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This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.
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7 1 A Critical Review of Single Particle Inductively
Journal of Analytical Atomic Spectrometry Accepted Manuscript

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2 Coupled Plasma Mass Spectrometry – A Step
Open Access Article. Published on 25 July 2019. Downloaded on 7/26/2019 3:25:58 AM.
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3 Towards the Ideal Method for Nanomaterials
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20 4 Characterization
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25 5 Darya Mozhayeva1 and Carsten Engelhard*1, 2
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28 6 1University of Siegen, Department of Chemistry and Biology,
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31 7 Adolf-Reichwein-Str. 2, D-57076 Siegen, Germany.
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34 8 2Center of Micro- and Nanochemistry and Engineering, University of Siegen,
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37 9 Adolf-Reichwein-Str. 2, D-57076 Siegen, Germany
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18 6 Table of content entry:
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23 8 A Critical Review of Single Particle Inductively Coupled Plasma Mass Spectrometry
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26 9 – A Step Towards the Ideal Method for Nanomaterials Characterization
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10 Single particle inductively coupled plasma mass spectrometry (spICP-MS) is becoming an
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31 11 important tool for the characterization of nanoparticles. This critical review discusses the
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13 introduction system to the detector. Recent literature on separation methods coupled to
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39 14 spICP-MS including capillary electrophoresis, field flow fractionation, and differential
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42 15 mobility analysis are reviewed as well. Nanoanalysis application papers from the recent
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16 literature are summarized in tabular form including important experimental parameters,
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1 Dedication:
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Dedicated to Professor Gary M. Hieftje on the occasion of his retirement from Indiana
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1 ABSTRACT
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7 2 Single particle inductively coupled plasma mass spectrometry (spICP-MS or SP-

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10 3 ICP-MS depending on the author) is becoming an important tool for the characterization
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4 of nanoparticles (NPs). The method allows to determine size, size distribution, and particle
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15 5 number concentrations of NPs in suspensions after a mere few minutes of measurement.
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18 6 This review is modeled after the concept of “an ideal method for atomic spectroscopy”
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7 introduced by Gary M. Hieftje in his publication dedicated to Howard Malmstadt.1 This
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23 8 review discusses the instrumental developments in spICP-MS of recent years step-by-
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26 9 step, from the sample introduction system to the detector. The authors identify necessary
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10 improvements and suggest directions for further developments which have the potential
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13 including capillary electrophoresis (CE), field flow fractionation (FFF), and differential
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42 15 The second part of the review is dedicated to applications of spICP-MS. Key steps
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16 in sample preparation and selected instrumental conditions that were used in the
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47 17 published literature are summarized in tabular form. Most frequently, spICP-MS is used
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50 18 for silver (Ag), gold (Au), and titanium dioxide (TiO2) nanomaterials analysis. Data
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52 19 acquisition was typically performed with millisecond dwell times in the past while a time
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1 The table may serve as a guide to choose an experimental procedure depending on the
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matrix that is present in the sample under investigation.
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4 KEYWORDS: Single particle mode, spICP-MS, SP-ICP-MS, nanoparticle analysis, trends,
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14 5 environmental analysis, Au NPs, Ag NPs, TiO2 NPs
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1 Darya Mozhayeva received her B.Sc. in Chemistry (2013) from the
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Al-Farabi Kazakh National University, Kazakhstan, and her M.Sc. in
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9 3 Chemistry (2015) from the University of Siegen, Germany. In 2019,
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4 she received a Dr. rer. nat. degree in Analytical Chemistry from the
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14 5 University of Siegen. Her graduate work was focused on the
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17 6 development and optimization of capillary electrophoresis coupled to spICP-MS for
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7 nanomaterials applications and fundamental studies thereof.
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27 9 Carsten Engelhard is a Professor of Analytical Chemistry in the
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10 Department of Chemistry and Biology at the University of Siegen,
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32 11 Germany. He received his Dr. rer. nat. degree in Analytical
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13 was a postdoctoral associate at Indiana University, USA, with Prof.
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40 14 Gary M. Hieftje (2008–2010). His research interests include fundamentals and applications
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16 characterization, and ambient desorption/ionization.
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1 1 INTRODUCTION
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7 2 1.1 Nanomaterials

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11 3 Nanotechnology is a rapidly developing field of science which utilizes materials and
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4 their properties at the nanometer (10-9 m) scale. The basic idea of nanotechnology has
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16 5 been formulated already in 1960 by Richard P. Feynman: “What would the properties of
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19 6 materials be if we could really arrange the atoms the way we want them?”2 Indeed,
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7 materials at the nanometer scale possess unique properties different from those of the
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24 8 chemically identical bulk materials. The fact that matter has distinct size-dependent
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10 field were conducted by Michael Faraday when he described the properties of “ruby” gold
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32 11 (Au) suspensions in 1857.3 “The state of division of these particles must be extreme; they
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35 12 have not as yet been seen by any power of the microscope.”3 This statement is proof that
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13 the task of analyzing Au nanoparticles (NPs) was a challenge. The variety of states and
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40 14 properties of nanomaterials still presents a challenge for their characterization in
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16 coined.4 The invention of electron microscopes in the 20th century has allowed scientists
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1 preparation, limited area of analysis, and measurement of projections (not three-
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dimensional imaging). Therefore, alternative analysis methods are needed.
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10 3 An alternative method for nanomaterials characterization is single particle
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4 inductively coupled plasma mass spectrometry (spICP-MS, also referred to as SP-ICP-MS
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15 5 depending on the author).5 The technique utilizes a standard ICP-MS setup, and makes
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7 (ideally) one by one. Since the first publications, the field has grown rapidly (Figure 1) and,
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10 applications. The goal of this review is to critically discuss the latest developments and
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13 applications of spICP-MS when used with and without particle fractionation methods.
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16 The basic principle of spICP-MS is that NPs can be detected individually if they are
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1 microseconds above the continuous background.10 The signal abundance is proportional
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to the mass of an NP after careful calibration of the system. NP size can then be calculated
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26 9 The history of discrete particle detection has already been described.8 The first
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10 utilization of the ICP source for time-resolved particles analysis was published by
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13 based on optical emission spectrometry (OES) detection and intended for analysis of
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16 distribution.12 Later, the group of Kawaguchi adapted the technique to ICP-MS (the
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50 18 (LODs) and detect femtogram amounts of zinc.13 This method utilized monodisperse
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1 instrumental conditions significantly affect the resulting particle signal.14 Namely, the
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combination of radio frequency (RF) power, sampling position, and carrier gas (also
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9 3 referred to as “nebulizer gas”) flow were shown to influence the signal. For Zn-containing
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14 5 14 mm sampling position, and 0.8 L∙min-1 carrier gas flow; however, no other elements or
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7 were predicted to be environmental studies (detection of contaminants in air) and control
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22 8 of clean environments (e.g. clean rooms in industrial application).11, 13-16 Also, the
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10 Knight et al. studied micrometer-sized particles of refractory oxides and silicates.18 They
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13 analytes. Furthermore, the mass calibration “still has remained a problem” when the article
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16 A feasibility study for colloid suspension analysis with spICP-MS was published by
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47 17 Degueldre and Favarger in 2003.5 In the paper, results of spICP-MS with 10 ms dwell time
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50 18 for analysis of polydisperse 400 nm (median size) TiO2, 150 nm Al2O3, 400 nm FeOOH, and
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1 quadrupole ICP-MS (ICP-Q-MS), and 48Ti+, 27Al+, 57Fe+, and 44[SiO]+ were chosen for NP
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detection in a model water matrix. Similar studies were published by the same authors for
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28 4 (accessed on 28 May 2019). 314 publications in total. The search command: "SP-ICP-MS"
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1 2 A STEP TOWARDS THE IDEAL spICP-MS METHOD
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7 2 Title and idea of the article were inspired by plenary lectures of Gary M. Hieftje23, 24

