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At least 469 records · Page 26

Assimilation and transport of organic bound tritium in an irrigated pine forest

The speciation of radioactive tritium (T) in a naturally-established subtropical loblolly pine forest that has been irrigated with highly-contaminated pond water for the last 20 years is reported. This irrigation project was created to limit the underground transport of a tritium-rich plume which also contains low levels of toxic organics, metals and radionuclides such as carbon-14 ( 14 C) from a nearby low-level waste burial ground. The levels of tritiated water (HTO) in the wood cores were not influenced by recent irrigation activities. However, the tritium levels in the last 20 years of tree growth were more than 3-fold higher than that of tritium in the older growth. This was due to recent irrigation with organic-bound tritium (OBT)-rich water and subsequent accumulation of high levels tritium as OBT relative to tissue HTO. High levels of pond irrigation water OBT resulted from biogenic processes that converted HTO to OBT. Data for 14 C that were acquired for some of the forest materials indicated that the processes controlling the movement and accumulation of 14 C in this system are somewhat different than that of tritium. Spectroscopic characterization of tree core tissue of <20 years in age found no explanation for the unusually wide dark growth rings. Here, it was concluded that the trees were over-irrigated based on results from other published studies with wood from severely-flooded areas. Although HTO is indeed toxic to biota, OBT represents a relatively greater hazard to biota because it can be bioaccumulated and retained for long periods of time in living tissues.

54 ENVIRONMENTAL SCIENCES↗

Synthesis of High Surface Area VS2 for Nitrogen Reduction

Ammonia synthesis from dinitrogen provides a critical chemical feedstock to agriculture worldwide. The dominant process for ammonia synthesis is the Haber-Bosch process, which is fossil-fuel dependent and energy intensive. The electrochemical nitrogen reduction reaction (NRR) could provide a more environmentally friendly route to industrial ammonia synthesis. We have worked to realize electrochemical NRR by developing transition metal dichalcogenide NRR catalysts. In the first part of this presentation, a VS2-based NRR electrocatalyst, which has shown promising activity and selectivity, will be presented. The synthesis of this VS2-based catalyst is straightforward and results in few-layer VS2 or VSx, (x < 2) nanoflakes. Additionally, the proposed mechanism of NRR on VS2 will be discussed, and we will discuss DFT simulation of NRR on VS2 and MoS2 as well as planned in-situ Raman experiments to probe this mechanism. In the second part of this presentation, we will share several lessons learned during our early NRR research including important points of electrochemical cell design and experimental controls to reduce environmental ammonia contamination of experiments. Finally, we will address areas of opportunity for electrochemical NRR.

dichalcogenide↗

Monticello Mill Tailings Site Operable Unit III Annual Groundwater Report May 2014 Through April 2015, October 2015

This report provides the annual analysis of water quality restoration progress, cumulative through April 2015, for Operable Unit (OU) III, surface water and groundwater, of the U.S. Department of Energy (DOE) Office of Legacy Management Monticello Mill Tailings Site (MMTS). The MMTS is a Comprehensive Environmental Response, Compensation, and Liability Act National Priorities List site located in and near the city of Monticello, San Juan County, Utah. MMTS comprises the 110-acre site of a former uranium- and vanadium-ore-processing mill (mill site) and 1,700 acres of surrounding private and municipal property. Milling operations generated 2.5 million cubic yards of waste (tailings) from 1942 to 1960. The tailings were impounded at four locations on the mill site. Inorganic constituents in the tailings drained from the impoundments to contaminate local surface water (Montezuma Creek) and groundwater in the underlying alluvial aquifer. Mill tailings dispersed by wind and water also contaminated properties surrounding and downstream of the mill site. Remedial actions to remove and isolate radiologically contaminated soil, sediment, and debris from the former mill site (OU I) and surrounding properties (OU II) were completed in 1999 with the encapsulation of the wastes in an engineered repository located on DOE property 1 mile south of the former mill site. Contamination of groundwater and surface water remains within OU III at levels that exceed water quality protection standards. Uranium is the primary contaminant of concern. LM implemented monitored natural attenuation with institutional controls as the OU III remedy in 2004. Because groundwater restoration proceeded more slowly than expected and did not meet performance criteria established in the OU III Record of Decision (June 2004), LM implemented a contingency action in 2009 by an Explanation of Significant Difference to include a pump-and-treat system using a single extraction well and treatment by zero-valent iron (ex-situ treatment system). The contingency action was optimized in 2015 with the installation of 8 extraction wells and 16 monitoring wells in a focused area of the aquifer (area of attainment). Contaminated water is treated by solar evaporation at an existing onsite LM facility. Environmental monitoring at OU III consists of twice-yearly (April and October) collection and analysis of hydrologic and water-quality data from an established network of observation wells, seeps, and surface water locations. The scope of monitoring was expanded in 2009 for the ex situ treatment system and in 2015 for the remedy optimization system. Operation and monitoring of the ex situ treatment system was discontinued in 2014 with the start-up of the remedy optimization system. No data anomalies for OU III water quality trending or restoration progress are identified for the May 2014 through April 2015 reporting period. Although some regions of the aquifer demonstrate decreasing concentration trends, such trending is not evident for the bulk of the aquifer and a prolonged restoration period is indicated. The groundwater contingency remedy optimization system captures significant contaminant mass (primarily uranium) from the area of attainment; however, because that system only became operational in 2015, a long-term forecast of restoration progress is premature.

