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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Ultranano Titania: Selectively Ridding Water of Persistent Organic Pollutants

Persistent organic pollutants, including the EPA's “dirty dozen”, are difficult to remove from water supplies due to their chemical stability. Here, we report a stable oxide photocatalyst, ultranano titania (d < 2 nm) doped with iron, Fe•TiUNP, that efficiently mineralizes multiple persistent pollutants including aromatic compounds plus common troublesome, difficult-to-oxidize intermediates such as formaldehyde and acetone, netting mineralization of persistent pollutants. Efficiency stems from a direct charge-transfer pathway. The key role of iron doping is to lower the reduction potential of the photogenerated electron so that it is insufficient to reduce water, thus eliminating competition from the hydrogen evolution reaction. The reduction potential of the localized electron is similarly insufficient to reduce quinone, enabling breaking aromaticity. Specific results for degrading acetone, phenol, benzoic acid, and 1,4-benzoquinone are reported.

alcohols↗

Genomic Diversity and Phenotypic Variation in Fungal Decomposers Involved in Bioremediation of Persistent Organic Pollutants

Fungi work as decomposers to break down organic carbon, deposit recalcitrant carbon, and transform other elements such as nitrogen. The decomposition of biomass is a key function of wood-decaying basidiomycetes and ascomycetes, which have the potential for the bioremediation of hazardous chemicals present in the environment. Due to their adaptation to different environments, fungal strains have a diverse set of phenotypic traits. This study evaluated 320 basidiomycetes isolates across 74 species for their rate and efficiency of degrading organic dye. We found that dye-decolorization capacity varies among and within species. Among the top rapid dye-decolorizing fungi isolates, we further performed genome-wide gene family analysis and investigated the genomic mechanism for their most capable dye-degradation capacity. Class II peroxidase and DyP-type peroxidase were enriched in the fast-decomposer genomes. Gene families including lignin decomposition genes, reduction-oxidation genes, hydrophobin, and secreted peptidases were expanded in the fast-decomposer species. This work provides new insights into persistent organic pollutant removal by fungal isolates at both phenotypic and genotypic levels.

59 BASIC BIOLOGICAL SCIENCES↗

Novel catalysts with multivalence copper for organic pollutants removal from wastewater with excellent selectivity and stability in Fenton‐like process under neutral pH conditions

Abstract Fenton‐like reaction has been widely used for organics degradation. However, most Fenton‐like reaction works at low pH range (pH < 4) with uncontrollable selectivity of hydroxyl radicals from H 2 O 2 activation, and unsatisfied catalyst stability, which is compromised advanced oxidation performance for water/wastewater treatments. In this work, to solve the drawbacks, novel copper catalysts were fabricated via hydrogen reduction/calcination of Cu 2+ ‐supported Al/MCM‐41 with precisely controllable copper valence state. Compared with catalysts with monovalence copper (i.e., CuO, Cu, and Cu 2+ ), the obtained catalysts with multivalence copper present higher selectivity, excellent stability towards •OH radical pathways, and outperformance in p CBA degradation efficiency at neutral state. In addition, the fabricated catalysts also exhibited excellent phenol removal efficiency (75.5%) and H 2 O 2 utilization efficiency (47.9%) within neutral environment. Moreover, the degradation efficiency of phenol approaches to 100% within only 2 h. The catalyst also shows good stability for organic pollutants removal, which shows good potential in catalytic oxidation for phenolic compounds‐containing wastewater in Fenton‐like reaction, especially under neutral pH conditions. Practitioner Points Multivalence copper presents great potentials for organic compounds removal at neutral condition. Multivalence copper shows higher selectivity toward •OH and good stability at neutral condition. Multivalence copper exhibiters outperformed phenol removal efficiency at neutral condition.

Li, Haitao↗

Chapter 3: Nanostructured Iron Oxide Hybrid Composites as Heterogeneous Fenton-Like Catalyst for Remediation of Persistent Organic Pollutants

In water purification research and technologies, heterogeneous Fenton catalysts are evolving as an excellent material recently. A summary of present research on heterogeneous Fenton/Fenton-like processes is essential for developing novel and high-efficiency organic wastewater treatment methods. In this chapter, we discussed the basics of Fenton reactions taking the example of iron oxides and their different composites, such as bimetallic composites, composites with carbon compounds, and Fe metal-organic frameworks (MOFs). The important operating parameters (solution pH, H 2 O 2 dosage, amount of catalyst used, and reaction temperature) in heterogeneous Fenton-like reactions are discussed. Strategies to increase the rate and activities of heterogeneous Fenton catalysts by using energy sources are presented. The mechanistic aspects of heterogeneous Fenton processes and reusability of catalysts along with their application in real wastewater plants are summarized and discussed. Finally, we concluded with the scope and future prospects of heterogeneous Fenton catalysis research to motivate the readers to construct novel and efficient heterogeneous Fenton/Fenton-like systems for industrial applications.