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10 3 and his publication dedicated to Howard Malmstadt in 2006.1 Howard Malmstadt’s
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7 of such “an ideal method for atomic spectroscopy” were defined. These characteristics
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23 8 comprise, among others, LOD of a single atom, non-spectral or matrix interferences,
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50 17 “An ideal method for atomic spectroscopy” would require no sample preparation,
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1 samples); however, this still requires an abundance of factors to be considered
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beforehand, especially when a significant amount of matrix is present, in order not to alter
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7 with materials of the sampling or storage containers, storage conditions, and storage time
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22 8 may alter the surface coating or size of the NPs and cause aggregation. Moreover, a
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13 measurement time can be increased to enhance the number of detected particles. In some
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41 15 Nanomaterials often come in complex matrices (e.g. solid matrices, environmental
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46 17 successful extraction and spICP-MS analysis. Table 1 presents an overview of all papers
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1 reader is advised that the main challenges of sample preparation are discussed in some
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detail in other papers and reviews.25, 26
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42 15 In an ideal world, a sample introduction system would exist for spICP-MS that
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47 17 Today, commercially available nebulizers do not achieve a 100% particle transport
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50 18 efficiency, which necessitates the precise determination of the nebulizer transport
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1 through a spray chamber is aimed to eliminate larger droplets, which helps to reduce the
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solvent load and to improve analyte signal stability, but at the same time a considerable
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14 5 rates. With micronebulizers (e.g. at 10 µL min-1 sample uptake rate) the transport
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7 chambers (e.g. 15 cm3) and help to improve the transport efficiency. For example, a
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30 11 NPs surface charges, and assumptions made during PNC determination.28 In general, the
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33 12 higher the sample flow of a nebulizer, the lower its transport efficiency typically is.
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13 However, the matrix tolerance decreases from higher toward lower sample uptake rates.
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38 14 Micronebulizers can be more difficult to operate and maintain due to the dimensions of
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41 15 the inlet capillary (e.g. 0.15 mm),28 which might get obstructed, and sample interchange
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1 Another approach to achieve high transport efficiency for NPs is through a
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microdroplet generator (MDG), in which monodisperse droplets are generated by a
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9 3 piezoelectrically actuated quartz capillary.29 The droplets generated at a controlled
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10 materials.31, 32 In this setup, the MDG was used for system calibration, and the pneumatic
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33 12 A comparison of pneumatic nebulizers and MDG-based sample introduction
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38 14 techniques for NPs quantification.33, 34 It was found that losses are still possible at the
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16 improvements of sample introduction system are still needed to ensure high NP and
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46 17 dissolved ion transport efficiency, robust operation, automated sample introduction, and
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49 18 a high tolerance toward different matrices.
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51 19 One approach to the introduction of solid samples into the ICP-MS is laser ablation
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1 Instrumental parameters were optimized, and imaging of a sunflower plant root (cross
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44 11 a sunflower plant exposed to gold NPs with a mean size of 60 nm, overlaid with a high-
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47 12 resolution time-resolved signal of a single LA-spICP-MS line scan (in yellow). The pixel
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52 14 Reprinted with permission from Metarapi et al. 35 Copyright 2019 American Chemical
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1 2.3 NPs in the ICP Source
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7 2 When NPs enter the ICP, they would ideally get fully vaporized, atomized, and

