title: Transformations of citrate and Tween coated silver nanoparticles reacted with Na₂S.
abstract: Silver nanoparticles (Ag NPs) are susceptible to transformations in environmental and biological media such as aggregation, oxidation, dissolution, chlorination, sulfidation, formation/replacement of surface coatings following interaction with natural organic matter (NOM). This paper investigates the impact of surface coating and Suwannee River fulvic acid (SRFA) on the transformations and behavior of Ag NPs (citrate coated and Tween coated; cit-Ag NPs and Tween-Ag NPs, respectively), following reaction with different concentrations of Na2S solution (as a source of sulfide species, H2S and HS(-)). These transformations and the dominant mechanisms of transformations were investigated using UV-vis and scanning transmission electron microscopy coupled with electron energy loss spectroscopy. Here, we have shown that Ag NP surface coating impacts their dissolution following dilution in ultrahigh purity water, with higher extent of dissolution of Tween-Ag NPs compared with cit-Ag NPs. Tween-Ag NPs are susceptible to dissolution following their sulfidation at low S/Ag molar ratio. Suwannee River fulvic acid (SRFA) slows down the dissolution of Tween-Ag NPs at low sulfide concentrations and reduces the aggregation of cit-Ag NP in the presence of sodium sulfide. Sulfidation appears to occur by direct interaction of sulfide species with Ag NPs rather than by indirect reaction of sulfide with dissolved Ag species subsequent to dissolution. Furthermore, the sulfidation process results in the formation of partially sulfidized Ag NPs containing unreacted (metallic) subgrains at the edge of the NPs for Tween-Ag NPs in the presence of high sulfide concentration (2000nM Na2S), which occurred to less extent at lower Na2S concentration for Tween-Ag NPs and at all concentrations of Na2S for cit-Ag NPs. Thus, sulfidized Ag NPs may preserve some of the properties of the Ag NPs such as their potential to shed Ag(+) ions and their toxic potential of Ag NPs.
authors.affiliation: Center for Environmental Nanoscience and Risk, Department of Environmental Health Sciences, Arnold School of Public Health, University of South Carolina, Columbia, SC 29028, USA.
authors.forename: M
authors.initials: M
authors.lastname: Baalousha
authors.affiliation: School of Biochemistry, University of Bristol, Bristol BS8 1TD, United Kingdom.
authors.forename: K P
authors.initials: KP
authors.lastname: Arkill
authors.affiliation: School of Geography, Earth and Environmental Sciences, University of Birmingham, Birmingham B15 2TT, United Kingdom.
authors.forename: I
authors.initials: I
authors.lastname: Romer
authors.affiliation: School of Physics and Astronomy, University of Birmingham, Birmingham B15 2TT, United Kingdom.
authors.forename: R E
authors.initials: RE
authors.lastname: Palmer
authors.affiliation: Center for Environmental Nanoscience and Risk, Department of Environmental Health Sciences, Arnold School of Public Health, University of South Carolina, Columbia, SC 29028, USA; School of Geography, Earth and Environmental Sciences, University of Birmingham, Birmingham B15 2TT, United Kingdom.
authors.forename: J R
authors.initials: JR
authors.lastname: Lead
mesh_terms: D019343:Citric Acid / Q000737:chemistry*; D053768:Metal Nanoparticles / Q000737:chemistry*; D017348:Microscopy, Electron, Scanning Transmission; D008956:Models, Chemical; D011136:Polysorbates / Q000737:chemistry*; D012834:Silver / Q000737:chemistry; D013440:Sulfides / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000737:chemistry*
chemical_list: D011136:Polysorbates; D013440:Sulfides; D014874:Water Pollutants, Chemical; D019343:Citric Acid; D012834:Silver; C033479:sodium sulfide
keywords: Citrate; Dissolution; Silver nanoparticles; Sulfidation; Transformation; Tween