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At least 361 records · Page 20

Legacy mercury: A watershed scale cleanup challenge - 15559

Over the next three decades, the US Department of Energy (DOE) Oak Ridge Office of Environmental Management (OREM) will focus on reducing the flux of mercury contamination that exits at the Y-12 National Security Complex (Y-12 NSC) [1, 2]. OREM, Tennessee Department of Environment and Conservation (TDEC), and US Environmental Protection Agency (EPA) have identified mercury contamination within and released from the Y-12 NSC as the highest priority cleanup risk on the Oak Ridge Reservation (ORR). Furthermore, mercury contamination is a worldwide issue with more than 3,000 mercury-contaminated sites currently identified [3], and the United Nations Environment Programme has recently highlighted the risk of this contamination to human health [4]. Unlike other contaminants-metals, radionuclides, and organic solvents-that impact the DOE Environmental Management (DOE-EM) cleanup program at the ORR and other DOE sites, mercury has several unique characteristics that make environmental remediation of the Y-12 NSC one of the most complex efforts ever encountered. These distinctive physicochemical properties for mercury include the following: it is a dense non-aqueous liquid at ambient-temperature-pressure; it is the only metal that bio-magnifies; and it is the only contaminant transported as both a cation and/or a dissolved or gaseous elemental metal (similar to an organic solvent) under environmental conditions. Most importantly, mercury also undergoes biogeochemical transformation processes, which include aqueous and surface complexation, redox reactions, and atypical methylation reactions, producing the potent neurotoxin methylmercury [5, 6]. Each of the aforementioned distinctive characteristics for mercury is observed within this heterogeneous and dynamic watershed-scale system-which includes the Y-12 NSC boundary and 23 km of contaminated creek and flood plain downstream. Because of these complexities, implementing cost effective and sustainable solutions that reduce mercury flux from various primary and secondary contamination sources will require the linking of basic science understanding and applied research advancements into OREM's cleanup process. In 2009, the DOE-EM Office of Site Restoration's Soil and Groundwater Remediation Program and Oak Ridge National Laboratory (ORNL) initiated an applied field research initiative with the goal of developing a systems-based approach to control mercury flux in soil and water to protect surface water, groundwater, and ecological receptors. The Remediation of Mercury and Industrial Contaminants Applied Field Research Initiative (ROMIC-AFRI) represents the vehicle that enables the linking of science to remedial applications. Here we discuss the progress made to date in addressing key applied research and technology development needs to address this watershed scale conundrum. (authors)

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Green hydrogen from microalgal liquefaction byproducts with ammonia recovery and effluent recycle for developing circular processes

Hydrothermal liquefaction is a promising technology for microalgae-based biofuel production. However, hydrothermal liquefaction’s aqueous wastes have little established reuse, and contain significant fractions of toxic ammoniacal nitrogen. Careful reuse of this waste can assure microalgae-based biofuels are produced with less environmental impact and larger energy efficiency. Microbial electrolysis cells were investigated to valorize this waste product by converting the leftover organics into hydrogen and remove ammonia. Waste hydrothermal liquefaction aqueous phase from two microalgal strains, Tetraselmis sp. and Chlorella sp. were used as feedstocks for hydrogen production in microbial electrolysis cells. Chlorella and Tetraselmis aqueous phase-fed microbial electrolysis cells reach an average current density of 5.1 ± 0.19 A/m 2 and 3.8 ± 0.08 A/m 2 . Compound removal rates and mass removal percentages were also investigated for each feedstock. Additionally, acetic acid, propionic acid, ethanol, and glycerol were effectively removed from the aqueous byproduct. Further, microbial electrolysis cells separated up to 34.3% of ammoniacal nitrogen present in the aqueous phase. Charge transfer analysis indicated that proton transfer, not ammonium transfer, contributed to the majority of the hydrogen production in the cathode. Finally, the microbial electrolysis cell effluent was reused to grow the same microalgal strains, leading to the development of a circular biofuel production system. Microalgae regrowth studies using microbial electrolysis cell effluent showed nearly complete removal of total organic carbon, but significantly less removal of total nitrogen. Tetraselmis sp. growth occurred with the Tetraselmis-derived MEC effluent, however, the control medium without effluent produced the most growth. These findings support the possibility of a circular biofuel framework using MECs, but additional constraints, including the removal of inorganic contaminants, are necessary to realize the circular processes.