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15 5 (and other species such as their oxides) that the particles are made of including boiling
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18 6 points and ionization potentials. These differences are likely to result in different optimal
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23 8 micrometer-sized particles were studied in laser ablation ICP-MS and it was found that
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10 efficiency.36, 37 While our understanding of the behavior of micrometer-sized particles in
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34 12 of nanometer-sized particles in spICP-MS is still very limited. For example, Ho et al.
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13 focused on the determination of the maximum signal intensity as a function of the ion
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39 14 sampling position (frequently referred to as “sampling depth”) for different elements in
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42 15 aqueous solution and a selection of Au and ZrO2 NPs.38 It was shown that different
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16 elements have a different signal maximum in their sampling position profiles depending
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47 17 on the combination of element ionization potentials and boiling points of the
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50 18 corresponding oxides. 150 nm and 250 nm Au and 80 nm ZrO2 NPs were investigated in
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1 when calibration with dissolved metals is performed in spICP-MS, it is important to
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14 4 Incomplete ionization may occur due to a relatively larger mass of individual NPs,
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5 and, in turn, would lead to a limited upper size dynamic range for NP analysis.
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19 6 Additionally, matrix ions that reach the plasma together with the NPs may affect the
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22 7 ionization of the NPs. For example, Niemax et al. utilized an MDG to study atomization
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8 processes in the plasma.39 They reported a local plasma cooling effect during atomization
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27 9 which is dependent on the analyte mass. Another finding was that the matrix elements in
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35 12 injector gas flow, the size of the introduced droplet, and also on the mass of the analyte
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38 13 (e.g. particles).40 The presence of a matrix (SiO2 particles in Ca2+ matrix) affects both
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14 particles and matrix components atomization. Namely, there was a delay in complete
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43 15 atomization of two 1.55 µm SiO2 particles compared to one 0.83 µm SiO2 particle that
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46 16 translates to “a spatial shift of about 8 mm in the ICP.”40 It has also been shown that the
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17 position of atomization and ionization is important for ion sampling. If the ions are
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1 detected signal per particle decreases. If the sampling is performed too late, then after
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the particles are ionized, diffusion occurs, and the signal per particle may also decrease.27
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11 3 Ho et al. performed a simulation study focusing on incomplete particle vaporization.41 It
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5 ionization. For example, they reported that the mass calibration leveled off at higher mass
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19 6 values (above 34 fg) at 8 mm sampling position and concluded that Au particles larger
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22 7 than 150 nm may experience incomplete ionization; further experiments to confirm this
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8 hypothesis were not conducted in the study. A sampling position upstream in the plasma
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27 9 (closer to the coil) resulted in an even narrower linear dynamic range (LDR) for Au NP
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30 10 detection (e.g. 6 mm in the simulations results in incomplete vaporization for Au NPs
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11 above 60 nm). Additionally, smaller NPs are subjected to diffusion to a greater extent,
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35 12 causing analyte losses for smaller particles that already completely vaporize early in the
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38 13 ICP. Therefore, it was pointed out that it is important to match the NPs masses used for
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14 calibration with the analyzed particles. A literature search41 was done to determine the
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43 15 detected signal of the particles at which the size calibration is no longer linear (100 nm
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46 16 for Ag NPs34, 150 nm for Au NPs41); however, to what extent incomplete particle ionization
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17 and the limited LDR of the detector influence the obtained values was not studied.
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51 18 Borovinskaya et al. demonstrated that droplets that are off the central axis of the plasma
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1 computational study confirmed the advantages of introducing the samples on-axis to
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achieve higher transport efficiencies of the ions into the MS.43 Chan and Hieftje
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7 last longer than the residence time of droplets in the plasma.44 Here, the OH molecular
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22 8 band, Ar I and H I emission lines were measured with a monochromatic imaging
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30 10 The studies presented in the paragraph above demonstrate that it is indeed
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35 12 Namely, injector gas flow (only Ar and not He was considered in this review), plasma
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38 13 power, sampling position, and injector diameter should be optimized based on the
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14 analytes and matrix used. Other studies were done to find an optimal sampling position.
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43 15 These studied the effect of the ICP-MS sampling position on the signal intensity of Ag
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46 16 and Au NPs.45 It was shown that it is necessary to optimize the sampling position because
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17 it can decrease the size LODs by 25 – 30% for the studied NPs compared to the standard
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51 18 instrument tuning procedure. E.g. the sampling position of 4 mm was found to be optimal
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1 gold standards followed the same trend.45 It is important to note that the optimal
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sampling position would be different for different instruments, the elements of the
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14 5 particle ICP-OES approach to study and select an appropriate sampling position.46 The
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35 12 in spICP-MS application papers are summarized in Table 1 and discussed in the
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46 16 plasma power, and ion sampling efficiency (depends on sampling position), significantly
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17 affect NPs ionization and, in turn, the recorded signals, and should be optimized prior to
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1 point of complete ionization to limit ion cloud diffusion in the plasma and a loss of ions
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1 2.4 Ion Transport
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39 14 analysis. Niu and Houk47 described fundamental aspects of ion extraction in ICP-MS, and
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47 17 mass isotopes have lower ion kinetic energies compared to high-mass isotopes; therefore,
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50 18 the low-mass isotopes get forced out to the edges of the ion beam by high-mass isotopes
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1 have not been published yet. Clearly, such ion sampling and transport effects as are
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41 13 short (few hundreds of microseconds)10 NP signals. The mass analyzers that are available
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1 of conditions to be stable (ion travel time through the mass analyzer etc.). If one decides
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16 250 nm in diameter.54, 55 After passing through the mass analyzer, the ion detection itself
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14 5 with H2 (28Si+) and mass-shift detection with CH3F (28Si19F+) and significantly improve the
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17 6 size LODs (Figure 4).56 TiO2 NPs can be quantified with the use of NH3 as the reaction gas
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7 in candy products57 and water matrices with high Ca content58 (48Ca+ interferes with the
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22 8 most abundant 48Ti+ isotope, mass-shift detection of [48Ti(14N1H3)3(14N1H)]+). In contrast
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7 than with ICP-Q-MS34, 69, 70). In a follow-up study, the ICP-TOF-MS was used to perform
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30 11 (values determined with Poisson statistics).71 The benefit of all-isotope-information in a
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38 14 29 nm, 14 nm, and 7 nm LOD for Ti, Mo, and Au containing NPs respectively.74 It was used,
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45 5 suspension of CeO2 engineered NPs (a and b (zoomed on Ce)) and a pristine soil sample
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1 2.6 Detector Dwell Time
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15 5 they are most frequently used for ICP-Q-MS. Usually, ion detection occurs sequentially
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18 6 within defined time intervals called dwell times. In spICP-MS, dwell times in the
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7 millisecond time range are still the most frequently used (Table 1, also determined by the
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23 8 available settings of the instruments). As was demonstrated earlier, for example in a study
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26 9 on the effect of a CE buffer matrix on the particle ion cloud duration in CE-spICP-MS10,
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10 NPs typically result in ion cloud event durations on the order of a few hundreds of
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31 11 microseconds. One fundamental limitation of millisecond dwell times is that only one data
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34 12 point is used to describe a shorter transient. Additionally, a dead time between the
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13 individual dwell times5 may interrupt the time-resolved measurements and lead to count
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39 14 losses in pulse-counting mode of the SEM. The occurrence of a NP between two adjacent
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42 15 dwell time intervals may cause one NP to be detected as two smaller ones (split-particle
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16 events). Similarly, towards higher particle numbers in suspension, two or more particles
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47 17 may fall into one dwell time (particle coincidence), which results in a skewed PNC.
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50 18 Therefore, the users of millisecond dwell times in spICP-MS should always consider a
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52 19 suitable PNC range for their measurements and be aware of the limitations of the method
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1 when the data is used to draw conclusions e.g. from particle stability and toxicology
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studies.
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11 3 One possible approach to overcome the measurement artifacts is to use
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14 4 integration times that are significantly shorter than the duration of NPs ion clouds (on the
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5 microsecond time scale). This way allows for obtaining time-resolved profiles of the NP
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19 6 ion clouds with an adequate number of data points per transient. The main challenge then
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22 7 arises in the data acquisition, storage, and processing of µs time-resolved data. For
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8 example, if the dwell time would be 10 µs, then each 1 s 100,000 data points are obtained.
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27 9 Therefore, a special data processing for visualization and quantification is required that is
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30 10 different from standard ICP-MS data acquisition (DAQ) and software, respectively. In
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11 addition, the accurate extraction of NP ion clouds and their unambiguous identification
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35 12 above possible background counts are critical in µs-spICP-MS. To the best of our
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38 13 knowledge, the first system for time-resolved particles analysis with ICP-MS was
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14 presented by Nomizu et al. in 2002.16 The detection was performed with 20 µs time
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43 15 resolution for 1 min in the pulse-counting mode; however, it is stated that the
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46 16 measurement time was limited by the computer hard disc space. Later, ICP-MS became
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17 commercially available that allow data acquisition with 100, 50 and 10 µs dwell times. For
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51 18 example, several authors utilized a dwell time as low as 10 µs and highlighted the
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54 19 advantages and disadvantages compared to millisecond time.49, 75, 76 In the study by
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1 Montaño et al., NPs signal extraction from the background was carried out by applying a
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three time standard deviation (SD) of the background criterion.49 One limitation of
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9 3 commercially available ICP-MS instrumentation is the fact that the total measurement
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4 time with high time resolution is currently limited to minutes. An ideal spICP-MS
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14 5 instrument would be able to operate continuously with microsecond time resolution
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17 6 (hours rather than minutes), without significant dead time, and be able to process the
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7 data online. As a contribution from our group to help to get closer to such an ideal system,
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22 8 we presented a DAQ system developed in-house for spICP-MS with 5 µs time resolution
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25 9 and truly continuous data acquisition (Figure 6).77 The system allows to perform the
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10 acquisition for any measurement length (only limited by the hard disk space). It was used
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30 11 for continuous measurements of up to 60 min with the coupling of a separation
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33 12 technique.10 The obtained data was processed with in-house written software and particle
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13 events were extracted on a particle-by particle level by setting defined count thresholds.77
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14 SF-ICP-MS has also been used with microsecond time resolution (as short as 10 µs).59, 60,
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43 15 63, 64 NPs identification in the raw data was carried out by determining the peak maxima
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46 16 above a certain threshold.59, 64 Tuoriniemi et al. introduced a peak recognition algorithm
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17 to an SF-ICP-MS using a 100 µs dwell time based on cluster detection.60 Another mass
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51 18 analyzer that can be used for fast detection of NPs is ICP-TOF-MS that can be operated
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1 While the majority of spICP-MS studies investigate spherical shaped nanomaterials
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(or assume spherical shape), first attempts have been undertaken to distinguish NPs with
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9 3 different shapes and high aspect ratios. For example, microsecond time resolution helped
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4 to distinguish spherical NPs from nanorods and to perform dimensional characterization
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14 5 of the NPs based on their ion cloud signal duration.78 The composition of NPs of gold and
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17 6 silver alloys has also been assessed using profiles of the ion clouds.79 The detection of
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7 silica colloids, which otherwise would require the use of a collision gas to remove
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22 8 polyatomic interferences (from nitrogen dimer ions), has been simplified with
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25 9 microsecond time resolution detection.80
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30 10 As reported above, the advent of microsecond time resolution helped to
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11 significantly improve the performance of spICP-MS compared to millisecond time
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35 12 resolved data. The number of data points per ion cloud event is improved, the background
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38 13 is divided between adjacent dwells,76, 77 and, thus, the detection of NPs is possible in a
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14 wider range of PNCs and in the presence of higher background and dissolved ions
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43 15 concentrations. However, it should also be noted that the data obtained with microsecond
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46 16 time resolution represents in most of the cases only several counts per dwell time (with
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17 5-10 µs dwell times) and that the normal distribution statistics may not apply to this data
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51 18 anymore. In fact, we suggest that Poisson statistics should be considered in order to
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27 3 Figure 6. Representative ICP-MS signal (monitoring m/z 197Au+) due to 30 nm Au NPs
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30 4 (CNP = 2.5 × 105 NP mL−1) acquired simultaneously for 2 s with (a) 10 ms dwell time
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32 5 (vendor software), and (b) 5 μs dwell time (home-built data acquisition system). First zoom
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35 6 level shows several particle events in (c) and (d) for 500 ms (of highlighted section in a
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7 and b). Second zoom level (e) shows the temporal profile of a single particle's ion cloud
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40 8 identified with the home-built data acquisition system in (d). Reproduced from Strenge
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43 9 and Engelhard77 with permission from The Royal Society of Chemistry.
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1 2.7 Quantification Considerations
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7 2 The principles of quantification with spICP-MS were described in previous reviews

