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At least 145 records · Page 8

NASA Technology Evaluation for Environmental Risk Mitigation Remediation Technology Collaboration Development

NASA is committed to finding solutions to agency cleanup problems that are better, cheaper, and more effective than the status quo. Unfortunately, some potential solutions involve innovative technologies for which NASA remediation managers may not have a high level of understanding or confidence. Since 2004, NASA's Stennis Space Center (SSC) in Mississippi has been pumping groundwater contaminated with trichloroethylene (TCE) and other halogenated volatile organic compounds (HVOC) from their cleanup location designated "Area G" through extraction wells to an aboveground treatment system. Over time, however, the effectiveness of this treatment strategy has diminished and an alternative approach is needed. In 2012, professionals from NASA's Principal Center for Technology Evaluation for Environmental Risk Mitigation (TEERM) introduced SSC managers to an innovative technology for enhancing the performance of SSC's existing pump and treat system. The technology, generally referred to as in situ chemical oxidation (ISCO), involves slowly and continuously injecting a strong but safe chemical oxidant into the groundwater. Treatment is enhanced by a "surfactant-type effect" which causes residual contamination from saturated soil to be released into the dissolved-phase where it can be readily oxidized. Any dissolved-phase contamination that was not oxidized can be collected by the extraction well network and treated aboveground. SSC was not familiar with the technology so to increase their confidence, TEERM identified a contractor who was willing to demonstrate their product and process at a significantly reduced price. An initial, small-scale demonstration of ISCO began at sse in March 2012 and completed in August 2012. This successful demonstration was followed by three larger-scale ISCO demonstrations between August and December 2012. The contractor's innovative Continuous Injection System (CIS) incorporated "green" and sustainable technologies and practices. A slow injection rate was maintained autonomously by the CIS, eliminating the need for multiple mobilizations of personnel and powered equipment. The CIS was calibrated to deliver only as much reagent as the formation would accept without "short circuiting", minimizing material waste. Public utility water pressure was used to mix, dilute, and inject the reagent. NASA personnel were trained to operate and maintain the system and remote monitoring and injection control capabilities were developed, further reducing the need for contractor mobilizations to the site. An integrated solar photovoltaic panel was used to power the control valves and web monitoring telemetry. SSC provided hydrogen peroxide for the process using their existing supplier for the aboveground pump and treat systems. The only consumable required from the contractor was their proprietary activator to catalyze SSC's peroxide.

Romeo, James↗

Part IV: Remedial Action

This part of the book focuses on the remedial action where the remedy is selected and approved with associated regulatory documentation, detailed designs are prepared, and construction and/or implementation of the remedy is completed. The application may include remediation of environmental media (e.g., subsurface sediments or surface water sources), waste processing, and/or deactivation and decommissioning of historical facilities. Once a preferred remedy is implemented, the final steps include long-term stewardship and site closure (discussed in Part V). Refer to Section 3.2 of Chapter 1, Remediation Strategy for Complex Waste Sites, for context on how these steps fit into the broader remediation process.

Johnson, Christian D.↗

PART II - Site Assessment and Characterization

This part of the book, includes site assessment and characterization case studies from remediating different areas and historical processes and operations across the Hanford Site

