Controlled Evaluation of Metal-Based Nanomaterial Transformations

dc.contributor.authorKent, Ronald Douglasen
dc.contributor.committeechairVikesland, Peter J.en
dc.contributor.committeememberDove, Patricia M.en
dc.contributor.committeememberDietrich, Andrea M.en
dc.contributor.committeememberMarr, Linsey C.en
dc.contributor.departmentCivil and Environmental Engineeringen
dc.date.accessioned2017-02-12T07:00:19Zen
dc.date.available2017-02-12T07:00:19Zen
dc.date.issued2015-08-21en
dc.description.abstractMetal-based nanoparticles (MNPs) are becoming increasingly common in commercial products. Release of these materials into the environment raises concerns about the potential risks they pose to aquatic life. Predicting these risks requires an understanding of MNPs' chemical transformations. In this study, arrays of immobilized MNPs fabricated by nanosphere lithography (NSL) were used to investigate environmental transformations of MNPs. Specifically, sulfidation of silver nanoparticles (Ag NPs) and dissolution of copper-based nanoparticles (Cu NPs) were investigated. Atomic force microscopy (AFM) and transmission electron microscopy were the primary analytical techniques for these investigations. Because the MNPs were immobilized on a solid surface, the samples were field deployable, environmentally relevant metal concentrations were maintained, and the confounding influence of MNP aggregation was eliminated. Ag NP samples were deployed in a full-scale wastewater treatment plant. Sulfidation occurred almost exclusively in anaerobic zones of the WWTP, where the initial sulfidation rate was 11-14 nm of Ag converted to Ag2S per day. Conversion to Ag2S was complete within 7-10 d. Dissolution rates of Cu-based NPs were measured in situ over a range of pH by flow-cell AFM. Based on the measured rates, CuO/Cu(OH)2 NPs dissolve completely within a matter of hours at any pH, metallic Cu NPs persist for a few hours to days, and CuxS NPs do not dissolve significantly over the time scales studied. Field deployment of samples in a freshwater stream confirmed these conclusions for a natural aquatic system. This research demonstrates that environmental transformations of MNPs will be a key factor in determining the ultimate form and concentration of NPs that aquatic organisms will be exposed to.en
dc.description.degreePh. D.en
dc.format.mediumETDen
dc.identifier.othervt_gsexam:5972en
dc.identifier.urihttp://hdl.handle.net/10919/74998en
dc.publisherVirginia Techen
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subjectNanomaterialsen
dc.subjectsilveren
dc.subjectcopperen
dc.subjectOxidationen
dc.subjectdissolutionen
dc.subjectsulfidationen
dc.subjectnanosphere lithographyen
dc.subjectfateen
dc.subjecttransformationsen
dc.subjectconvective self-assemblyen
dc.subjectatomic force microscopyen
dc.titleControlled Evaluation of Metal-Based Nanomaterial Transformationsen
dc.typeDissertationen
thesis.degree.disciplineCivil Engineeringen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.leveldoctoralen
thesis.degree.namePh. D.en

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