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10 3 in detail.6, 8, 9 Briefly speaking, quantification can be performed using NPs standards of the
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4 same elemental composition or dissolved standards solutions of the element after taking
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15 5 into account the nebulization efficiency in order to obtain particle size and size
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18 6 distributions with a pneumatic nebulizer. The PNC determination requires a NP standard
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7 with the known PNC of the same element, or of a different element, if the same transport
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23 8 and nebulization efficiencies are assumed. The main limitations today is the fact that only
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26 9 a limited variety of the NPs standards of different composition and certified PNC exists,9
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10 and difficulties in determination of the nebulization efficiency can occur.82 Interlaboratory
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31 11 studies have shown that the determination of median particle diameter (2 – 5%
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34 12 repeatability SD, 15 –25% reproducibility SD) is much more repeatable and reproducible
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13 compared to the determination of PNC (7 – 18% repeatability SD, 70 – 90%
37
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39 14 reproducibility SD). The lack of stability of the NPs in initial suspensions and different
40
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42 15 matrices depending on the handling and storage conditions may have a significant
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16 contribution to this fact.82, 83 Recently, a metrological study assessing the determination
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47 17 and validation of Au NP size and size distribution was performed.84 High-resolution
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50 18 scanning electron microscopy (HR-SEM) was used as one of the methods to validate the
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52 19 results obtained with spICP-MS. The two methods show a good agreement with relative
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55 20 precision of 0.5%. It was emphasized that the NP size characterization provided by their
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1 suppliers is not sufficient, and that more characterization is needed if the NPs are intended
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to be used in research. Alternative methods including the use of MDG30, 32, 33, isotope
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9 3 dilution66, 67, and flow injection85, 86 are promising new quantification approaches.
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4 However, more studies on the metrology of these methods are required to ensure
12
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14 5 accurate NPs analysis.
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19 6 The counting stage of the electron multiplier is typically used up until 2·106 cps27
20
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22 7 because there is a detector dead time (on the order of 50 ns)77 between the acquisitions
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8 caused by physical and detector construction limitations. Because NPs result in short but
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27 9 intense ion signals, some of the counts per NP are lost due to the dead time (e.g. 6.2%
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30 10 for 40 nm and 24.4% for 60 nm Au NPs).77 This phenomenon leads to a limited LDR for
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11 NPs size detection. Liu et al. extended the LDR for Au NPs from 10 nm to 70 nm in “highest
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35 12 sensitivity mode” to 200 nm in “less sensitive modes”.54 The approaches that can be used
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38 13 to extend the LDR are based on decreasing the temporal ion signal abundance by the use
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14 of low extraction voltage54 or collision-reaction cell.54, 55 The effect of the plasma
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43 15 conditions on the LDR for Au NPs was investigated by Lee and Chan and 250 nm Au NPs
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46 16 were reportedly outside of the LDR.87
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51 17 The size LODs depend on the sensitivity of the instrument, and the ideal LOD of
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18 one atom cannot be achieved nowadays with the current ICP-MS systems. The main
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1 reasons are a low nebulization efficiency, low ionization efficiencies of some elements in
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the argon plasma, and ion transfer into and inside the mass spectrometer. Lee et al.
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9 3 calculated the size LODs for 40 elements for an ICP-Q-MS.70 So far, most of the elements
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4 still have LODs well above 10 nm6, 70 and spICP-MS instruments are yet to be developed
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14 5 that can cover the complete nanoscale from 1 nm to 100 nm routinely.
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19 6 PNC and size LODs are both based on a statistical evaluation of the data, therefore,
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22 7 data processing plays an important role in spICP-MS. For millisecond time resolution, the
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8 size LOD is usually determined as 3×SDBG (SD of the background) or 5×SDBG above the
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27 9 background.69, 88 Real world samples may have higher size LODs due to a continuous
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30 10 background. If the blank is well known and no NP events are detected, then the PNC LOD
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11 was proposed to be three detected NP events by Laborda et al.88 based on the Currie
34
35 12 Poisson-Normal approximation (2.71 + 3.29 𝑆𝐷𝐵𝐺 for a “well-known” blank). This PNC
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38 13 LOD may need recalculation if some NP events are detected even in blanks. The data
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14 obtained with microsecond time resolution usually requires even more data processing,
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43 15 because each NP is presented by several data points. Until now there is still no established
44
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46 16 approach to extract NPs from the raw data, and each developed system utilizes its own
47
48
17 algorithm (discussed in the previous chapter). Therefore, there is still a need to develop
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51 18 statistical approaches based on counting statistics for the quantitative extraction of NPs
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54 19 from the time-resolved data.
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1 Another issue in NPs quantification is the differentiation of NPs from the
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background. The continuous background in ICP-MS may be a result of dissolved ions,
6 2
7

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9 3 natural background, or interferences. Bi et al. proposed an approach to differentiate NPs
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4 from the background with the use of K-means clustering to improve the differentiation of
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14 5 the NPs from the BG compared to “traditional standard deviation approach”.89 Cornelis
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17 6 and Hassellöv developed an approach for data deconvolution taking into the account the
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7 noise components of the ICP-MS to differentiate the NP that are not fully resolved from
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22 8 the background.90 An approach that utilizes modelling of the background based on the
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25 9 noise components with Monte Carlo simulation was developed for the data obtained with
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10 ICP-TOF-MS with 200 Hz resolution.91 The method allows to distinguish small NPs from
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30 11 the background, and the decision criteria for NP detection were revisited. Alternatively,
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33 12 dissolved ions can be removed with ion exchange resins92 or the samples can be analyzed
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13 after dilutions.93 Microsecond time resolution helps to distinguish NPs from continuous
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38 14 background (up to 1,000,000 cps), and quantify both the dissolved ions and NPs.81
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43 15 2.8 Coupling of spICP-MS to Separation Techniques
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47 16 A promising approach to obtain more information about mixtures of NPs is the
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17 online coupling of spICP-MS to a separation technique. As spICP-MS is used for NPs size
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52 18 and size distribution determination, different separation techniques allow to obtain
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55 19 complimentary information. However, the main challenge is that spICP-MS requires the
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1 discrete detection of individual NPs while separation techniques will result in a local
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preconcentration of analytes of a certain type (in a peak), which then elute/migrate
6 2
7

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9 3 together from the column/capillary. Additionally, separation techniques usually require a
10
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4 separation medium (mainly organic compounds), that is introduced into the ICP-MS and
12
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14 5 may cause matrix effects. Therefore, the combined use of a separation/fractionation
15
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17 6 technique and spICP-MS requires a careful method development to ensure that:
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22 7  the NPs are separated based on their properties but not focused in time to the
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8 extent that the detection of single NPs is significantly hindered;
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27 9  the organic buffer does not interfere with the NP detection (instrumental
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30 10 parameters optimization);
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11  the suitable dwell time is chosen;
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35 12  the NPs do not undergo size transformations during the separation;
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38 13  the best size and PNC LODs are achieved.
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43 15 An overview of the separation techniques that were coupled online to spICP-MS is
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46 16 presented in Table 2, and the main features are highlighted. The first online coupling of
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17 spICP-MS to hydrodynamic chromatography (HDC) was presented by Pergantis et al. in
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51 18 2012, where Au NPs were separated by their size.94 In 2016, spICP-MS was coupled online
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54 19 to asymmetric field flow fractionation (AF4) to fractionate the NPs by their size and also
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1 core-shell NPs (Ag core with SiO2 shell) from mono-component NPs (Ag NPs) (Figure 7).95
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Electrospray-differential mobility analysis (ES-DMA) was also coupled online to spICP-
6 2
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8
9 3 MS.96 This method allows to distinguish different sizes of NPs, assess their aggregation,96
10
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4 and distinguish nanorods from spherical NPs.97 The coupling of capillary electrophoresis
12
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14 5 (CE) to spICP-MS98 allows to separate the NPs not only by their size, but also in some
15
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17 6 cases to separate NPs with different coatings (Figure 8).99 According to Table 2, most of
18
19
7 the separation method utilize surfactants, most commonly sodium dodecyl sulfate (SDS),
20
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22 8 to enhance the separation of NPs from each other. The coupling of separation techniques
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25 9 online to spICP-MS has the potential to answer non-trivial questions in NPs mixtures
26
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10 analysis, where spICP-MS alone does not provide sufficient information.
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35 2 Figure 7. (a) Size distribution of a mixture containing 40 (1 ng/L), 60 (2 ng/L), and 80 nm
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37 3 (6 ng/L) Ag NPs and Ag-SiO2 NPs (1 ng Ag/L) obtained using spICP-MS. (b) Contour plot
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40 4 result of an AF4-spICP-MS analysis on a suspension containing 40, 60, and 80 nm Ag NPs
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43 5 (678 ng/L, 1.39 μg/L, and 3.73 μg/L, respectively) and Ag-SiO2 NPs (624 ng Ag/L). In (a)
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45 6 and (b), the Ag mass concentration ratio of 40, 60, and 80 nm AgNPs, and Ag-SiO2 NPs
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48 7 was about 1:2:6:1. Reprinted with permission from Huynh et al.95 Copyright 2016 American
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33 2 Figure 8. Comparison of a standard CE-ICP-MS plot (A) and first CE-spICP-MS two-
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3 dimensional color map (B) acquired from a complex five-component mixture of different
37
38 4 nanomaterials (5 µg L-1 citrate-coated 20 nm sized, 35 µg L-1 each citrate and PVP-coated
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41 5 40 nm sized, 100 µg L-1 PVP-coated 60 nm sized, and 200 µg L-1 citrate-coated 60 nm
42
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6 sized Ag NPs). The analysis was conducted by monitoring at 107Ag+ with 5 µs dwell time,
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Table 2: Separation methods coupled to spICP-MS for NP analysis.
5
6 Techniqu Analytes Nebulizer and Plasma parameters Dwell Separation Referenc

7
8 e spray chamber time features e
9
10 coupled
11
12 online
13
14 CE 10, 20, 30, 40, Microflow RF power 1500 W, cooling gas 2 ms 70 mM SDS, 98
15
16 60 nm citrate- nebulizer with low 15 L min-1, auxiliary gas 1 L min-1, 10 mM CAPS at
17
18 coated Au NPs volume spray nebulizer gas 0.8 L min-1, sampling pH 10 buffer
19
20 chamber position 7 mm
21
22 CE 20, 40, 60 nm Microflow RF power 1450 W, cooling gas 5 µs 60 mM SDS, 10
23
24 citrate-coated Ag nebulizer with low 14 L min-1, auxiliary gas 0.8 L min-1, 10 mM CAPS at
25
26 NPs volume spray nebulizer gas 0.8 L min-1, sampling pH 10 buffer,
27
28 chamber position 3.5 mm online
29
30 preconcentration
31
32
33
34
35
36
37
38
39
40
41
42
43 48
44
45
46
47
1
2
3
4
Table 2: Separation methods coupled to spICP-MS for NP analysis.
5
6 Techniqu Analytes Nebulizer and Plasma parameters Dwell Separation Referenc