carbon composites↗

Efficient electrocatalytic valorization of chlorinated organic water pollutant to ethylene

Electrochemistry can provide an efficient and sustainable way to treat environmental waters polluted by chlorinated organic compounds. However, the electrochemical valorization of 1,2-dichloroethane (DCA) is currently challenged by the lack of a catalyst that can selectively convert DCA in aqueous solutions into ethylene. Here, in this work, we report a catalyst comprising cobalt phthalocyanine molecules assembled on multiwalled carbon nanotubes that can electrochemically decompose aqueous DCA with high current and energy efficiencies. Ethylene is produced at high rates with unprecedented ~100% Faradaic efficiency across wide electrode potential and reactant concentration ranges. Kinetic studies and density functional theory calculations reveal that the rate-determining step is the first C–Cl bond breaking, which does not involve protons—a key mechanistic feature that enables cobalt phthalocyanine/carbon nanotube to efficiently catalyse DCA dechlorination and suppress the hydrogen evolution reaction. The nanotubular structure of the catalyst enables us to shape it into a flow-through electrified membrane, which we have used to demonstrate >95% DCA removal from simulated water samples with environmentally relevant DCA and electrolyte concentrations.

Choi, Chungseok↗

Direct analysis of organic priority pollutants by IMS

Many routine methods for monitoring of trace amounts of atmospheric organic pollutants consist of several steps. Typical steps are: (1) collection of the air sample; (2) trapping of organics from the sample; (3) extraction of the trapped organics; and (4) identification of the organics in the extract by GC (gas chromatography), HPLC (High Performance Liquid Chromatography), or MS (Mass Spectrometry). These methods are often cumbersome and time consuming. A simple and fast method for monitoring atmospheric organics using an IMS (Ion Mobility Spectrometer) is proposed. This method has a short sampling time and does not require extraction of the organics since the sample is placed directly in the IMS. The purpose of this study was to determine the responses in the IMS to organic 'priority pollutants'. Priority pollutants including representative polycyclic aromatic hydrocarbons (PAHs), phthalates, phenols, chlorinated pesticides, and polychlorinated biphenyls (PCB's) were analyzed in both the positive and negative detection mode at ambient atmospheric pressure. Detection mode and amount detected are presented.

Giam, C. S.↗

Membrane-Confined Iron Oxychloride Nanocatalysts for Highly Efficient Heterogeneous Fenton Water Treatment

Heterogeneous advanced oxidation processes (AOPs) allow for the destruction of aqueous organic pollutants via oxidation by hydroxyl radicals ( • OH). However, practical treatment scenarios suffer from the low availability of short-lived • OH in aqueous bulk, due to both mass transfer limitations and quenching by water constituents, such as natural organic matter (NOM). In this work, we overcome these challenges by loading iron oxychloride catalysts within the pores of a ceramic ultrafiltration membrane, resulting in an internal heterogeneous Fenton reaction that can degrade organics in complex water matrices with pH up to 6.2. With • OH confined inside the nanopores (~ 20 nm), this membrane reactor completely removed various organic pollutants with water fluxes of up to 100 L m –2 h –1 (equivalent to a retention time of 10 s). This membrane, with a pore size that excludes NOM (>300 kDa), selectively exposed smaller organics to •OH within the pores under confinement and showed excellent resiliency to representative water matrices (simulated surface water and sand filtration effluent samples). Moreover, the membrane exhibited sustained AOPs (>24 h) and could be regenerated for multiple cycles. Our results suggest the feasibility of exploiting ultrafiltration membrane-based AOP platforms for organic pollutant degradation in complex water scenarios.

