Single particle ICP-MS has evolved rapidly as a quantitative method for determining nanoparticle size and number concentration at environmentally relevant exposure levels. Central to the application of spICP-MS is a commonly used, but not rigorously validated, calibration approach based on the measured transport efficiency and the response of ionic standards. In this work, we present a comprehensive and systematic study of the accuracy, precision and robustness of spICP-MS using the rigorously characterized reference material (RM) 8017 (Polyvinylpyrrolidone Coated Nominal 75 nm Silver Nanoparticles), recently issued by the National Institute of Standards and Technology (NIST). We report for the first time, statistically significant differences in frequency-based and size-based measures of transport efficiency with NIST RM 8013 Gold Nanoparticles and demonstrate that the size-based measure of transport efficiency is more robust and yields accurate results for the silver nanoparticle RM relative to TEM-based reference values. This finding is significant, because the frequency-based method is more widely applied. Furthermore, we demonstrate that the use of acidified ionic standards improves measurement of ICP-MS Ag response, but does not degrade the accuracy of the results for AgNP suspensions in water or various other diluents. Approaches for controlling AgNP dissolution were investigated and are shown to effectively improve particle stability in dilute suspensions required for spICP-MS analysis, while minimally affecting the measured intensity and allowing for more robust analysis. This study is an important and necessary advancement toward full validation and adoption of spICP-MS by the broader research community.
Reported reaction kinetics of metal nanoparticles in natural and engineered systems commonly have used proxy measurements to infer chemical transformations, but extension of these methods to complex media has proven difficult. Here, we compare the sulfidation rate of AgNPs using two ion selective electrode (ISE)-based methods, which rely on either (i) direct measurement of free sulfide, or (ii) monitor the free Ag+ available in solution over time in the presence of sulfide species. Most experiments were carried out in moderately hard reconstituted water at pH 7 containing fulvic acid or humic acid, which represented a broad set of known interferences in ISE. Distinct differences in the measured rates were observed between the two proxy-based methods and details of the divergent results are discussed. The two ISE based methods were then compared to direct monitoring of AgNP chemical conversion to Ag2S using synchrotron-based in situ X-ray diffraction (XRD). Using XRD, distinct rates from both ISE-based technique were observed, which demonstrated that ISE measurements alone are inadequate to discriminate both the rate and extent of AgNP sulfidation. XRD rate data elucidated previously unidentified reaction regimes that were associated with AgNP coating (PVP and citrate acid) and NOM components, which provided new mechanistic insight into metallic NP processing. In general, the extent of Ag2S formation was inversely proportional to surface coverage of the initial AgNP. Overall, methods to determine reaction kinetics of nanomaterials in increasingly complex media and heterogeneous size distributions to improve NP-based design and performance will require similar approaches.
Understanding the structure transformation of engineered nanomaterials (ENMs) is a grand measurement challenge, which impacts many aspects of ENMs applications, such as their efficacy, safety, and environmental consequence. To address the significant knowledge gap regarding the fundamental kinetic rate and extent of ENM transformation in the environment, we present a comprehensive and mechanistic structural investigation of the transformation, aggregation, and dissolution behavior of a polyvinylpyrrolidone-coated silver nanoparticle (AgNP) suspension upon sulfidation in moderately reduced hard water with fulvic acid and dissolved Na 2 S. This reaction is among the most prevalent and industrially and environmentally relevant ENMs transformation. Using ex situ transmission electron microscopy (TEM) and both in situ and ex situ synchrotron-based small angle X-ray scattering (SAXS) and X-ray diffraction (XRD), we find that sulfidation of faceted AgNPs strongly depends on the crystallographic orientation of the facets, with nanometer-scale passivation layers developed on {111} and {100} facets and continuous nucleation and growth on {110} facets. Nanobeam electron diffraction and atomic resolution imaging show Ag and Ag 2 S domains both possess a high degree of crystalline order, contradicting amorphous structures as previously reported. In situ SAXS/XRD allowed simultaneous determination of the morphological changes and extent of sulfidation of AgNPs. SAXS/XRD results strongly indicate sulfidation follows first-order reaction kinetics without any aggregation. Aided by their size monodispersity, for the first time, using direct, in situ morphology and atomic-structure probes whose results mutually corroborate, we unequivocally determined the sulfidation rate constant of AgNPs under an environmentally relevant condition (z0.013 min À1 for 68 nm diameter AgNPs). A rigorous analysis of the long-term sulfidation product of the AgNPs under different S/Ag ratios using ex situ SAXS/ XRD clearly demonstrates that the silver mass in the original AgNP and transformed Ag/Ag 2 S NP is preserved. This result has important environmental implications, strongly suggesting that Ag + ions, a known highly effective antimicrobial agent, are not leached into the solution during sulfidation of AgNPs. The combined nondestructive methodology can be extended to unfold the structure transformation pathway and kinetics in a broad range of ENM systems.
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