09 BIOMASS FUELS↗

Integrated Systems-Based Approach to Monitoring Environmental Remediation - 13211

The US Department of Energy (DOE) is responsible for risk reduction and cleanup of its nuclear weapons complex. Remediation strategies for some of the existing contamination use techniques that mitigate risk, but leave contaminants in place. Monitoring to verify remedy performance and long-term mitigation of risk is a key element for implementing these strategies and can be a large portion of the total cost of remedy implementation. Especially in these situations, there is a need for innovative monitoring approaches that move away from the cost and labor intensive point-source monitoring. A systems-based approach to monitoring design focuses monitoring on controlling features and processes to enable effective interpretation of remedy performance. (authors)

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Simulation of In Situ Bioremediation of Chromium (VI) Using Consortium Cultures and Column Studies - 19357

Chromium contaminated soil and ground water has become a serious problem caused by the rapid expansion of industries, leading to direct or indirect discharge of Cr(VI). The conventional methods that include pump and treat result into toxic byproducts and residual. Cr(VI) reducing bacteria in the contrary have been envisioned as an economically and ecologically friendly method to treat contaminated sites. Biological Cr(VI) reduction processes include biotransformation, biosorption which involve detoxification/ removal of hazardous substances and bioaccumulation. A continuous flow column system for Cr(VI) reduction was investigated in three different treatments and the control, using dried sludge and soil from target site. Cultures identified using effluent samples in the 16S rRNA sequencing showed a prominent of Exiguobacterium aestuarii species as it was identified from all column systems. Other cultures that showed 100% query cover included; Enterobacter aerogenes, Enterobacter kobei and Pseudomonas aeruginosa. More than 90% of Cr(VI) reduction was observed in all columns over a 60 day period at 40 mgL{sup -1}. Cr(VI) was reduced from 38.12 mgL{sup -1} to 0.39 mgL{sup -1}. A more unstable profile was observed at 60 mgL{sup -1} over 60 days. Subsequently, there was near complete reduction from System 1 and 3 of 1.152 mgL{sup -1} and 1.215 mgL{sup -1} Cr(VI) concentration, respectively. A Cr(VI) reduction profile along the column proved to be uniform at assumed quasi-steady state from the influent to the effluent for both 40 and 60 mgL{sup -1} Cr(VI) concentration. Biological remediation strategies for Cr(VI) contaminated soil and groundwater is an emerging field that has been proposed to successfully treat Cr(VI) contaminated sites using Cr(VI) reduction species of bacteria. (authors)

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Mercury in Water

Mercury (Hg) is a global pollutant threatening our water resources and human health. Every one of us contains some levels of Hg or methylmercury (MeHg) in our body due to consumption of contaminated food such as fish and rice. Our understanding of the behavior of Hg in natural aquatic environments is limited as the major factors controlling microbial uptake and conversion of inorganic Hg to neurotoxic MeHg remain obscure. MeHg concentrations in water can bioaccumulate up to eight orders of magnitude in the food chain. Metallic or elemental Hg can evaporate and transport around the globe, and also readily undergoes chemical, photochemical and biological transformations (i.e., oxidation, reduction, methylation and demethylation) in water and sediments. Natural dissolved organic matter (DOM) plays a critical role in mediating these transformations because of its exceptionally strong binding affinity for Hg and its dual functional roles in reducing and oxidizing Hg. While the discovery of Hg-methylation genes significantly advanced our understanding of MeHg biosynthesis, the simultaneous degradation of MeHg at low concentrations (i.e., picomolar to nanomolar) by a range of methanotrophic and anaerobic bacteria has recently been recognized possibly as an important process for controlling net MeHg production, a key factor that determines Hg concentrations and bioaccumulation in biota. Although treatment technologies for Hg removal from water are available, they are mostly applicable to industrial waste streams and at localized contamination sites with high Hg concentrations (i.e., micromolar to millimolar). Reductions in Hg human exposure may be achievable by decreasing anthropogenic releases, such as coal combustion, over the long-term since Hg methylation responds to Hg inputs, particularly freshly deposited Hg in natural aquatic systems.