36 MATERIALS SCIENCE↗

High surface area magnetic double perovskite La 2 AlFeO 6 as an efficient and stable photo-Fenton catalyst under a wide pH range

Photo-Fenton process is an efficient way to treat the organic pollutants in wastewater. However, the efficiency is limited by serious leaching of iron ion, separation of spent catalyst from reaction system for facile recycling, low (pH<4) reaction environment. Herein, we report a preparation of a novel magnetic double perovskite photocatalyst La2AlFeO6, and refractory organic pollutants like phenol, etc. were used as probes to test the efficiency of catalyst. The results showed that the catalytic material retained high surface area and high ratio of Fe 3+ on its surface, and the generated ·OH, ·O 2 - and 1 O 2 lead to a highly photocatalytic efficiency even at neutral pH condition. In addition, the as prepared double perovskite photocatalyst La 2 AlFeO 6 also exhibits excellent stable and magnetic properties. There is no iron ion leaching detected during the courses of the reaction. Furthermore, the spent catalyst can be separated by magnetic field easily, and thus can be reused after simple air drying without any further treatment or calcination.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bisphenol A degradation by manganese oxides at circumneutral pH: Quantitative evaluation of dissolved Mn(III) species with pyrophosphate

Although trivalent manganese (Mn(III)) species have been recognized as crucial intermediates in the degradation of organic contaminants by Mn oxides, quantitative research on their specific roles remains scarce. Here, our study investigated the degradation processes of an organic pollutant, Bisphenol A (BPA), by dissolved Mn(III) and Mn(III)-bearing oxides, and elucidated the differences of the underlying mechanisms and reaction pathways between several Mn oxides and dissolved Mn(III). Our results indicated that BPA degradation rates with Mn(III)-bearing oxides alone follow the order: δ-MnO 2 >> γ-MnOOH > Mn 3 O 4 . Adding pyrophosphate (PP) significantly enhanced BPA degradation by promoting the formation of Mn(III)-PP complexes and exposing more reactive sites, achieved through destabilizing the crystal structure and mitigating of Mn(II) readsorption, particularly in γ-MnOOH and Mn 3 O 4 . Our kinetic model revealed that heterogeneous degradation by Mn oxides is the predominant reaction pathway, accounting for 61.4 %, 87.8 %, and 73.8 % of the total degraded BPA for δ-MnO 2 , γ-MnOOH, and Mn 3 O 4 , respectively, even in the presence of significant amount of dissolved Mn(III) intermediates due to high PP concentrations. These results offer mechanistic details on BPA degradation by Mn oxides and the influence of ligand concentration, providing helpful insights for optimizing degradation strategies of organic pollutants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Toward the Next Generation of Air Quality Monitoring Indicators

This paper introduces an initiative to bridge the state of scientific knowledge on air pollution with the needs of policymakers and stakeholders to design the "next generation" of air quality indicators. As a first step this initiative assesses current monitoring and modeling associated with a number of important pollutants with an eye toward identifying knowledge gaps and scientific needs that are a barrier to reducing air pollution impacts on human and ecosystem health across the globe. Four outdoor air pollutants were considered e particulate matter, ozone, mercury, and Persistent Organic Pollutants (POPs) e because of their clear adverse impacts on human and ecosystem health and because of the availability of baseline data for assessment for each. While other papers appearing in this issue will address each pollutant separately, this paper serves as a summary of the initiative and presents recommendations for needed investments to provide improved measurement, monitoring, and modeling data for policyrelevant indicators. The ultimate goal of this effort is to enable enhanced public policy responses to air pollution by linking improved data and measurement methods to decision-making through the development of indicators that can allow policymakers to better understand the impacts of air pollution and, along with source attribution based on modeling and measurements, facilitate improved policies to solve it. The development of indicators represents a crucial next step in this process.

Particulate matter↗

Comparing the extraction performance of cyclodextrin-containing supramolecular deep eutectic solvents versus conventional deep eutectic solvents by headspace single drop microextraction

A headspace single drop microextraction (HS-SDME) method coupled with high performance liquid chromatography was developed to compare the extraction of eighteen aromatic organic pollutants from aqueous solutions using cyclodextrin-based supramolecular deep eutectic solvents (SUPRADESs) and alkylammonium halide-based conventional deep eutectic solvents (DESs). Different derivatives of beta-cyclodextrin (β-CD) were employed as hydrogen bond acceptors (HBA) in SUPRADESs and the extraction performance investigated. SUPRADES comprised of the 20 wt% native β-CD HBA provided the highest enrichment factors of analytes compared to SUPRADESs comprised of other derivatives of β-CD (random methylated β-cyclodextrin, heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin, and 2-hydroxypropyl β-cyclodextrin). In addition, native β-CD and its derivatives were dissolved in the neat DESs and their effect on the extraction of analytes examined. Dissolution of 20 wt% native β-CD in the choline chloride ([Ch + ][Cl - ]):2Urea DES resulted in a significant increase in the extraction efficiencies of target analytes compared to the neat [Ch + ][Cl - ]:2Urea DES. Under optimum conditions, the extraction method required a solvent microdroplet of 6.5 μL, 1000 rpm stir rate, 30% (w/v) salt concentration, and a temperature of 40 °C. The tetrabutylammonium chloride: 2 lactic acid DES resulted in the highest enrichment factors while the [Ch + ][Cl - ]:2Urea DES had the lowest for most of the analytes among the evaluated solvents. The method provided limits of detection (LODs) down to 35 μg L -1 . Finally, the developed method was applied for the analysis of spiked tap and lake water, where relative recoveries ranging from 83.7% -119.7% and relative standard deviations lower than 19.2% were achieved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Industrial waste pollution