environmental remediation↗

Lawrence Livermore National Laboratory Annual Environmental Report 2019

The purposes of the Lawrence Livermore National Laboratory (LLNL) Environmental Report 2019 are to record LLNL's compliance with environmental standards and requirements, describe LLNL’s environmental protection and remediation programs, and present the results of environmental monitoring at the two LLNL sites—the Livermore Site and Site 300. The report is prepared for the U.S. Department of Energy (DOE) by LLNL’s Environmental Functional Area. Submittal of the report satisfies requirements under DOE Order 231.1B, “Environment, Safety and Health Reporting,” and DOE Order 458.1, “Radiation Protection of the Public and Environment.” The report begins with an executive summary, which provides the purpose of the report and an overview of LLNL’s compliance and monitoring results. The first three chapters provide background information: Chapter 1 is an overview of the location, meteorology, and hydrogeology of the two LLNL sites; Chapter 2 is a summary of LLNL’s compliance with environmental regulations; and Chapter 3 is a description of LLNL’s environmental programs with an emphasis on the Environmental Management System including pollution prevention. The majority of the report covers LLNL’s environmental monitoring programs and monitoring data for 2019: effluent and ambient air monitoring and dose assessment (Chapter 4); waters, including wastewater, storm water runoff, surface water, rain, and groundwater (Chapter 5); and terrestrial, including soil, sediment, vegetation, foodstuff, ambient radiation, and special status wildlife and plants (Chapter 6). The remaining two chapters discuss LLNL’s groundwater remediation program (Chapter 7), and quality assurance for the environmental monitoring programs (Chapter 8). Complete monitoring data, which are summarized in the body of the report, are provided in Appendix A.

54 ENVIRONMENTAL SCIENCES↗

Lawrence Livermore National Laboratory Environmental Report 2021

The purposes of the Lawrence Livermore National Laboratory Environmental Report 2021 are to record Lawrence Livermore National Laboratory’s (LLNL’s) compliance with environmental standards and requirements, describe LLNL’s environmental protection and remediation programs, and present the results of environmental monitoring at the two LLNL sites—the Livermore Site and Site 300. The report is prepared for the U.S. Department of Energy (DOE) by LLNL’s Environmental Functional Area. Submittal of the report satisfies requirements under DOE Order 231.1B, “Environment, Safety and Health Reporting,” and DOE Order 458.1, “Radiation Protection of the Public and Environment.” The report is distributed electronically and is available at https://saer.llnl.gov/, the website for the LLNL annual environmental report. Previous LLNL annual environmental reports beginning with 1994 are also on the website. Some references in the electronic report text are underlined, which indicates that they are clickable links. Clicking on one of these links will open the related document, data workbook, or website. Sampling location maps throughout this report were created using ArcGIS® software by Esri. The report begins with an executive summary, which provides the purpose of the report and an overview of LLNL’s compliance and monitoring results. The first three chapters provide background information: Chapter 1 is an overview of the location, meteorology, and hydrogeology of the two LLNL sites; Chapter 2 is a summary of LLNL’s compliance with environmental regulations; and Chapter 3 is a description of LLNL’s environmental programs with an emphasis on the Environmental Management System including pollution prevention. The majority of the report covers LLNL’s environmental monitoring programs and monitoring data for 2021: effluent and ambient air monitoring and dose assessment (Chapter 4); waters, including wastewater, storm water runoff, surface water, rain, and groundwater (Chapter 5); and terrestrial, including soil, sediment, vegetation, foodstuff, ambient radiation, and special status wildlife and plants (Chapter 6). The remaining two chapters discuss LLNL’s groundwater remediation program (Chapter 7), and quality assurance for the environmental monitoring programs (Chapter 8). Complete monitoring data, which are summarized in the body of the report, are provided in Appendix A. The report uses Système International units, consistent with the federal Metric Conversion Act of 1975 and Executive Order 12770, “Metric Usage in Federal Government Programs” (1991). For ease of comparison to environmental reports issued prior to 1991, dose values and many radiological measurements are given in both metric and U.S. customary units. A conversion table is provided in the glossary. The report is the responsibility of LLNL’s Environmental Functional Area. Monitoring data were obtained through the combined efforts of the Environmental Functional Area; Environmental Restoration Department; Physical and Life Sciences Environmental Monitoring Radiological Laboratory; and the Radiation Protection Functional Area.

