater concentrations. One mitigation approach is to lower the overall rate of net methylmercury production by creating conditions unfavorable for sulfate and iron reduction or methanogenesis, the primary pathways for methylation of inorganic mercury. Manganese oxides and other redox-active amendments are a promising and novel in situ amendment technology aimed at reducing net methylation of mercury though control of redox conditions in mercury-contaminated sediment-water systems. This paper reviews the thermodynamic and kinetic framework for this remediation technology, presents experimental and spectroscopic data illustrating the approach using solid manganese oxides, and discusses potential advantages, disadvantages, and applications. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Investigation robot on cables - 15250

The Decontamination and Decommissioning (D and D) Operations take place in hostile environments to the human intervention. In this context, robotic systems are a solution to achieve these operations while minimizing human intervention. Among these operations, the monitoring of lengthwise plant has to be performed in places where the radioactive contaminations make hostile environments. These monitoring operations need to measure several physics parameters in several locations in a precise and safe manner. These repetitive tasks can be made by robots that are simple, small sized and easily adaptable. In this scope, a robotic system on cables has been designed to control and monitor the inside of lengthwise nuclear facilities. In lengthwise installations, the using of cables allows to increase the covered zone of the robots which is an essential quality in such places. Unlike cable-driven parallel robots used in workspaces of 2D or 3D controlled by redundant tensioning motors, the current robot moves in a 1D workspace. Thus a tractors cable controlled by one tensioning motor is used to drive the robot on carrier cables. In this paper, we will describe the first results of this work by bringing out the innovation of our system. Then, we will discuss the perspective to upgrade the actual system whose applications could be perfectly imagined outside the nuclear D and D industry. (authors)

42 ENGINEERING↗
DOE OSTI2025

Controlling Oxidation of Nb in Oxygen Abundant Environments.

Superconducting Radio Frequency (SRF) cavities, the core of modern particle accelerators, rely on high-purity niobium (Nb) to achieve high quality factors and accelerating gradients. However, native oxidation in ambient conditions introduces a complex oxide layer with increased surface defects and contamination, particularly from carbon. This research explores a controlled oxidation processes in an oxygen-abundant environment to try to control this complex oxide stack, with the goal of improving surface purity and uniformity. Using standard surface preparation techniques—including electropolishing, vacuum baking, and sonication—followed by a custom oxidation protocol, we compared structural and chemical changes through Confocal Microscopy, Scanning Electron Microscopy (SEM), and X-Ray Photoelectron Spectroscopy (XPS). Results show that iterative oxidation cycles can significantly reduce carbon-related defects, even without baking. Aditionally, baked samples with a specific oxidation technique demonstrated a measurable 25\% decrease in carbide formation.

Romero, Juan [Fermilab]↗
DOE OSTI2017

Electrical tuning of a quantum plasmonic resonance

Surface plasmon (SP) excitations in metals facilitate confinement of light into deep-subwavelength volumes and can induce strong light–matter interaction. Generally, the SP resonances supported by noble metal nanostructures are explained well by classical models, at least until the nanostructure size is decreased to a few nanometres, approaching the Fermi wavelength λ F of the electrons. Although there is a long history of reports on quantum size effects in the plasmonic response of nanometre-sized metal particles systematic experimental studies have been hindered by inhomogeneous broadening in ensemble measurements, as well as imperfect control over size, shape, faceting, surface reconstructions, contamination, charging effects and surface roughness in single-particle measurements. In particular, observation of the quantum size effect in metallic films and its tuning with thickness has been challenging as they only confine carriers in one direction. Here, we show active tuning of quantum size effects in SP resonances supported by a 20-nm-thick metallic film of indium tin oxide (ITO), a plasmonic material serving as a low-carrier-density Drude metal. An ionic liquid (IL) is used to electrically gate and partially deplete the ITO layer. The experiment shows a controllable and reversible blue-shift in the SP resonance above a critical voltage. As a result, a quantum-mechanical model including the quantum size effect reproduces the experimental results, whereas a classical model only predicts a red shift.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Deciphering controls on metal migration within floodplains: The critical role of redox environments on metal-organic complexes (Final Technical Report)

Our project elucidates the effect of differing hydrologic regimes on nutrient and contaminant dynamics within floodplains, and we explore the impact of varying sources of hydrologic extremes on nutrient-contaminant fate and transport. We use a combination of field measurements and laboratory experiments to examine the relationships between redox conditions, functionality of dissolved organic matter, metal speciation (specifically examining metal-ligand complexes), and nutrient-contaminant fate, particularly during hydrologic extremes. Floodplain biogeochemical variation through climatic extremes and beaver-induced hydrologic variation provide a unique look at controls on nutrient-contaminant fate and transport. Through our work, we have developed a novel approach that provides an unprecedented ability to resolve aqueous metal-organic complexes that reveals metal binding preferences for natural organic matter based on metal-ligand chemistry. We have developed novel methods to separate, quantify, and characterize organic-metal complexes in natural DOM that pair with field experiments comprising floodplains having systematic variation in biogeochemical conditions. We also developed a comprehensive computational approach for molecular characterization of metal-organic species that merges LC-coupled high resolution (HR) mass spectrometry and ICP-MS analysis. Importantly, we show that beaver dams have an outsized influence on hydrologic extremes, dwarfing the impact of climatic variation, that ultimate control biogeochemical conditions and water quality. Additionally, beaver dams impose a hydrologic driver that leads to improved, river water quality by divert water through soils and the hyporheic zone. We further show that iron(III) minerals have a dominant control on carbon mineralization across floodplains independent of hydrologic conditions, and that iron and aluminum associations with organic matter are a controlling factor in carbon mineralization. Ultimately, our work is helping to advancing a robust predictive understanding of how hydrologic changes in watersheds affect water quality and carbon and metal cycling in riparian zones.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Molecular Dynamics Simulations of the Adsorption of Phthalate Esters on Smectite Clay Surfaces

The partitioning of organic contaminants between water and solid surfaces is a key process controlling their fate and transport in natural environments. A novel methodology was developed to predict the adsorption of organic contaminants by smectite clay minerals (high specific surface area adsorbents abundant in natural soils) using molecular dynamics (MD) simulations. The methodology models a stack of flexible Ca- montmorillonite lamellae in direct contact with a bulk aqueous reservoir and uses the metadynamics technique to facilitate the exploration of the free energy landscape. The methodology was tested and validated in the case of six phthalate esters, widely used chemical plasticizers with endocrine disrupting properties. Simulation predictions reveal strong phthalate adsorption, especially for the larger and more hydrophobic phthalates. Predicted partition coefficients (K d values) are consistent with collected batch experimental data. Adsorption was observed on both the exterior basal surfaces and within the interlayer nanopore, with phthalate molecules predominately adopting a flat orientation on the clay surface. Intercalation was also detected in complementary X-ray diffraction (XRD) experiments. A strong inverse relationship between extent of adsorption and clay surface charge density was observed, as phthalate molecules preferentially occupied the more hydrophobic uncharged patches on each surface. Detailed analysis of the free energy of adsorption revealed that phthalate affinity for the clay surface results from a small favorable van der Waals contribution and a large favorable entropic contribution. Overall, this research demonstrates the substantial affinity of smectite clays for phthalate esters and establishes a computational methodology capable of predicting the water-clay partition coefficients of organic contaminants, a key parameter in environmental fate and transport models.

36 MATERIALS SCIENCE↗