54 ENVIRONMENTAL SCIENCES↗

Maintenance of Maywood Laboratory Operations Support During Contractor Transition and Replacement of the Project Databases - 16329

In December 2013, Cabrera Services (Cabrera) executed transition of the FUSRAP Maywood Superfund Site remediation project operations, including an on-site accredited environmental lab, from a large business that had established technology infrastructure in place for over a decade which required updating to support the expected remediation scope and client needs. As of November 2015, Cabrera has shipped over 116,000 yd{sup 3} of contaminated soil to disposal facilities. During the transition, the USACE FUSRAP Maywood Laboratory (UFML) continued to support project operations, providing the expected timely and reliable results and maintaining their New Jersey Department of Environmental Protection certification for all parameters of concern, while having to cope with new challenges and additional tasks having the potential to disrupt the laboratory's ability to support project operations. This case study examines the challenges with maintaining a certified radiochemistry laboratory and an aggressive remediation schedule during a period of prime contractor transition which included a complete IT infrastructure overhaul, and conversion of the existing Microsoft Access laboratory database and project Electronic Data Management System (EDMS) to a customized commercial solution. Challenges: I. Procurement of a new database subcontractor and working closely with them to achieve the following: a. Migration of all environmental (including radiological, chemical, and quality control), health and safety, and spatial data as well as reports, queries, and analytical instrument software processes from a MS Access data management system to a SQL server system; and b. Verification that the functionality and data integrity of the databases remained intact. II. The onsite laboratory was changed over to a new onsite network and the following tasks were completed with little or no interruption to site operations by January 10, 2014: i. Installation of new instrument personal computers (PCs) and making them fully operational; ii. Configuration of the lab domain and server to host the LIMS (replaced all servers/domain/workstations with Windows 7 and Server 2012 machines). iii. Networking of the laboratory building into the rest of the project site via fiber optic cabling across the site. iv. Upgrade of the wide area network (WAN) data connection to high-speed Fiber Optic service; v. Upgrade of the telephones into voice over internet protocol (VOIP) phones. vi. Splitting of the database into front ends and a centralized back-end hosted on the new server to allow simultaneous access for fixes and improvements. III. Phone service interruption; phone systems were operational by January 10, 2014. Additional Tasks: I. Revision of the USACE FUSRAP Maywood Laboratory (UFML) Quality Systems Manual Rev. 1 Submitted 01/16/14; II. Writing of the Uniform Federal Policy Quality Assurance Project Plan Rev. 1 (UFP-QAPP) submitted 1/21/14. This document replaced the prior project data quality plan, the Chemical Data Quality Management Plan. III. Support of USACE communications to the New Jersey Department of Environmental Protection (NJDEP) on lab management and personnel transition to Cabrera. This work was important since it ensured a smooth transition and shows how critical project records infrastructure such as databases, can be upgraded with minimal interruption of project support. Such work may provide benefit to other similar projects, especially long term projects where database infrastructure upgrades may be beneficial in terms of improved efficiencies in data recording and transfer, and improved security in data storage. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Bench-Scale Silicone Process for Low-Cost CO 2 Capture