54 ENVIRONMENTAL SCIENCES↗

Biogeochemical controls on iron speciation and cycling across upland to shoreline gradients in freshwater and estuarine coastal soils (Lake Erie and Chesapeake Bay, United States)

Coastal environments are dynamic interfaces that mediate carbon and nutrient exchanges between terrestrial landscapes and open waters, and understanding the biogeochemical factors controlling these exchanges, particularly iron (Fe) redox transformations, is crucial for predicting coastal ecosystem functions. Here, we investigated the mechanisms controlling Fe speciation changes across upland-to-shoreline gradients in freshwater and estuarine soils using Fe K-edge X-ray absorption spectroscopy, solid and porewater composition analysis, and 16S rRNA sequencing analysis. We show that Fe transformations depend primarily on inundation patterns. In unsaturated uplands, Fe occurs as Fe(III) oxyhydroxides, mainly goethite (9–35 %), Fe(II,III)-phyllosilicates (39–89 %), and Fe(III)-organic species (0–61 %). Soils influenced by estuarine waters exhibit porewater sulfide concentrations reaching up to 221 μM, Fe- and S-cycling bacteria, and up to 81 % pyrite (FeS 2 ), indicating that sulfur-driven redox dynamics control Fe transformations. In lacustrine wetlands, Fe(III) reduction is indicated by porewater Fe(II) concentrations increasing to 1.0–2.1 mM, and ~10–15 % of Fe as Fe(II,III)-(hydr)oxides (green rust), vivianite (Fe 3 (PO 4 ) 2 ·8H 2 O), and/or adsorbed Fe(II) species. EXAFS data also indicate reduction of structural Fe(III) to Fe(II) in phyllosilicates. The presence of Fe- and S-cycling bacteria, as well as sulfide (0–10 μM), suggests that Fe-cycling is microbially driven and potentially coupled with cryptic S-cycling. Fe(II) oxidation was indicated above/near the water table by the presence of Fe(III) oxyhydroxides (ferrihydrite, lepidocrocite). Furthermore, negligible Fe(III) or sulfate reduction was observed at some water-saturated sites located at the upland-wetland transition, likely due to oxic (sub-)surface water inputs. Overall, our results highlight the importance of considering both Fe-speciation and hydro-biogeochemical dynamics when predicting Fe-cycling at coastal interfaces.

54 ENVIRONMENTAL SCIENCES↗

Oxide– and Silicate–Water Interfaces and Their Roles in Technology and the Environment

Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nanofabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic- and nanometer-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously, namely, interfacial chemical reactions are frequently driven by “anomalies” or “non-idealities” such as defects, nanoconfinement, and other nontypical chemical structures. Third, progress in computational chemistry has yielded new insights that allow a move beyond simple schematics, leading to a molecular model of these complex interfaces. In combination with surface-sensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide– and silicate–water interfaces. This critical review discusses how science progresses from understanding ideal solid–water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. Further, we anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spatial Engineering Direct Cooperativity between Binding Sites for Uranium Sequestration

Preorganization is a basic design principle used by nature that allows for synergistic pathways to be expressed. Herein, a full account of the conceptual and experimental development from randomly distributed functionalities to a convergent arrangement that facilitates cooperative binding is given, thus conferring exceptional affinity toward the analyte of interest. The resulting material with chelating groups populated adjacently in a spatially locked manner displays up to two orders of magnitude improvement compared to a random and isolated manner using uranium sequestration as a model application. This adsorbent shows exceptional extraction efficiencies, capable of reducing the uranium concentration from 5 ppm to less than 1 ppb within 10 min, even though the system is permeated with high concentrations of competing ions. The efficiency is further supported by its ability to extract uranium from seawater with an uptake capability of 5.01 mg g -1 , placing it among the highest-capacity seawater uranium extraction materials described to date. The concept presented here uncovers a new paradigm in the design of efficient sorbent materials by manipulating the spatial distribution to amplify the cooperation of functions.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Iodate interactions with calcite: implications for natural attenuation