Gu, Baohua↗

Lawrence Livermore National Laboratory Experimental Test Site 300 (S300): S300 Roadway Improvements - 817 Complex Soil Sampling and Analysis Plan, Addendum 1 (June 2023)

The purpose of this addendum is to amend and update the S300 Roadway Improvements – 817 Complex [project] Soil Sampling and Analysis Plan (SAP) dated May 2023. Field activities to implement the SAP were completed in May 2023 except for SB-17. SB-17 is therefore included in this addendum. In addition, this addendum amends the SAP by covering an expanded scope of work and project limits. The project limits have been expanded to include areas around Building 818. Sampling at the expanded project area is addressed in this addendum by two additional borings for geotechnical and environmental analyses. The project area consists of the access gate and existing access roads for the Process Area complex. Excavation depths are anticipated to be no deeper than 5 feet from current grade. None of the proposed disturbance areas are within known areas of contamination or mapped controlled excavation area (LLNL 2008). Therefore, this addendum proposes a sampling spacing in the vicinity of Building 818 of about 172 feet (Tier 2) in accordance with the Soil Screening and Management Plan (LLNL 2022). The information contained in this addendum supersedes the May 2023 SAP. However, this addendum only addresses elements of the May 2023 SAP that were modified. Elements of the May 2023 SAP that have not been modified are relevant and will remain in effect.

54 ENVIRONMENTAL SCIENCES↗

Catalytic methods using molecular oxygen for treatment of PMMS and ECLSS waste streams, volume 2

Catalytic oxidation has proven to be an effective addition to the baseline sorption, ion exchange water reclamation technology which will be used on Space Station Freedom (SSF). Low molecular weight, polar organics such as alcohols, aldehydes, ketones, amides, and thiocarbamides which are poorly removed by the baseline multifiltration (MF) technology can be oxidized to carbon dioxide at low temperature (121 C). The catalytic oxidation process by itself can reduce the Total Organic Carbon (TOC) to below 500 ppb for solutions designed to model these waste waters. Individual challenges by selected contaminants have shown only moderate selectivity towards particular organic species. The combined technology is applicable to the more complex waste water generated in the Process Materials Management System (PMMS) and Environmental Control and Life Support System (ECLSS) aboard SSF. During the phase 3 Core Module Integrated Facility (CMIF) water recovery tests at NASA MSFC, real hygiene waste water and humidity condensate were processed to meet potable specifications by the combined technology. A kinetic study of catalytic oxidation demonstrates that the Langmuir-Hinshelwood rate equation for heterogeneous catalysts accurately represent the kinetic behavior. From this relationship, activation energy and rate constants for acetone were determined.

Akse, James R.↗

Red Plague Control Plan (RPCP)

SCOPE: Prescribes the minimum requirements for the control of cuprous / cupric oxide corrosion (a.k.a. Red Plague) of silver-coated copper wire, cable, and harness assemblies. PURPOSE: Targeted for applications where exposure to assembly processes, environmental conditions, and contamination may promote the development of cuprous / cupric oxide corrosion (a.k.a. Red Plague) in silver-coated copper wire, cable, and harness assemblies. Does not exclude any alternate or contractor-proprietary documents or processes that meet or exceed the baseline of requirements established by this document. Use of alternate or contractor-proprietary documents or processes shall require review and prior approval of the procuring NASA activity.