GE Global Research is developing technology to remove carbon dioxide (CO 2 ) from the flue gas of coal-fired power plants. A mixture of 3-aminopropyl end-capped polydimethylsiloxane (GAP-1m) and triethylene glycol (TEG) is the preferred CO 2 capture solvent. GE Global Research was contracted by the Department of Energy to test a bench-scale continuous CO 2 absorption/desorption system using a GAP-1m/TEG mixture as the solvent. SiVance LLC was sub-contracted to provide the GAP-1m material and conduct an Environmental, Health, and Safety (EH&S) assessment for a 550 MW coal-fired power plant. 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 dodecylbenzenesulfonic acid (DDBSA) were also identified for analysis. All of the solvent components and DDBSA are listed on the EPA’s TSCA Inventory allowing companies to manufacture and use the chemicals commercially. The toxicological effects of each component were defined, and control mechanisms necessary to comply with U.S. EH&S regulations are summarized. An engineering and control system, including environmental abatement, was 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.

20 FOSSIL-FUELED POWER PLANTS↗

Impact of Standing Bleed Water on Saltstone Placement

The amount of water present during placement and subsequent curing of saltstone has the potential to impact several properties important for grout quality. An active drain water system can remove residual standing water and expose the surface of the placed saltstone to air. Oxidation of the saltstone may result in an increase in the leachability of redox sensitive elements. A dry surface can lead to cracking, causing an increase in hydraulic conductivity. An inactive drain water system can allow standing water that generates unnecessary hydrostatic head on the vault walls. Standing water that cannot be removed via the drain system will be available for potential incorporation into subsequent grout placements. The objective of this work is to study the impact of standing water on grout quality pertaining to disposal units. A series of saltstone mixes were prepared, and cured at ambient temperature to evaluate the impact of standing water on saltstone placement. The samples were managed to control drying effects on leachability by either exposing or capping the samples. The water to premix ratio was varied to represent a range of processing conditions. Samples were analyzed for density, leachability, and hydraulic conductivity. A monolith of each composition was cut into four sections to analyze the homogeneity of the sample with respect to vertical position within the sample. The density of each section was measured by two methods, helium pycnometry and by ASTM 642-06. The results show a trend of increasing density with increasing depth in the samples. This effect is more pronounced with the inclusion of excess bleed water and indicative of increased settling. The leachability of the eight different samples was analyzed by ANS/ANSI 16.1 method. These results indicate that drying of the saltstone during curing leads to decreased Leachability Indices (indicative of more release) for potassium, sodium, rhenium, nitrite, and nitrate. This may be caused by shrinkage cracking in the samples creating additional pathways for contaminant release. There was no noticeable effect on leachability by changing the water to premix ratio or by including excess bleed water. There was no detectable chromium release in any of the samples. Chromium and rhenium were added in equal amounts to determine whether rhenium might be an acceptable surrogate for chromium, a hazardous material. This testing shows no correlation between the behavior of the two elements, as chromium is not released at detectable levels and rhenium is released at a comparable rate to nitrate, the most prevalent and mobile species in saltstone.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Accounting for hydrological and microbial processes on greenhouse gas budgets from river systems (Final Report)