7
8 e spray chamber time features e
9
10 coupled
11
12 online
13
14 CE 20, 40, and 60 nm Microflow RF power 1450 W, cooling gas 5 µs 60 mM SDS, 99
15
16 citrate-coated; 20, nebulizer with low 14 L min-1, auxiliary gas 0.8 L min-1, 10 mM CAPS at
17
18 40, and 60 nm PVP- volume spray nebulizer gas 0.8 L min-1, sampling pH 10 buffer,
19
20 coated; 40 and chamber position 3.5 mm online
21
22 60 nm PEG-coated; preconcentration,
23
24 40 nm BPEI-coated separation of NPs
25
26 Ag NPs with different
27
28 coatings
29
30 1
31
32
33
34
35
36
37
38
39
40
41
42
43 49
44
45
46
47
1
2
3
4
Table 2: Continued.
5
6
Techniqu Analytes Nebulizer and Plasma parameters Dwell Separation Referenc

7
8
e spray chamber time features e
9
10
coupled
11
12
online
13
14
ES-DMA 30, 40, 60, 80, n/s n/s 10 ms Ammonium 96
15
16
100 nm Au NPs acetate was used
17
18
for electrospray,
19
20
aggregates
21
22
detection
23
24 ES-DMA CTAB- and citrate- n/s n/s 10 ms Quantification of 97
25
26 coated Au length and
27
28 nanorods diameter of
29
30
(diameters 11.8 to nanorods,
31
32
38.2 nm, aspect
33
34
ratios 1.8 to 6.9)
35
36
37
38
39
40
41
42
43 50
44
45
46
47
1
2
3
4
Table 2: Continued.
5
6

7
8
9
10
coupled
11
12
online
13
14
FFF 40, 60, 80, 100 nm Concentric Nebulizer gas 0.88-0.96 L min-1 5 ms 10 kDa 95
15
16
citrate-coated Ag nebulizer with regenerated
17
18
NPs, 60 nm citrate cyclonic spray cellulose
19
20
coated Au NPs, chamber membrane, 0.02%
21
22
51 nm Ag core and FL-70 carrier,
23
24
21.6 nm SiO2 shell separation of
25
26
citrate-coated NPs Au/SiO2 core/shell
27
28
NPs from Au NPs
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43 51
44
45
46
47
1
2
3
4
Table 2: Continued.
5
6

7
8
9
10
coupled
11
12
online
13
14
FFF AgPURE® (<20 nm Concentric RF power 1550 W, cooling gas 5 ms 10 kDa 100
15
16
polyoxyethylene nebulizer with 14 L min-1, auxiliary gas 0.8 L min- regenerated
17
18
fatty acid ester- cyclonic spray 1, nebulizer gas 1 L min-1 cellulose
19
20
coated) in food chamber membrane,
21
22
simulants (water, ultrapure water as
23
24
10% ethanol, 3% mobile phase
25
26
acetic acid)
27
28
extracted from
29
30
model films
31
32
HDC 30, 60, 80, 100 nm V-groove n/s 10 ms 10 mM SDS at 94
33
34
citrate-coated Au nebulizer with pH 11 eluent
35
36
NPs double pass Scott
37
38
spray chamber
39
40
41
42
43 52
44
45
46
47
1
2
3
4
Table 2: Continued.
5
6

7
8
9
10
coupled
11
12
online
13
14
HDC 10, 30, 50, 100, 150, PTFE spray RF power 1400 W, auxiliary gas 5 ms 2 mM Na2PO4, 101
15
16
250 nm citrate- chamber 0.82 L min-1, nebulizer gas 60 mM
17
18
coated Au NPs 0.78 L min-1, sampling position formaldehyde,
19
20
40 mm 1.8 mM SDS,
21
22
3.2 mM Brij L23,
23
24
3.2 mM Triton X-
25
26
100 at pH 7.5-8
27
28
eluent
29
30
HDC 40, 80 nm Ag NPs n/s n/s 100 µs 1 mM NaNO3, 102
31
32
spiked in Milli Q 0.0013% w/w SDS,
33
34
water, WWTP 0.0013% w/w
35
36
influents and Triton X-100 at
37
38
effluents pH 7.5 eluent
39
40 1
41
42
43 53
44
45
46
47
View Article Online
DOI: 10.1039/C9JA00206E
1
2
3
4
1 3 APPLICATIONS OF spICP-MS
5
6
7 2 3.1 Applications of spICP-MS

8
9
10
11 3 There has been a significant increase in the number of published studies that utilize
12
13
4 spICP-MS in recent years (Figure 1) and the majority of these publications is dedicated to
14
15
16 5 applications thereof. Table 1 summarizes the papers that include applications of spICP-
17
18
19 6 MS for analysis of different samples and different matrices (note that fundamental studies
20
21
7 on spICP-MS are not included). The works included in Table 1 are grouped by the analysis
22
23
24 8 matrix and then sorted by the year of publication. Table 1 is a summary of the articles with
25
26
27 9 a short description of the sample preparation and selected instrumental parameters. The
28
29
10 reader is advised to check the original publications for more details.
30
31
32
33 11 It became apparent when compiling this table that many publications do not
34
35
36 12 include all experimental conditions that the authors of this review consider important for
37
38
13 spICP-MS. As discussed above, the combination of RF power, sampling position, and
39
40
41 14 carrier gas flow is crucial for best spICP-MS performance. The parameters dwell time and
42
43
44 15 measured isotopes are very important as well. Most of the article state the dwell time that
45
46
16 was used for the measurements, with microsecond time resolution (most frequently
47
48
49 17 0.1 ms dwell time) becoming more widely used in recent years. The majority of the articles
50
51
52 18 do not include the sampling position or injector diameter in the experimental
53
54
55
56
57
58 54
59
60
View Article Online
DOI: 10.1039/C9JA00206E
1
2
3
4
1 descriptions. Some articles cite their previous works and do not cite the exact conditions
5
that were used for the study.
6 2
7

8
9
10 3 The majority of the spICP-MS application papers (Table 1) utilize a method for
11
12
4 direct analysis of aqueous media (exposure media, model and real environmental water
13
14
15 5 samples, etc.) with or without dilution. Dilution is an effective tool to reduce the matrix
16
17
18 6 load. A filtration step is introduced frequently to avoid clogging of the nebulizer; however,
19
20
7 this step may lead to partial losses of NPs due to interactions with the filter membrane
21
22
23 8 materials, even if the NPs are smaller than the membrane pores.103 Therefore, more
24
25
26 9 research is required to determine suitable filter materials for NPs with different coating to
27
28
10 reduce these interactions or identify membranes that show a somewhat reproducible
29
30
31 11 adsorption behavior. When enzymatic or alkaline digestions are used for more complex
32
33
34 12 matrices (tissue, plants, etc.), care must be taken to ensure that the NPs keep their initial
35
36
13 state after these procedures. The ultimate goal of any sample preparation step must be a
37
38
39 14 high particle recovery rate and little to no species transformation.
40
41
42
43 15
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 55
59
60
1
2
3
4
Table 1: Summary of peer-reviewed spICP-MS nanoanalysis papers with selected experimental conditions, sample matrix, and
5
6
particle size LOD.