Cooke, Robert W.↗

CHAP Enhances Versatility in Colloidal Probe Fabrication

A colloidal probe, comprising a colloidal particle attached to an atomic force microscope cantilever, is employed to measure directly interaction forces between the particle and a surface. It is possible to change or even destroy a particle while attaching it to a cantilever, thus limiting the types of systems to which the colloidal probe technique may be applied. Here we present the Controlled Heating and Alignment Platform (CHAP) for fabricating colloidal probes without altering the original characteristics of the attached particle. The CHAP applies heat directly to the atomic force microscope chip to rapidly and precisely control cantilever temperature. This minimizes particle heating and enables control over the viscosity of thermoplastic adhesive, to prevent it from contaminating the particle surface. 3D-printed components made the CHAP compatible with standard optical microscopes and streamlined the fabrication process while increasing the platform’s versatility. Using the CHAP with a thermoplastic wax adhesive, colloidal probes were fabricated using polystyrene and silica particles between 0.7 and 40 μm in diameter. We characterized the properties and interactions of the adhesive and particles, as well as the properties of the completed probes, to demonstrate the retention of particle features throughout fabrication. Pull-off tests with CHAP’s probes measured adhesive force values in the expected ranges and demonstrated that particles were firmly attached to the cantilevers.

Schmitz, Russell C.↗

Genesis Solar Wind Sample Curation Documentation

Introduction: A scientist with experience as a sample science analyst, provider of flight hardware for multiple missions, and senior engineer in an ISO 2000-rated manufacturing plant has described the timeline of key participants in any PI-led sample return mission, the breadth of the organizations involved [1,2], and, of interest to this meeting, choosing the types of data to preserve and issues of future data accessibility. This work broadens that perspective by giving similar lessons from Genesis sample curation point-of-view. Curation participation regarding data gathering was part of the mission review process from the beginning. Genesis’ story illustrates outcome of several choices about types of data to record and preserve. Precision analysis of solar wind atoms captured in pure, ultraclean substrates is the driving science goal; therefore, detailed documentation was captured from all mission and curation phases and from investigator laboratories because these processes affect the final analytical results [3]. Pre-flight: Design and fabrication of the spacecraft. Like many modern small sample return missions, Genesis was a tightly managed team integrated across science, engineering and curation. Communication across the team was excellent, and, for the most part, the hands-on engineering technicians understood the impacts of “small choices” they routinely make, and the eyes-on oversight of manufacturing processes by scientists was mindful of details. The payload was designed by the Jet Propulsion Laboratory and the spacecraft by Lockheed Martin. Solar wind collectors and instruments were fabricated by multiple vendors and laboratories. The main portion of the payload was assembled at JSC. Fabrication procedures and contamination-control data (with witness coupons) were stored primarily at JSC. The original composition, dimensions and configuration of components, results of thermal testing, etc. are still needed for interpretation of analytical data. At times, these must be estimated from secondary information acquired pre-flight. Moreover, some files (e.g., original 3-D models and early Powerpoint) cannot be opened using software. Archived curation data includes 2-D drawings, material usage lists, QA documentation and analyses of consumables used during fabrication. Important chemical information still resides in archived hardware, paints and lubricants, material coupons, cleaning coupons, environmental witness plates and reference materials from manufacturing facilities. Purity and cleanliness of collector substrates. Semi-conductor vendors provided surface cleanliness data and some purity data. Purity for specific elements of interest was verified by science team members in their laboratories [4]. Curation archived procurement and shipping records, analysis reports, and non-proprietary fabrication data. A physical archive of flight collector reference materials is maintained for future use so additional data can be collected as analytical techniques improve. These are of increased value due to the hard landing upon re-entry. Cleaning and cleanliness assessments of flight hardware. Cleaning of the science canister payload was performed at JSC in a dedicated ISO 4 cleanroom using ultrapure water (UPW). The cleanliness of this UPW was monitored throughout processing. The archive for the clean lab also includes airborne particle counts, airborne molecular and inorganic contamination measurements as well as cleanroom construction material coupons and witness coupons. Hardware cleanliness was assessed by particle counts in rinse water batches. This information is recorded in batch cleaning forms and logbooks, and are, perhaps, of decreased value due to the hard landing. Post-flight: Curation-generated data. The curation handling history of each Genesis sample is documented in a typical astromaterials sample database which captures sample location, physical description and characterization data. Samples have a “shelf life”. Crucial to the preservation of samples is ongoing documentation of the sample environment, initially under curatorial control but is now a separate facility function with requires coordination. PI-generated data. Data on sample characterization and cleaning techniques continues to be generated by sample users [5]. These are often captured in LPSC abstracts, but these “engineering” results often are not publishable as stand-alone papers. We are actively looking for ways to make this information more accessible to users. Ion implants into samples have aided science return and can be shared among investigators. These (and similar) materials should be added to the curatorial collection with appropriate process and characterization data generated externally. Summary: Complete data archives for returned astromaterial samples must be broad in types and formats, and inclusive of environmental monitoring.