River systems have a disproportionately large impact on carbon and nitrogen cycling on this planet. For instance, despite their much smaller size in area, it is estimated that global carbon dioxide emission from river systems exceed the emission from lakes and reservoirs, and are on par with the estimated oceanic and land carbon sinks. Closing carbon and nitrogen budgets in river systems requires knowledge of end member greenhouse gas (GHG) products (e.g. carbon dioxide, nitrous oxide, methane), which typically have not been measured in river systems. Moreover, while the production of these gasses is thought to be microbially derived, little is known about microbial activities in sediments of large rivers, despite their potentially high influence on biogeochemical budgets. Typically, when we think of rivers we visualize the channels that carve through the earth, but this only represents a small part of the hydrologic exchange that a river participates in. Rivers are more than conduits; they are dynamically exchanging water and materials with surrounding terrestrial and subsurface environments. In fact, 96% of the carbon dioxide produced within river systems occurs in hyporheic zones, or sediment regions beneath and alongside a river where groundwater and river water mix. In fact, it is widely recognized that microbial processes in hyporheic zones, also known as the river’s liver, strongly influence the fate of carbon, nutrients, and contaminants transported through watersheds. Despite this general knowledge, observational studies linking nitrogen and carbon gas production to microbial activity, and studies of overall gas emissions, are limited across river systems, but especially absent from larger rivers. To identify microbial processes responsible for GHG emissions from large rivers, and to quantify their environmental drivers and dependencies, we selected the Columbia River as a representative field site. This is the largest river west of the North American Continental Divide, and produces a drainage and discharge roughly double of the Nile in Egypt. This river is also an important source for agricultural irrigation and generates more hydroelectric power than any other North American river. Dams manage the release of water in the river, with these changes in river discharge patterns strongly impacting microbial activities in hyporheic zones. Specifically, we target a region down-river from the Priest Rapids Dam (WA) associated with the PNNL SFA, where water discharge from the dam is highly controlled, resulting in 1.5 m fluctuations in river stage daily. This dynamic river stage creates an ideal research opportunity for investigating hydrological perturbations in GHG production, uptake, and emission from large river systems. In this exploratory 1-year project, we conducted data-driven field research to provide observations needed to support predictions about GHG flux from river ecosystems. Using porewater dialysis and surface flux measurements, we observed where and when GHGs were produced and is the emission impacted by river stage. Using meta-omics tools, we determined what microbial processes control production and consumption of GHG in these systems. Finally, we provided key observations to parameterize models that could predict the effect of environmental conditions on GHG emission in the Columbia River near shore environment, at the scale that the modeled processes operate. Closing knowledge gaps in the linkages between river stage, microbial processes, and GHG production and emission, as well as the spatial distribution and ecosystem dependencies of these processes, is necessary to better parameterize land surface models. We provide some of the first, detailed GHG measurements paired microbial activity from large river systems. Our findings have direct relevance to many other large rivers with flows altered by hydroelectric energy, reservoirs, snowmelt, tides, or agriculture.

54 ENVIRONMENTAL SCIENCES↗

Managing Low-Level Waste at Dounreay - 16269

Dounreay Site Restoration Limited (DSRL) is the site licence company responsible for the clean-up and demolition of Britain's former centre of fast reactor research and development. The Dounreay site requires facilities to dispose of up to 175,000 cubic metres of low level waste (LLW) that has been and will continue to be generated during the decommissioning and restoration of the site. In May 2014, construction of two new vaults for the disposal of LLW at Dounreay was completed, including the necessary roads, infrastructures and services, followed by an encapsulation plant in September 2014. The vaults are located immediately to the northeast of the Dounreay licensed site, on NDA-owned land. The facilities are for disposal of the solid LLW generated at Dounreay and the adjacent Vulcan site only. In 2004, following consultation with stakeholders and members of the public, Dounreay issued the 'Best Practicable Environmental Option (BPEO) Report' on the management of Dounreay LLW. This report assessed potential management options for LLW against a range of criteria, including technical, environmental, cost, health and safety issues. The study was conducted in line with best practice and involved consultation with a range of people, including the local community and organisations with an interest in radioactive waste management. The recommendations and conclusions from the study provided the basis for the 'Dounreay Solid LLW Overall Strategy', which was published in March 2005. A fundamental component of this strategy was the development of new below-ground disposal vaults for LLW at Dounreay. Siting the vaults on land at Dounreay avoids any need to transport the LLW away from Dounreay on public roads. Disposal at Dounreay therefore satisfies the proximity principle of managing the waste at source. Disposal at Dounreay is also consistent with UK Government Policy on LLW management, the Scottish Government's Radioactive Waste Management Policy and the Nuclear Decommissioning Authority's (NDA's) strategy on management of LLW from the UK nuclear industry. A planning application was initially lodged with the Highland Council in June 2006. The period for the determination of this application was extended to allow the Scottish Environment Protection Agency (SEPA) sufficient time to assess fully the supporting Environmental Safety Case (ESC). The planning application was re-activated in May 2008, and planning permission was granted by Highland Council in April 2009. The planning permission included 26 conditions on DSRL, covering a wide range of environmental issues such as construction noise/dust, traffic, visual impact and also a condition to develop a community fund aimed at socio-economic development of the area around the Dounreay site. After undertaking the necessary detailed design work, construction of the phase one vaults commenced in November 2011 by principal contractor, Graham Construction. Work was undertaken on both vaults simultaneously, excavating around 243,000 m{sup 3} of rock. When excavation was complete, steel reinforcement was placed and concrete poured to construct the floor slabs. This was followed by the construction of the reinforced walls and then the installation of the steel support structure and materials that form the roof. Mechanical and electrical installation then followed, in parallel with the construction of the vault apron, ramps and access roads. A pumping system and control building was also constructed to remove groundwater from around the vaults to allow the vaults to be kept dry while they are being filled with waste. A layer of excavated material, approximately 3 m thick, was placed across the existing ground surface between the vaults and the coast, to ensure the water table lies well below the new ground surface after closure of the vaults, and that any future trace contaminated groundwater flows out to the sea rather than to the soil zone. This layer is referred to in project documents as the 'enhanced geosphere'. After disposals are completed and the vaults are closed, this layer will be joined to the capping over the vaults so that the ensemble merges visually with the surrounding landscape. The original vegetation and soil mix will be returned as far as is practicable. An encapsulation plant has been constructed to fill the LLW containers with grout prior to disposal in the vault, similar to the process used at the national Low-Level Waste Repository facility (LLWR), near Drigg in Cumbria. The plant has the capacity to grout up to four containers per day. The grout fills voids in the container and helps provide chemical conditions in the vault that limit the release of radionuclides in the far future, after the vault has been penetrated by groundwater. On April 24 2015, active commissioning began at the Encapsulation Plant and LLW Vaults. Half-height ISO containers packed with low level waste are currently being filled with grout and disposed of in the LLW Vault. Also packaged Demolition Low Level Waste (DLLW) is being processed and disposed of in the Demolition Low Level Waste Vault. To date over 2500 packages of DLLW and 70 containers LLW have been disposed of. Completion of construction and the start of operating the Phase One vaults and encapsulation plant are fundamental to the successful and efficient decommissioning of the Dounreay site, upon which many millions of pounds of investment and hundreds of jobs rely.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Impact of Ti Incorporation on Hydroxylation and Wetting of Fe 3 O 4