7 Year NP types Matrix Sample Nebulizer and Plasma Mass Measured Dwell Size LOD Features Reference
8
analyzed preparation spray chamber parameters analyzer isotopes time (ESD)
9
10 Animal Tissue
11
12 2012 <20 nm NM- Rat tissue Enzymatic Babington RF power Q 107 Ag+, 3 ms 20 nm Oral exposure to 104
13 300K or digestion with nebulizer 1400 W 109 Ag+ rats over a period
14
<15 nm PVP- proteinase K of 28 days
15
16 coated Ag NPs
17 2013 30, 80, 1500 nm Lumbriculus Sonication with n/s n/s Q n/s n/s n/s NPs detected in 105
18
Ag NPs variegatus tissue water and tissue even after
19
20 powders, 30, 0.45 µm 48 h depuration
21 70 nm PVP- filtering
22
coated Ag NPs
23
24 2013 100 nm PVP- Spiked ground Alkaline Glass nebulizer, n/s Q n/s 10 ms n/s 106
25 coated Au NPs, beef, Daphnia digestion with cyclonic spray
26
60 and 100 nm magna, TMAH chamber
27
28 PVP-coated Ag Lumbriculus
29 NPs variegatus tissues,
30
aqueous samples
31
32 2013 Ag nanowires Daphnia magna Dilutions, where n/s n/s Q 107 Ag+, 10 ms <30 nm ESD 107
33 with PVP or hemolymph, necessary 197 Au+
34
aluminum aqueous samples
35
36 doped SiO2
37 coatings
38
39
40
41
42
43 56
44
45
46
47
1
2
3 2014 60 nm Au NPs Rat tissue Alkaline TMAH MicroFlow PFA RF power Q 197 Au+ 3 ms Only NPs Intravenous 108
4
digestion and nebulizer, 1550 W, >44 nm administration of
5
6 enzymatic cyclonic spray cooling gas were the NPs