Genesis↗

Adaptive Site Management Strategies for the Hanford Central Plateau Groundwater

Adaptive site management (ASM) is a systematic and iterative management approach that can be used to expedite the remediation of large and/or complex sites. ASM is defined as a formal and systematic project or site management approach centered on rigorous site planning and a firm understanding of site conditions and uncertainties, using science and technology to routinely re-evaluate and prioritize site remedial actions and characterization activities. The goal of the approach is to create a framework of structured and continuous planning, implementation, and assessment processes that accommodates new information and changing site conditions to develop effective and efficient cleanup approaches that achieves the required outcome(s) while optimizing costs, cleanup timeframe, and performance. Central to ASM is an evolving conceptual site model (CSM). Over time, incremental reductions in uncertainty associated with the CSM will occur, while supporting continued progress toward site cleanup and closure through remedy optimization and evaluation. ASM has the potential to expedite cleanup for the Central Plateau area at Hanford through a planned and systematic approach for reducing uncertainty with targeted characterization activities, while continuing remediation activities that advance cleanup for key risk-driving contaminants. A core component of cleanup within the Central Plateau is the 200 West Pump-and-Treat (P&T) system. Even with an active P&T remedy, uncertainty exists with respect to plume distributions, total mass in the aquifer, and currently known continuing sources. Additional uncertainty is associated with multiple contaminant source locations in the vadose zone, which have the potential to create new groundwater plumes in the absence of any source control measures, although not all contaminant fluxes to groundwater will result in contaminant concentrations above cleanup levels. Collectively, these uncertainties need to be addressed in the CSM to support effective and efficient site progress toward cleanup goal(s). Other nontechnical factors that may warrant an ASM approach at the Hanford Central Plateau are associated with the formation of operable units (OUs) used to manage cleanup. With the exception of the 200-ZP-1 OU, the three remaining groundwater OUs only have interim action records of decision. Nine vadose zone source area OUs are also in the early stages of the remedial investigation and feasibility study process, with pending characterization and technology identification activities. A set of proposed site objectives for the Central Plateau are provided in this document as an initial consideration/example and basis for discussion for ASM implementation. These example site objectives were selected with the goal of maintaining protectiveness at the Columbia River through confinement of contaminant plumes within an administratively controlled area below existing surface waste sites and waste disposal facilities. Although site decision makers and regulators need to provide concurrence, these site objectives are used in this document to describe the elements of an ASM approach, including selection of interim objectives and a long-term adaptive management plan. Interim objectives are also defined to yield measurable incremental progress toward the overall site goals. This document identifies initial technical considerations for developing an ASM framework for the Central Plateau cleanup decisions. These considerations are intended to facilitate more specific decisions, such as objectives, near- and long-term actions, and performance metrics, to develop an overall approach that maintains protectiveness but recognizes the uncertainty, long timeframe, and technical challenges that need to be considered in selecting, implementing, and managing remediation at the Hanford Central Plateau.