Understanding the interaction of water with compositionally tuned metal oxides is central to exploiting their unique catalytic and magnetic properties. However, processes such as hydroxylation, wetting, and resulting changes in electronic structure at ambient conditions are challenging to probe in situ. Here, we examine the hydroxylation and wetting of Fe(3-x)TixO4 epitaxial films directly using ambient pressure X-ray photoelectron spectroscopy under controlled relative humidity. Fe2+ formation promoted by Ti4+ substitution for Fe3+ increases with hydroxylation, commensurate with a decrease in the surface work function or change in the surface dipole. The incorporation of small amounts of Ti (x=0.25) as a bulk dopant dramatically impacts hydroxylation, in part due to surface segregation, leading to coverages closer to that of TiO2 than Fe3O4. However, the Fe(3-x)TixO4 compositional series shows a similar affinity for water physisorption, which begins at notably lower relative humidity than on TiO2. The findings suggest that relative humidity rather than surface hydroxyl density controls wettability. Studies of this kind directly relate to rational design of doped magnetite into more active catalysts for UV/Fenton degradation, the adsorption of contaminants, and the development of spin filters.

Environmental Molecular Sciences Laboratory↗

Bioprocessing-Based Approach for Bitumen/Water/Fines Separation and Hydrocarbon Recovery from Oil Sands Tailings

Oil sands are a major source of oil, but their industrial processing generates tailings ponds that are an environmental hazard. The main concerns are mature fine tailings (MFT) composed of residual hydrocarbons, water, and fine clay. Tailings ponds include toxic contaminants such as heavy metals, and toxic organics including naphthenics. Naphthenic acids and polyaromatic hydrocarbons (PAHs) degrade very slowly and pose a long-term threat to surface and groundwater, as they can be transported in the MFT. Research into improved technologies that would enable densification and settling of the suspended particles is ongoing. In batch tests, BioTiger™, a microbial consortium that can metabolize PAHs, demonstrated improved oil sands tailings settling from a Canadian tailings pond. Results also showed, depending on the timing of the measurements, lower suspended solids and turbidity. Elevated total organic carbon was observed in the first 48 hours in the BioTiger™-treated columns and then decreased in overlying water. Oil sands tailings mixed with BioTiger™ showed a two-fold reduction in suspended solids within 24 hours as compared to abiotic controls. The tailings treated with BioTiger™ increased in microbial densities three orders of magnitude from 8.5 × 105 CFU/mL to 1.2 × 108 CFU/mL without any other carbon or energy source added, indicating metabolism of hydrocarbons and other available nutrients. Results demonstrated that bioaugmentation of BioTiger™ increased separation of organic carbon from particles in oil sands and enhanced settling with tailings with improved water quality.