Solid-phase interactions and speciation are important to radioiodine transport in groundwater. At the Hanford Site in Southeastern Washington State, iodate (IO 3 - ) is the main aqueous species in dilute radioiodine groundwater plumes. Like other oxyanions, IO 3 - may be incorporated into and/or adsorbed onto calcite, a common mineral at Hanford, decreasing its mobility in the environment. A series of macroscale batch experiments combined with solid phase characterization were conducted to identify variables impacting time-dependent aqueous IO 3 - removal via calcite precipitation and determine the location of IO 3 - within the calcite crystal structure. Results demonstrated 11.5-97% aqueous IO 3 - removal during initial rapid calcite precipitation. Incorporation was apparently the main removal mechanism, although later slower precipitation and/or adsorption may have also contributed to IO 3 - removal. Using a higher concentration of the calcite forming solutions (i.e., using 1M vs. 0.1M concentrations) resulted in an increase in the amount of precipitated calcite and a greater percentage of IO 3 - removed; however, calcite formed with lower molarity solutions resulted in higher IO 3 - mass (µg/g) removal. Solubility testing of laboratory produced calcites showed only small differences in solubility for calcite with and without IO 3 - incorporated into the structure. Evidence collected from SEM/FIB and TEM/SAED suggested that the IO 3 - incorporated into calcite was present in regions close to surface (implying potential easy release upon calcite dissolution).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Application of machine learning to evaluating and remediating models for energy and environmental engineering

Machine learning (ML) algorithms have been increasingly successful in their applications to solve energy and environmental engineering problems. ML algorithms have the advantage of being able to solve highly nonlinear issues effectively. Furthermore, considering the limited sample size of data collected in energy and environmental engineering, obtaining a ML model with reasonable accuracy is simple. Unfortunately, the vast majority of the current applications of ML algorithms lack effective screening of dominant factors and comprehensive model validation, which weakens the predictive ability of the models. The present study takes the minimum miscible pressure (MMP) of CO 2 - oil systems as an example. It establishes a systematic and robust predictive model to address this issue. Based on 147 sets of slim tube tests, the predictive models of the MMPs are investigated by application of eight ML algorithms. The paper concludes that most of the published ML models in the field of energy and environmental engineering prediction are not reliable. Furthermore, it addresses the main reasons for the poor performance of some predictive models built by ML and provides guidelines on how to make such models robust. Further, to the best of our knowledge, this is the first study to point out the defects of current ML modeling methods and propose countermeasures for their application in energy and environmental engineering problems.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Aryl Diazonium-Assisted Amidoximation of MXene for Boosting Water Stability and Uranyl Sequestration via Electrochemical Sorption

Despite that two-dimensional transition metal carbides and carbonitrides (MXenes) are burgeoning candidates for remediation of environmental pollutants, the construction of robust functionalized MXene nanosheets with a high affinity for target heavy metal ions and radionuclides remains a challenge. Here we report the successful placement of amidoxime chelating groups on Ti 3 C 2 T x MXene surface by diazonium salt grafting. The introduction of amidoxime functional groups significantly enhances the selectivity of Ti 3 C 2 T x nanosheets for uranyl ions and also greatly improves their stability in aqueous solution, enabling efficient, rapid, and recyclable uranium extraction from aqueous solutions containing competitive metal ions. Benefiting from the excellent conductivity of MXenes, the amidoxime functionalized Ti 3 C 2 T x nanosheets show outstanding electrochemical performance such that when loaded on carbon cloth the application of an electric field increases the uranium adsorption capacity from 294 to 626 mg/g, outperforming all organic electrochemical sorption materials reported previously. Finally, the present work provides an effective strategy to functionalize MXene nanosheets with fundamental implications for the design of MXene-based selective electrosorption electrode materials.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Actinide Separation Inspired by Self-Assembled Metal–Polyphenolic Nanocages