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Spacecraft Cabin Air Quality Control and Its Application to Tight Buildings

Air quality is an important consideration not only for the external environment, but also for the indoor environment. Most people spend a majority of their lives indoors and the air that they breathe is important to their physical and emotional well being. Since most modern building designs have focused on energy efficiency, less fresh air is brought from the outside. As a result, pollutants from building materials, furniture, cleaning, and cooking have no place to go. To make matters worse, most ventilation systems do not include any means for removing pollutants from the recycled air. Unfortunately, pollution at even a small level can result in eye, throat, and lung irritation in addition to chronic headaches, nausea, and fatigue. A spacecraft cabin, which represents the worst case in tight building design, requires special consideration of air quality since any effects pollutants may have on a crewmember can potentially place a mission or other crewmembers at risk. A detailed approach has been developed by the National Aeronautics and Space Administration (NASA) to minimize cabin atmosphere pollution and provide the crew with an environment which is as free of pollutants as possible. This approach is a combination of passive and active contamination control concepts involving the evaluation and selection of materials to be used onboard the spacecraft, the establishment of air quality standards to ensure crew health, and the use of active control means onboard the spacecraft to further ensure an acceptable atmosphere. This approach has allowed NASA to prevent illness by providing crewmembers with a cabin atmosphere which contains pollutant concentrations up to 100 times lower than those specified for terrestrial indoor environments. Standard building construction, however, does not take into account the potentially harmful effects of materials used in the construction process on the health of future occupants and relies primarily on remedial rather than preventive techniques when addressing contamination. This approach results in a building that theoretically has low operating costs, but may actually have high costs associated with lost work days, increased medical claims, decreased productivity, and problem remediation. A similar approach to NASA's may be adopted by the building construction community which can tap the extensive database of material offgassing properties that has been collected to support the space program. Many materials used by NASA are commercially available and are frequently used in building construction. In addition, computer models which have been developed for assessing various methods of active contamination control can be applied to building ventilation system design and the analysis of their economics. Through using NASA' s experience, the expense associated with the current remedial approach can be avoided.

Perry, J. L.↗

Techno Economic Analysis for Production of Renewable Natural Gas and Value-Added Chemicals from Forest Biomass Residues (CRADA Final Report)

West Biofuels - in collaboration with the University of California San Diego, the University of California Davis, the National Laboratory of the Rockies (NLR), the Colorado School of Mines’ Center for Hydrate Research, Placer County Air Pollution Control District, the Sierra Business Council, and the Southern California Gas Company (SoCalGas)-will demonstrate an innovative pathway to convert forest biomass to renewable gas (RG). The project, Production of Pipeline Grade Renewable Natural Gas and Value-Added Chemicals from Forest Biomass Residues, will utilize an existing pilot-scale gasification system and data and lessons learned from a lab-scale catalytic reactor design, develop, and demonstrate an integrated pilot-scale RG process with a scaled-up catalytic reactor and hydrate-based gas separation process. This robust and simple process uses a commercial proven gasifier, a commercially available catalyst that can tolerate gas contaminants, and a gas separation process that simplifies the downstream processing. Current testing has shown that the process can yield a large amount of methane rich renewable gas in addition to a mixture of propanol, ethanol and other higher alcohols and the relative amounts can be controlled by shifting the process conditions. This process is novel and groundbreaking because the product mixture of RG and valuable alcohols byproducts makes RG production economically feasible at $\$$12 per million British thermal units (MMBtu) or less using forest biomass from high hazard zones.