04 OIL SHALES AND TAR SANDS↗

Vanadate Retention by Iron and Manganese Oxides

Anthropogenic emissions of vanadium (V) into terrestrial and aquatic surface systems now match those of geogenic processes, and yet, the geochemistry of vanadium is poorly described in comparison to other comparable contaminants like arsenic. In oxic systems, V is present as an oxyanion with a +5 formal charge on the V center, typically described as H x VO 4 (3–x)– , but also here as V(V). Iron (Fe) and manganese (Mn) (oxy)hydroxides represent key mineral phases in the cycling of V(V) at the solid–solution interface, and yet, fundamental descriptions of these surface-processes are not available. Here, we utilize extended X-ray absorption fine structure (EXAFS) and thermodynamic calculations to compare the surface complexation of V(V) by the common Fe and Mn mineral phases ferrihydrite, hematite, goethite, birnessite, and pyrolusite at pH 7. Inner-sphere V(V) complexes were detected on all phases, with mononuclear V(V) species dominating the adsorbed species distribution. Our results demonstrate that V(V) adsorption is exergonic for a variety of surfaces with differing amounts of terminal –OH groups and metal–O bond saturations, implicating the conjunctive role of varied mineral surfaces in controlling the mobility and fate of V(V) in terrestrial and aquatic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Irreversible Trace Metal Binding to Goethite Controlled by the Ion Size

The dynamics of trace metals at mineral surfaces influence their fate and bioaccessibility in the environment. Trace metals on iron (oxyhydr)oxide surfaces display adsorption–desorption hysteresis, suggesting entrapment after aging. However, desorption experiments may perturb the coordination environment of adsorbed metals, the distribution of labile Fe(III), and mineral aggregation properties, influencing the interpretation of labile metal fractions. In this study, we investigated irreversible binding of nickel, zinc, and cadmium to goethite after aging times of 2–120 days using isotope exchange. Dissolved and adsorbed metal pools exchange rapidly, with half times <90 min, but all metals display a solid-associated fraction inaccessible to isotope exchange. The size of this nonlabile pool is the largest for nickel, with the smallest ionic radius, and the smallest for cadmium, with the largest ionic radius. Spectroscopy and extractions suggest that the irreversibly bound metals are incorporated in the goethite structure. Rapid exchange of labile solid-associated metals with solution demonstrates that adsorbed metals can sustain the dissolved pool in response to biological uptake or fluid flow. Trace metal fractions that irreversibly bind following adsorption provide a contaminant sequestration pathway, limit the availability of micronutrients, and record metal isotope signatures of environmental processes.

58 GEOSCIENCES↗

Selenite and Selenate Sequestration during Coprecipitation with Barite: Insights from Mineralization Processes of Adsorption, Nucleation, and Growth

Coprecipitation of selenium oxyanions with barite is a facile way to sequester Se in the environments. However, the chemical composition of Se-barite coprecipitates usually deviates from that predicted from thermodynamic calculations. This discrepancy was resolved by considering variations in nucleation and growth rates controlled by ion–mineral interactions, solubility, and interfacial energy. For homogeneous precipitation, ~10% of sulfate, higher than thermodynamic predictions (<0.3%), was substituted by Se(IV) or Se(VI) oxyanion, which was attributed to adsorption-induced entrapment during crystal growth. For heterogeneous precipitation, thiol- and carboxylic-based organic films, utilized as model interfaces to mimic the natural organic-abundant environments, further enhanced the sequestration of Se(VI) oxyanions (up to 41–92%) with barite. Such enhancement was kinetically driven by increased nucleation rates of selenate-rich barite having a lower interfacial energy than pure barite. In contrast, only small amounts of Se(IV) oxyanions (~1%) were detected in heterogeneous coprecipitates mainly due to a lower saturation index of BaSeO 3 and deprotonation degree of Se(IV) oxyanion at pH 5.6. Finally, these roles of nanoscale mineralization mechanisms observed during composition selection of Se-barite could mark important steps toward the remediation of contaminants through coprecipitation.