7 digestion with chamber 14 L min ,-1 considered
8
proteinase K auxiliary gas
9
10 0.8 L min-1,
11 nebulizer
12
gas 0.96-
13
14 0.99 L min-1
15
16
1
17
18 Table 1: Continued.
20
21 analyzed preparation spray chamber parameters analyzer isotopes time (ESD)
22 2014 60 nm citrate- Spiked chicken Enzymatic Conical glass RF power Q 107 Ag+ 3 ms n/s 109
23
coated Ag NPs meat digestion with concentric 1400 W,
24
25 proteinase K nebulizer, cooling gas
26 quartz impact 13 L min-1,
27
bead spray auxiliary gas
28
29 chamber 0.7 L min-1,
30 nebulizer
31
gas
32
33 1.1 L min-1
34 2014 <25 nm Rat spleen Enzymatic PFA n/s Q 49 Ti+ 3 ms n/s Oral exposure 110
35
anatase TiO2 digestion with micronebulizer,
36
37 proteinase K heated cyclonic
38 spray chamber,
39
desolvation
40
41 system
42
43 57
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2015 50 nm PVP- Earthworms tissue Enzymatic Conical glass RF power Q 107 Ag
+ 3 ms 30 nm In vivo exposure 111
9 coated Ag NPs digestion with concentric 1400 W, in soil
10
proteinase K nebulizer, cooling gas
11
12 quartz impact 13 L min-1,
13 bead spray auxiliary gas
14
chamber 0.7 L min-1,
15
16 nebulizer
17 gas
18
1.1 L min-1
19
20 2015 42 nm PVP- Spiked chicken Reference to Reference to Reference to n/s n/s n/s n/s Two laboratories 112
21 coated Ag NPs meat previous previous studies previous carried out the
22
studies studies analysis with
23
24 different
25 methods
26
2017 18-20 nm Ag Mouse maternal Alkaline Quartz n/s Q 107 Ag
+ 0.1 ms 13 nm Nose-only 113
27
28 NPs tissues, placentas, digestion with concentric inhalation of a
29 foetuses TMAH nebulizer, NPs aerosol for
30
cyclonic spray pregnant mouse
31
32 chamber females
33
34
35
36
37
38
39
40
41
42
43 58
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2017 20 nm PVP- Hens livers and Enzymatic n/s RF power SF mass 109 Ag + 2 ms 10 nm Oral 114
9 coated Ag NPs yolks digestion with 1000 W, analyzer administration to
10
proteinase K cooling gas was used hens
11
12 15 L min ,-1 in low
13 auxiliary gas resolutio
14
1.2 L min ,
-1 n mode
15
16 nebulizer
17 gas
18
1.1 L min-1
19
20 2017 30, 60 nm Au Caenorhabditis Alkaline C-type n/s Q 197 Au+ 10 ms n/s Sucrose density 115
21 NPs elegans nematode digestion with nebulizer, gradient
22
TMAH impact bead centrifugation
23
24 spray chamber was used to
25 remove non-
26
ingested NPs
27
28 2017 40 to 750 nm Game meat Enzymatic Low-flow RF power Q 208 Pb+ 5 ms 40 to 80 nm Lead from the 116
29 Pb NPs digestion with concentric 1550 W, bullets; size LOD
30
proteinase K nebulizer, cooling gas was reported to
31
32 cyclonic spray 14 L min ,-1 depend on the
33 chamber auxiliary gas lead background
34
0.65 L min , -1
35
36 nebulizer
37 gas
38
1.10 L min-1
39
40
41
42
43 59
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2017 26 nm Ag NPs Chicken meat Dilution of MicroMist RF power Q 107 Ag + 10 ms n/s 117
9 paste after in vitro digest extracts nebulizer, 1500 W,
10
model, saliva, Scott-type cooling gas
11
12 gastric, intestinal spray chamber 15 L min-1,
13 digestions auxiliary gas
14
0.73 L min-1,
15
16 nebulizer
17 gas
18
0.68 L min-1
19
20 (these
21 conditions
22
specified
23
24 only for total
25 silver
26
analysis)
27
28 2017 15 to 75 nm Spiked chicken Enzymatic Varied among Varied Q or n/s n/s 3 ms 15-20 nm Interlaboratory 82
29 PVP-coated Ag muscle meat digestion with the participants among the method
30
NPs proteinase K participants performance
31
32 study with over
33 10 laboratories
34
2017 60, 80 nm Au LA-SP-ICP-MS Intravenous n/s RF power Q 197 Au
+ 1 ms n/s 118
35
36 NPs imaging of mice injection 1400 W,
37 heart, lung, spleen, nebulizer
38
liver, kidney gas
39
40 0.7 L min-1
41
42
43 60
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2018 CeO2 NPs Liver and lungs Enzymatic Low-flow RF power Q 140 Ce + 3 ms 18 nm Intravenous 119
9 tissue of female digestion with concentric 1550 W, injection of NPs;
10
mice proteinase K nebulizer, cooling gas no NPs in liver
11
12 cyclonic spray 14 L min , -1 were detected
13 chamber auxiliary gas after oral
14
0.8 L min ,-1 exposure
15
16 nebulizer
17 gas
18
1.1 L min-1
19
20 2018 30, 80 nm PVP- Liver, gill, intestine Alkaline n/s RF power Q 107 Ag+, 1 ms n/s 120
21 coated Ag and tissue of zebrafish digestion with 1550 W, 197 Au +
22
Au NPs (Danio rerio), TMAH nebulizer
23
24 aqueous samples gas
25 1.14 L min-1,
26
sampling
27
28 position
29 8.0 mm
30
31
32
33
34
35
36
37
38
39
40
41
42
43 61
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2018 50, 100 nm Bivalve mollusk Ultrasound Glass concentric RF power Q 49 Ti + 0.1 ms 24.4 - 121
9 rutile TiO2 NPs assisted or PFA nebulizer 1600 W, 30.4 nm
10
enzymatic (n/s clearly), cooling gas
11
12 digestion with cyclonic spray 16 L min-1,
13 pancreatine chamber auxiliary gas
14
and lipase 1.2 L min-1,
15
16 mixture nebulizer
17 gas
18
0.95 L min-1
19
20 2018 TiO2 and CeO2 Spiked zebrafish Enzymatic Conical glass RF power Q 48 Ti+, 140Ce+ 3 ms 100 nm Method for NP 122
21 NPs (Danio rerio) digestion with nebulizer, 1400 W, TiO2, 30- extraction from
22
(intestine, liver, proteinase K, impact bead cooling gas 40 nm CeO2 tissue was
23
24 gills, brain) H2O2 treatment, spray chamber 13 L min ,-1 optimized
25 SDS auxiliary gas
26
stabilization 0.7 L min-1,
27
28 nebulizer
29 gas
30
1.1 L min-1
31
32
33
34
35
36
37
38
39
40 Biological Applications
41
42
43 62
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2009 20, 40, 80 nm Immunoassay with 2% HNO3 to Glass concentric RF power Q 197 Au+ 10 ms 15 nm 123
9 Au NPs NPs as tags to release the tags, nebulizer, 1400 W,
10
antibody dilution impact bead cooling gas
11
12 spray chamber 13 L min-1,
13 auxiliary gas
14
0.8 L min-1,
15
16 nebulizer
17 gas
18
0.85 L min-1
19
20 2014 25 nm Au, Multiplex DNA Melting wash, n/s RF power Q 107 Ag+, 0.5 ms 124
21 25 nm Ag, assay with NP tags dilution 1200 W, 197 Au ,
+
22
20 nm Pt cooling gas 195 Pt+
23
24 citrate-coated 13 L min-1,
25 NPs auxiliary gas
26
0.8 L min-1,
27
28 nebulizer
29 gas
30
0.82 L min-1
31
32
33
34
35
36
37
38
39
40
41
42
43 63
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2015 80 nm citrate- Primary human Alkaline MicroFlow PFA RF power Q 197 Au + 10 ms n/s 125
9 coated Au NPs umbilical vein digestion with nebulizer, 1550 W,
10
endothelial cells TMAH cyclonic spray cooling gas
11
12 chamber 14 L min-1,
13 auxiliary gas
14
0.8 L min-1,
15
16 nebulizer
17 gas 0.96-
18
0.99 L min-1
19
20 2016 7, 20 nm TiO2 Mouse Lysis in Triton n/s RF power Q 107 Ag+, 48Ti+ 3 ms 22 nm Ag, 126
21 NPs; 50, 75 nm neuroblastoma X-100 1400 W, 69 nm TiO2
22
citrate-coated cells additional
23
24 Ag NPs gas flow (Ar)
25 0.95 L min-1
26
2016 10, 30, 70 nm OECD 201 culture Filtration n/s n/s TQ 107 Ag+ 3 ms n/s 127
27
28 PEG- BPEI-, medium with (0.45 µm pore
29 citrate-coated Pseudokirchiniella size), dilution
30
Ag NPs subcapitata
31
32 2018 18 nm Al NPs, Model cell culture n/s PFA nebulizer, Cooling gas Q n/s 3 ms 54 nm Al, Several methods 128
33 20 nm Al2O3 medium cyclonic spray 13 L min ,-1 50 nm Al2O3, for NP
34
NPs, 25 nm chamber auxiliary gas 60-100 nm characterization
35
36 TiO2 NPs 0.7 L min ,
-1 TiO2 are described
37 nebulizer
38
gas
39
40 0.89 L min-1
41
42
43 64
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2018 NPs formed Medium for algal Dilution MicroMist RF power Q 52 Cr+ 0.05 ms 90 nm 129
9 from Cr salts
III ecotoxicity testing nebulizer 1500 W, Cr(OH)3
10
cooling gas
11
12 13.5 L min-1,
13 auxiliary gas
14
0.77 L min-1,
15
16 nebulizer
17 gas
18
0.87 L min-1
19
20 2019 30 nm citrate- Oligonucleotide- The detailed Glass concentric RF power Q 197 Au+ 3 ms n/s 130
21 coated Au NPs functionalized Au procedure is nebulizer, 1750 W,
22
NPs after sandwich presented in impact bead cooling gas
23
24 hybridization the article spray chamber 17 L min-1,
25 reaction-capture auxiliary gas
26
1 L min-1,
27
28 nebulizer
29 gas
30
1.05 L min-1
31
32 Body Fluids and Tissue
33
34
35
36
37
38
39
40
41
42
43 65
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2012 60 nm citrate- Model saliva, Dilution Babington type RF power Q 107 Ag + n/s n/s 131
9 coated Ag NPs gastric, duodenal, nebulizer, 1400 W,
10
bile juices with and impact bead cooling gas
11
12 without proteins spray chamber 13 L min-1,
13 auxiliary gas
14
0.7 L min-1,
15
16 nebulizer
17 gas
18
1.1 L min-1
19
20 2015 44.5±9.2 nm Spiked whole Dilution MicroMist glass Nebulizer Q 197 Au+ 10 ms n/s 132
21 Citrate-coated blood of rats nebulizer gas
22
Au NPs 1.05 L min-1
23
24 2017 Respirable Exhaled breath n/s n/s Q with 28 Si+ 3 ms 300 nm 133
25 crystalline silica condensate KED (He)
26
2017 10, 30, 50, 60, Spiked human Dilution with Concentric Nebulizer Q 107 Ag+, 50 µs 30 nm 134
27
28 80, 100 nm whole blood Triton X, TMAH, glass nebulizer, gas 197 Au +
29 citrate- or and water conical spray 1.06 L min -1
30
carboxylic acid- chamber
31
32 coated Ag and
33 Au NPs
34
35
36
37
38
39
40
41
42
43 66
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2018 40 nm PEG- Spiked human Alkaline MicroMist RF power TQ 107 Ag+ 3 ms 25 nm 135
9 coated Ag NPs, placental tissue digestion with nebulizer, Scott 1550 W,
10
broadly TMAH, spray chamber cooling gas
11
12 distributed enzymatic 15 L min-1,
13 PEG-, sodium digestion with nebulizer
14
carboxylate- Proteinase K gas
15
16 coated Ag NPs 1.03 L min-1
17 2018 Broadly Human ex vivo Enzymatic MicroMist RF power Q, TQ 107 Ag+ 3 ms 25 nm 136
18
distributed placenta perfusion digestion with nebulizer, Scott 1550 W,
19
20 PEG-, sodium model Proteinase K spray chamber cooling gas
21 carboxylate- for TQ; 15 L min-1,
22
coated Ag NPs MicroFlow PFA nebulizer
23
24 nebulizer, gas 1.03-
25 cyclonic spray 1.05 L min-1
26
chamber for Q
27
28 2019 20 nm citrate- Water, RPMI 1640 Dilution, PFA-ST RF power Q 197 Au+ 5 ms 10 nm 137
29 coated Au NPs culture medium, sonication nebulizer 1500 W
30
cell and exosome
31
32 lysates
33
34
Carbon Nanotubes (CNTs)
35 2013 Intercalated Co Single walled CNTs Dilution of n/s n/s Q Y , Co+
89 + 59 10 ms n/s Detection of 138
36
and Y NPs dispersions dispersed CNTs trace catalytic
37
38 metals
39 intercalated in
40
the CNTs
41
42
43 67
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2016 Intercalated Y Single walled CNTs Dilution and n/s RF power Q 89 + Y 0.1, n/s 139
9 dispersions, sonication for 1600 W, 10 ms
10
Daphnia magna in Daphnia magna cooling gas
11
12 Nanopure water samples 16 L min-1,
13 after CNT auxiliary gas
14
exposure 1.02 L min-1,
15
16 nebulizer
17 gas 0.85-
18
1 L min -1
19
20 2017 Intercalated Y Single walled Surfactant n/s n/s Q 89 + Y 0.1 ms n/s CNT fragments 140
21 CNTs, release addition, were released
22
supernatants sonication, due to
23
24 containing dilution photodegradatio
25 degradation n of CNTs and
26
products polycaprolactone
27
28 nanocomposite
29
Cosmetics
30
31 2015 32 to 40 nm Sunscreens Dispersion in Cyclonic spray RF power Q 48 Ti+ 0.1 ms 27-29 nm 141
32
TiO2 NPs Triton X-100, chamber, 1600 W,
33
34 dilution Meinhard nebulizer
35 nebulizer gas 1.06-
36
1.08 L min-1
37
38
39
40
41
42
43 68
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2017 30 to 120 nm Cosmetics and Defatting with Cyclonic spray RF power Q 48 Ti ,
+ 197 Au
+ 0.1 ms 35 nm TiO2 No Au NPs were 142
9 TiO2 NPs personal care hexane, chamber, 1450 W found in the
10
products suspension in Meinhard tested samples
11
12 water, dilution nebulizer
13 or suspension
14
in SDS, dilution
15
16 2018 ≤107 nm TiO2 Cream and spray Dispersion in PFA nebulizer n/s Q with 48 Ti+, 64Zn+ 5 ms 25 nm TiO2, 143
17 and ≤98 nm sunscreens Triton X-100, KED (He) 50 nm ZnO
18
ZnO NPs dilution
19
20 2018 TiO2 NPs Sunscreen, coating Defatting with Meinhard n/s Q 48 Ti+ 0.1 ms 32 nm 144
21 of chocolate hexane, nebulizer,
22
candies filtration, cyclonic spray
23
24 dilution for chamber
25 sunscreen;
26
extraction with
27
28 water,
29 sonication,
30
filtration,
31
32 dilution for
33 coating
34
2018 TiO2 and ZnO Sunscreen powder Dispersion in n/s n/s n/s n/s n/s n/s 145
35
36 NPs Triton X-100,
37 dilution
38
39
40
41
42
43 69
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2018 Al2O3, TiO2, SiO2 AF4 fractions after Dilution, see the Low-flow RF power Q 27 Al , Ti
+ 47 + 10 ms 55-65 nm 146
9 NPs toothpaste article for concentric 1549 W, Al2O3 and
10
fractionation detailed sample nebulizer, cooling gas TiO2 NPs
11
12 preparation cyclonic spray 14 L min ,-1
13 procedure chamber auxiliary gas