09 BIOMASS FUELS↗

Lessons Learned from Demolition of Hanford's Plutonium Finishing Plant - 20507

U.S. Department of Energy (DOE) contractor CH2M Hill Plateau Remediation Company (CHPRC), a Jacobs owned company, is making significant progress demolishing the Plutonium Finishing Plant (PFP), which has long been known as one of the most hazardous buildings in the DOE Environmental Management Complex (DOE Complex). The facility is located on the Hanford Site and produced plutonium metal during the Cold War. Production was stopped in 1989, the facility was formally shut down in 1996, and material processing was completed in 2004. After approximately 25 years of demolition preparations, open-air demolition of the main portions of the Hazard Category II nuclear facility began in November 2016. To prepare the PFP for demolition, CHPRC employees performed some of the most hazardous work across the DOE Complex. In addition to extensive demolition preparations, including a wide-reaching communication strategy across the Hanford Site, CHPRC implemented robust controls and monitoring during demolition, and when necessary, adjusted demolition practices and sequence to maintain employee safety and project efficiency. Demolition of the main PFP building began in November 2016. The technical complexity, high hazards and radiological concerns have all led to a difficult demolition environment. Following a spread of contamination at the project site beyond the radiological boundaries in December 2017, work was halted and a recovery plan was generated to allow the demolition work to continue. After the implementation of additional controls and concurrence from regulatory agencies and DOE, the demolition was ready to resume work and reinitiated in August 2018. There are a number of lessons learned from the demolition activities and recovery plan process. This paper allows CHPRC and DoE's Richland Operations Office (RL) to share lessons learned and progress to date with other challenging and hazardous projects across the DOE Complex. Understanding the risk acceptance level is critical to execution of any open-air demolition project and is unique to each facility. Four key lessons learned from this project include: 1) plan execution issues, 2) stakeholder communication issues, 3) watching for summit fever and 4) minimizing exposed contaminated surfaces during demolition. (authors)

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Photocatalytic Oxidation of Dissolved Mn 2+ by TiO 2 and the Formation of Tunnel Structured Manganese Oxides

The redox reaction of manganese (Mn) is of great environmental, geological, and public health significance, as Mn oxides control the distribution and electron flow of numerous nutrients and contaminants in natural and engineered environments. Current understanding on the oxidation pathways of Mn(II) to Mn(III/IV) mainly focuses on biotic processes due to their much higher oxidation rates than those of abiotic processes. This study demonstrates rapid photocatalytic oxidation of Mn 2+ (aq) under circumneutral conditions catalyzed by naturally abundant semiconducting TiO 2 minerals. Notably, the photocatalytic oxidation rates are comparable to or even higher than those of reported biotic/abiotic processes. In addition, the rapid photocatalytic oxidation leads to the formation of large tunnel structured Mn oxides (todorokite and romanechite) on the surface of TiO 2 . These findings suggest that photocatalytic oxidation of Mn 2+ (aq) by natural semiconducting minerals is likely an important yet previously overlooked pathway for understanding the occurrence of natural Mn oxide coatings on rock surfaces. In addition, considering the increasing input of photoreactive engineered nanoparticles into environmental systems, this work shows the potential impacts of nanoparticles on influencing natural redox cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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

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

42 ENGINEERING↗

Detection of Apparent Early Rabies Infection by LN34 Pan-Lyssavirus Real-Time RT-PCR Assay in Pennsylvania

The Pennsylvania Department of Health Bureau of Laboratories (PABOL) tested 6855 animal samples for rabies using both the direct fluorescent antibody test (DFA) and LN34 pan-lyssavirus reverse transcriptase quantitative PCR (RT-qPCR) during 2017–2019. Only two samples (0.03%) were initially DFA negative but positive by LN34 RT-qPCR. Both cases were confirmed positive upon re-testing at PABOL and confirmatory testing at the Centers for Disease Control and Prevention by LN34 RT-qPCR and DFA. Rabies virus sequences from one sample were distinct from all positive samples processed at PABOL within two weeks, ruling out cross-contamination. Levels of rabies virus antigen and RNA were low in all brain structures tested, but were higher in brain stem and rostral spinal cord than in cerebellum, hippocampus or cortex. Taken together, the low level of rabies virus combined with higher abundance in more caudal brain structures suggest early infection. These cases highlight the increased sensitivity and ease of interpretation of LN34 RT-qPCR for low positive cases.

59 BASIC BIOLOGICAL SCIENCES↗