54 ENVIRONMENTAL SCIENCES↗

Irreversible Trace Metal Binding to Goethite Controlled by the Ion Size

The dynamics of trace metals at mineral surfaces influence their fate and bioaccessibility in the environment. Trace metals on iron (oxyhydr)oxide surfaces display adsorption–desorption hysteresis, suggesting entrapment after aging. However, desorption experiments may perturb the coordination environment of adsorbed metals, the distribution of labile Fe(III), and mineral aggregation properties, influencing the interpretation of labile metal fractions. Here, in this study, we investigated irreversible binding of nickel, zinc, and cadmium to goethite after aging times of 2–120 days using isotope exchange. Dissolved and adsorbed metal pools exchange rapidly, with half times <90 min, but all metals display a solid-associated fraction inaccessible to isotope exchange. The size of this nonlabile pool is the largest for nickel, with the smallest ionic radius, and the smallest for cadmium, with the largest ionic radius. Spectroscopy and extractions suggest that the irreversibly bound metals are incorporated in the goethite structure. Rapid exchange of labile solid-associated metals with solution demonstrates that adsorbed metals can sustain the dissolved pool in response to biological uptake or fluid flow. Trace metal fractions that irreversibly bind following adsorption provide a contaminant sequestration pathway, limit the availability of micronutrients, and record metal isotope signatures of environmental processes.

58 GEOSCIENCES↗

The Role of Technical Guidance and Analysis Tools in Remedy Decisions, Implementation, and Closure - 18307

Selection, design, and implementation of environmental remedies are conducted under regulatory frameworks that define the activities, communication, and documentation requirements for the remediation process. However, there are site situations that are not well described in the basic regulatory frameworks, and technical guidance and analysis tools can help facilitate remedy decisions and actions. An example where technical guidance and analysis tools are helpful is in the transition from pump-and-treat (P and T) remediation to monitored natural attenuation (MNA). Standard MNA regulatory guidance does not account for a plume initially controlled by P and T hydraulic conditions rather than natural-gradient conditions. For instance, MNA guidance discusses demonstrating plume stability as a means to evaluate the suitability of MNA. However, plume stability under long-term natural gradient conditions cannot be directly demonstrated while the plume is being contained by a P and T system. Thus, additional guidance is needed to describe other measures that can be used to support transition from P and T to MNA. As an additional example, standard MNA regulatory guidance is not written to provide suitable information for application to vadose-zone contamination; discussion and examples in the regulatory guidance are predominantly for groundwater. Use of contaminant transport assessments is an important component of vadose-zone remedy decisions where technical guidance and analysis tools can facilitate these decisions. For volatile compounds, the assessment may need to also consider flux to the surface and constraints associated with vapor intrusion. Recent technical guidance and associated analysis tools provide sites with approaches to support remedy decisions for the above conditions. In particular, these recent approaches target developing and implementing P and T and soil vapor extraction remediation exit strategies and facilitating assessment and implementation of remedies for coupled vadose-zone/groundwater contamination. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Coupling-Assisted Renormalization of Excitons and Vibrations in Compressed MoSe 2 –WSe 2 Heterostructure

Vertical heterostructures (HSs) constructed with two-dimensional (2D) materials is expected to generate fascinating properties due to interlayer coupling between neighboring layers. However, interlayer coupling can be easily obscured by cross-contamination during transfer processes, rendering their experimental demonstration challenging. Here, we explore the coupling-assisted renormalization of excitons and vibrations in a mechanically fabricated MoSe 2 –WSe 2 HS through high-pressure photoluminescence, Raman spectra, and density functional theory calculations. Accompanied by the interlayer coupling enhancement, the excitonic and vibrational renormalizations involving dimensionality and composition variations were achieved. A cycle of 2D–3D–2D excitonic evolution was disclosed and pressure-induced emergence of X – exciton of MoSe 2 in HS was found reflecting the band structure transition in the MoSe 2 –WSe 2 HS. The Raman spectra reveals that the coupled A 2 " vibrations of WSe 2 and MoSe 2 in HS was stiffened and out-of-plane A 1 ' vibrations of WSe 2 and MoSe 2 in HS got coherent upon pressure modulation. Here, this coupling-assisted renormalization in MoSe 2 –WSe 2 HS can be extended to other 2D layered HSs, which indicates the possibility to design a flexible HS with controlled excitonic and vibrational system for light-emitting diodes, excitonic, and photovoltaic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparison of sugar content for ionic liquid pretreated Douglas-fir woodchips and forestry residues