The characteristics and effects of industrial waste pollution in the Chesapeake Bay are discussed. The sources of inorganic and organic pollution entering the bay are described. The four types of pollutants are defined as: (1) inorganic chemical wastes, (2) naturally occurring organic wastes, (3) synthetic organic wastes (exotics) and (4) thermal effluents. The ecological behavior of industrial wastes in the surface waters is analyzed with respect to surface film phenomena, interfacial phenomena, and benthis phenomena

Jensen, L. D.↗

Drawing on Membrane Photocatalysis for Fouling Mitigation

Photocatalysis is an effective and environmentally friendly approach for degrading organic pollutants, particularly in scenarios where sunlight can be utilized as the energy source. Opportunities are emerging to apply materials and methods from photocatalytic pollutant degradation to address the challenge of fouling. Membrane fouling, attributed to organic foulants, is a prevalent problem for all membrane-based technologies and represents a major deleterious impact on membrane performance. Integration of tactics developed in photocatalysis more broadly to membranes reveals new strategies for membrane fouling control-an approach taken by an increasing number of researchers. Furthermore, this review summarizes key developments in photocatalytic materials and methods in water treatment and presents recent progress in the development of processes for photocatalytic alleviation of membrane fouling, including photocatalyst design and modification strategies aimed at enhancing photocatalytic efficiency, as well as different configurations of photocatalysis-membrane systems (PMS). Perspectives on future research and development opportunities for photocatalytic membrane fouling control are also provided.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Shed Light in the DaRk LineagES of the Fungal Tree of Life—STRES

The polyphyletic group of black fungi within the Ascomycota (Arthoniomycetes, Dothideomycetes, and Eurotiomycetes) is ubiquitous in natural and anthropogenic habitats. Partly because of their dark, melanin-based pigmentation, black fungi are resistant to stresses including UV- and ionizing-radiation, heat and desiccation, toxic metals, and organic pollutants. Consequently, they are amongst the most stunning extremophiles and poly-extreme-tolerant organisms on Earth. Even though ca. 60 black fungal genomes have been sequenced to date, [mostly in the family Herpotrichiellaceae (Eurotiomycetes)], the class Dothideomycetes that hosts the largest majority of extremophiles has only been sparsely sampled. By sequencing up to 92 species that will become reference genomes, the “Shed light in The daRk lineagES of the fungal tree of life” (STRES) project will cover a broad collection of black fungal diversity spread throughout the Fungal Tree of Life. Interestingly, the STRES project will focus on mostly unsampled genera that display different ecologies and life-styles (e.g., ant- and lichen-associated fungi, rock-inhabiting fungi, etc.). With a resequencing strategy of 10- to 15-fold depth coverage of up to ~550 strains, numerous new reference genomes will be established. To identify metabolites and functional processes, these new genomic resources will be enriched with metabolomics analyses coupled with transcriptomics experiments on selected species under various stress conditions (salinity, dryness, UV radiation, oligotrophy). The data acquired will serve as a reference and foundation for establishing an encyclopedic database for fungal metagenomics as well as the biology, evolution, and ecology of the fungi in extreme environments.

59 BASIC BIOLOGICAL SCIENCES↗

Intercontinental Transport of Air Pollution

The development of the global economy goes beyond raising our standards of living. We are in an ear of increasing environmental as well as economic interdependence. Long-range transport of anthropogenic atmospheric pollutants such as ozone, ozone precursors, airborne particles, heavy metals (such as mercury) and persistent organic pollutants are the four major types of pollution that are transported over intercontinental distances and have global environmental effects. The talk includes: 1) an overview of the international agreements related to intercontinental transport of air pollutants, 2) information needed for decision making, 3) overview of the past research on intercontinental transport of air pollutants - a North American's perspective, and 4) future research needs.

Rogers, David↗