The separation of actinides has a vital place in nuclear fuel reprocessing, recovery of radionuclides, and remediation of environmental contamination. Here we propose a new paradigm of nanocluster-based actinide separation, namely, nanoextraction, that can achieve efficient sequestration of uranium in an unprecedented form of giant coordination nanocages using a cone-shaped macrocyclic pyrogallol[4]arene as the extractant. The U 24 -based hexameric pyrogallol[4]arene nanocages with distinctive [U 2 (PG) 2 ] binuclear units (PG = pyrogallol) that rapidly assembled in situ in monophasic solvent were identified by single-crystal X-ray diffraction, MALDI-TOF mass spectrometry, NMR spectroscopy, and small-angle X-ray and neutron scattering. Furthermore, comprehensive biphasic extraction studies showed that this novel separation strategy has enticing advantages such as fast kinetics, high efficiency, and good selectivity over lanthanides, thereby demonstrating its potential for efficient separation of actinide ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metal-organic frameworks as effective sensors and scavengers for toxic environmental pollutants

Abstract Metal-organic frameworks (MOFs) constructed from a rich library of organic struts and metal ions/clusters represent promising candidates for a wide range of applications. The unique structure, porous nature, easy tunability and processability of these materials make them an outstanding class of materials for tackling serious global problems relating to energy and environment. Among them, environmental pollution is one aspect that has increased at an alarming rate in the past decade or so. With rapid urbanization and industrialization, toxic environmental pollutants are constantly released and accumulated leading to serious contamination in water bodies and thereby having adverse effects on human health. Recent studies have shown that many toxic pollutants, as listed by the World Health Organization and the US Environmental Protection Agency, can be selectively detected, captured, sequestered and removed by MOFs from air and aquatic systems. Most of these sensing/capture processes in MOFs are quantifiable and effective for even a trace amount of the targeted chemical species. The functional sites (ligands and metals) play a critical role in such recognition processes and offer an extensive scope of structural tunability for guest (pollutants, toxic entities) recognition. Whereas on the one hand, the underlying mechanisms governing such sensing and capture are important, it is also crucial to identify MOFs that are best suited for commercial applications for the future. In this review article, we provide an overview of the most recent progress in the sensing, capture and removal of various common toxic pollutants, including neutral and ionic, inorganic and organic species, with brief discussions on the mechanism and efficacy of selected MOFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Beneficial Use Impairments, Degradation of Aesthetics, and Human Health: A Review

In environmental programs and blue/green space development, improving aesthetics is a common goal. There is broad interest in understanding the relationship between ecologically sound environments that people find aesthetically pleasing and human health. However, to date, few studies have adequately assessed this relationship, and no summaries or reviews of this line of research exist. Therefore, we undertook a systematic literature review to determine the state of science and identify critical needs to advance the field. Keywords identified from both aesthetics and loss of habitat literature were searched in PubMed and Web of Science databases. After full text screening, 19 studies were included in the review. Most of these studies examined some measure of greenspace/bluespace, primarily proximity. Only one study investigated the impacts of making space quality changes on a health metric. The studies identified for this review continue to support links between green space and various metrics of health, with additional evidence for blue space benefits on health. No studies to date adequately address questions surrounding the beneficial use impairment degradation of aesthetics and how improving either environmental quality (remediation) or ecological health (restoration) efforts have impacted the health of those communities.

60 APPLIED LIFE SCIENCES↗

Sensor arrays for detecting analytes in fluids

A sensor array for detecting an analyte in a fluid, comprising at least first and second chemically sensitive resistors electrically connected to an electrical measuring apparatus, wherein each of the chemically sensitive resistors comprises a mixture of nonconductive material and a conductive material. Each resistor provides an electrical path through the mixture of nonconductive material and the conductive material. The resistors also provide a difference in resistance between the conductive elements when contacted with a fluid comprising an analyte at a first concentration, than when contacted with an analyte at a second different concentration. A broad range of analytes can be detected using the sensors of the present invention. Examples of such analytes include, but are not limited to, alkanes, alkenes, alkynes, dienes, alicyclic hydrocarbons, arenes, alcohols, ethers, ketones, aldehydes, carbonyls, carbanions, polynuclear aromatics, organic derivatives, biomolecules, sugars, isoprenes, isoprenoids and fatty acids. Moreover, applications for the sensors of the present invention include, but are not limited to, environmental toxicology, remediation, biomedicine, material quality control, food monitoring and agricultural monitoring.

Lewis, Nathan S.↗