The development of affordable woody biomass feedstocks represents a significant opportunity in the development of cellulosic biofuels. Primary woodchips produced by forest mills are considered an ideal feedstock, but the prices they command on the market are currently too expensive for biorefineries. In comparison, forestry residues represent a potential low-cost input but are considered a more challenging feedstock for sugar production due to complexities in composition and potential contamination arising from soil that may be present. We compare the sugar yields, changes in composition in Douglas-fir woodchips and forestry residues after pretreatment using ionic liquids and enzymatic saccharification in order to determine if this approach can efficiently liberate fermentable sugars. : These samples were either mechanically milled through a 2 mm mesh or pretreated as received with the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate [C 2 mim][OAc] at 120°C and 160°C. IL pretreatment of Douglas-fir woodchips and forestry residues resulted in approximately 71-92% glucose yields after enzymatic saccharification. X-ray diffraction (XRD) showed that the pretreated cellulose was less crystalline after IL pretreatment as compared to untreated control samples. Two-dimensional nuclear magnetic resonance spectroscopy (2D-NMR) revealed changes in lignin and hemicellulose structure and composition as a function of pretreatment. Mass balances of sugar and lignin streams for both the Douglas-fir woodchips and forestry residues throughout the pretreatment and enzymatic saccharification processes are presented. While the highest sugar yields were observed with the Douglas-fir woodchips, reasonably high sugar yields were obtained from forestry residues after ionic liquid pretreatment. Structural changes to lignin, cellulose and hemicellulose in the woodchips and forestry residues of Douglas-fir after [C 2 mim][OAc] pretreatment are analyzed by XRD and 2D-NMR, and indicate that significant changes occurred. Irrespective of the particle sizes used in this study, ionic liquid pretreatment successfully allowed high glucose yields after enzymatic saccharification. These results indicate that forestry residues may be a more viable feedstock than previously thought for the production of biofuels.

59 BASIC BIOLOGICAL SCIENCES↗

Monticello Mill Tailings Site, Operable Unit lll, Annual Groundwater Report, May 2015 Through April 2016

This report provides the annual analysis of water quality restoration progress, cumulative through April 2016, for Operable Unit (OU) III, surface water and groundwater, of the U.S. Department of Energy (DOE) Office of Legacy Management (LM) Monticello Mill Tailings Site (MMTS). The MMTS is a Comprehensive Environmental Response, Compensation, and Liability Act National Priorities List site located in and near the city of Monticello, San Juan County, Utah. MMTS comprises the 110-acre site of a former uranium- and vanadium-ore-processing mill (mill site) and 1700 acres of surrounding private and municipal property. Milling operations generated 2.5 million cubic yards of waste (tailings) from 1942 to 1960. The tailings were impounded at four locations on the mill site. Inorganic constituents in the tailings drained from the impoundments to contaminate local surface water (Montezuma Creek) and groundwater in the underlying alluvial aquifer. Mill tailings dispersed by wind and water also contaminated properties surrounding and downstream of the mill site. Remedial actions to remove and isolate radiologically contaminated soil, sediment, and debris from the former mill site, Operable Unit I (OU I), and surrounding properties (OU II) were completed in 1999 with the encapsulation of the wastes in an engineered repository located on DOE property 1 mile south of the former mill site. This effectively removed the primary source of groundwater contamination; however, contamination of groundwater and surface water remains within OU III at levels that exceed water quality protection standards. Uranium is the primary contaminant of concern (COC). LM implemented monitored natural attenuation with institutional controls as the OU III remedy in 2004. Because groundwater restoration proceeded more slowly than expected and did not meet performance criteria established in the OU III Record of Decision (June 2004), LM implemented a contingency action in 2009 by an Explanation of Significant Difference to include a pump-and­ treat system using a single extraction well and treatment by zero-valent iron (ex situ treatment system). The contingency action was optimized in 2015 with the installation of8 extraction wells and 16 monitoring wells in a focused area of the aquifer, the area of attainment (AOA). Contaminated water is treated by solar evaporation at an existing facility at the LM repository.

54 ENVIRONMENTAL SCIENCES↗