14
0.79 L min-1,
15
16 nebulizer
17 gas
18
1.04 L min-1
19
20
21
22
23
24
25
26
27
28 Model Environmental Aqueous Samples
29
30 2013 Nanoparticulat Model freshwater, Leaching n/s RF power Q with 66 Zn+, 30 ms n/s Leaching of CIGS 147
31 e Zn, Mo, Ag in seawater, acidic 1550 W, KED (He) 98 Mo+, and OPV cells
32
leachates rainwater cooling gas 107 Ag+ into model
33
34 15 L min-1, waters was
35 auxiliary gas studied
36 0.35 L min-1,
37
38 nebulizer
39 gas
40 0.79 L min-1
41
42
43 70
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2014 50 nm PVP- Spiked littoral Spiking, n/s n/s Q 107 Ag+ 10 ms 30 nm 148
9 coated Ag NPs mesocosms on a dilution
10
lake
11
12 2014 60 and 100 nm Spiked deionized, Spiking n/s n/s Q 107 Ag+ 10 ms 25-30 nm NPs dissolution 149
13 citrate-, tannic tap, surface, EPA kinetic study
14
acid-, PVP- moderately hard
15
16 coated Ag NPs reconstituted
17 laboratory waters
18
2014 50 nm citrate- Spiked purified Filtration Glass conical RF power Q 107 Ag+, 5 ms 40 nm Internal 66
19
20 coated, 80 nm water, waste water (0.45 µm pore nebulizer, 1450 W, 109 Ag+ calibration with
21 PVP-coated Ag influent and size), spiking conical spray cooling gas isotope dilution
22
NPs effluent, river chamber with 15 L min ,-1 (109Ag enriched
23
24 water impact bead nebulizer silver standard)
25 gas 0.85 and was used, both
26
0.93 L min -1 silver isotopes
27
28 were monitored
29 in one run with
30
1.9 ms settling
31
32 time
33
34
35
36
37
38
39
40
41
42
43 71
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2016 80-200 nm ZnO Spiked river water Spiking, water Meinhard RF power Q 67 Zn ,
+ 0.1 ms 35-40 nm 150
9 NPs, 30-50 nm after real and treatment, concentric 1600 W, 140 Ce + ZnO, 18-
10
CeO2 NPs, Zn- model drinking dilution; or no nebulizer, cooling gas 20 nm CeO2
11
12 and Ce- water treatment treatment cyclonic spray 18 L min ,-1
13 containing NPs facility, river water chamber auxiliary gas

14
1.2 L min-1,
15
16 nebulizer
17 gas 1.02-
18
1.06 L min-1
19
20 2016 Ti-containing Spiked river water Spiking, water Meinhard RF power Q 47 Ti+, 197Au+, 0.1 ms 65-70 nm 151
21 NPs; 100, after real and treatment, concentric 1600 W, 107 Ag + TiO2, 21-
22
160 nm TiO2 model drinking dilution; or no nebulizer, cooling gas 23 nm Ag,
23
24 NPs; 40, 70, water treatment treatment cyclonic spray 18 L min ,-1 27-30 nm
25 100 nm citrate- facility, river water chamber auxiliary gas Au
26
coated Ag NPs; 1.2 L min ,
-1
27
28 50, 80, 100 nm nebulizer
29 citrate-coated gas 1.02-
30
Au NPs 1.06 L min-1
31
32 2016 80 nm citrate- Spiked waste Filtration Concentric RF power Q 107 Ag+ 0.1 ms, 10 nm for 152
33 and PVP- water effluent and (0.45 µm pore glass nebulizer, 1600 W 10 ms double
34
coated Ag NPs mixed liquor size), spiking cyclonic spray deionized
35
36 chamber water
37
38
39
40
41
42
43 72
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2016 20 and 50 nm Spiked lake water Filtration n/s RF power Q 107 Ag ,
+ 5 ms 24 nm 153
9 citrate-, PVP-, (0.22 µm pore 1550 W, 109 Ag+
10
lipoic acid- size), spiking cooling gas
11
12 coated Ag NPs 15 L min-1
13 2016 30, 60, 80, Spiked river and Filtration MicroMist RF power Q 197 Au+ 3 ms 19 nm for 154
14
100 nm tannic waste waters (0.45 µm pore nebulizer 1550 W, ultrapure
15
16 acid-coated Au size), spiking auxiliary gas water,
17 NPs 0.1 L min ,
-1 31 nm for
18
nebulizer 0.1 µg L -1
19
20 gas Au3+
21 1.05 L min-1
22
2016 75 nm PVP- Reaction in Spiking, Microflow n/s Q 107 Ag+ 10 ms 15 nm 155
23
24 coated Ag NPs aerated, sulfide- dilution concentric PFA
25 containing water nebulizer,
26
and EPA impact bead
27
28 moderately hard spray chamber,
29 reconstituted
30
water standard
31
32 2016 40, 80 nm Spiked waste Filtration Concentric n/s Q 107 Ag+ 0.1 ms 24 nm 102
33 citrate-coated water effluent and (0.45 µm pore nebulizer
34
Ag NPs influent, river size), spiking,
35
36 water HDC
37
38
39
40
41
42
43 73
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2016 50, 80 nm Spiked MilliQ Spiking Conical RF power Q 107 Ag+ 5 ms 40 nm Ozonation was 156
9 citrate- or PVP- water, chloride nebulizer, 1450 W, without Ag + used for selected
10
coated Ag NPs containing MilliQ impact bead cooling gas samples
11
12 water, MilliQ water spray chamber 15 L min ,-1
13 at pH 5, 7, and 7.6 nebulizer

14
gas
15
16 0.85 L min-1
17 2017 50 nm citrate-, Spiked waste Spiking, n/s n/s Q n/s 0.5 ms 17 nm 157
18
tannic acid- water effluent, dilution, IEC
19
20 coated Ag NPs MilliQ water,
21 modified TAP
22
medium
23
24 2017 10, 20, 30, 40, Spiked lake, tap Spiking, Cyclonic spray n/s Q 107 Ag+ 50 µs 12-15 nm 158
25 50, 60, 70, 80, waters; liquid dilution chamber,
26
100 nm PVP- consumer Meinhard
27
28 coated Ag NPs products, concentric
29 migration nebulizer
30
solutions from
31
32 plasters
33 2017 20, 40, 80, 100, Spiked waste Spiking, n/s n/s Q n/s 10 ms n/s 159
34
200 nm PVP- water effluent, centrifugation
35
36 coated and environmental
37 commercial Ag water
38
NPs
39
40
41
42
43 74
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2017 10-25 nm TiO2 Spiked river water Spiking, Reference to Reference to Q 47 Ti , Zn
+ 66 + 0.1 ms 64 nm TiO2, 160
9 and 10-30 nm dilution previous studies previous 43 nm ZnO
10
ZnO NPs studies
11
12 2017 30-50 nm PVP- Spiked MilliQ and Sonication, n/s n/s Q 107 Ag+ 5 ms 40 nm 161
13 coated Ag NPs lake waters with dilution
14
gum arabic
15
16 2017 60 nm Ag-Ag Spiked EPA Spiking Cyclonic spray RF power Q 107 Ag+, 0.1 ms 15.5 nm Ag 162
17 core-shell NPs moderately hard chamber, 1600 W 197 Au+
18
(30 nm core, water with or Meinhard
19
20 15 nm shell) without fulvic acid concentric
21 nebulizer
22
2017 40, 80, 100 nm Spiked wastewater Filtration Cyclonic spray n/s Q 107 Ag+ 0.5 ms n/s 163
23
24 citrate- or PVP- biosolids (raw or (0.45 µm pore chamber, type
25 coated Ag NPs supernatant) size), spiking C0.5 concentric
26
glass nebulizer
27
28 2017 40, 60 nm BPEI- Spiked microcosm Spiking Flow injection, Reference to Q 107 Ag+ 10 ms n/s 164
29 and PVP- tanks with pneumatic previous
30
31 coated Ag NPs seawater nebulizer studies
32
33
34
35
36
37
38
39
40
41
42
43 75
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2017 40 nm citrate- Spiked WWTP Filtration Cyclonic spray RF power SF n/s 0.1 ms From 5.4 nm 62
9 coated Ag NPs mesocosm (0.1 mm pore chamber, 1205 W, to 30-40 nm
10
size), spiking Burgener Mira cooling gas
11
12 Mist nebulizer 15.01 L min-
13 1, auxiliary
14
gas
15
16 0.75 L min-1,
17 nebulizer
18
gas
19
20 0.520 L min-1
21 2018 Aged 34 nm Remobilization Dilution, n/s n/s Q 107 Ag+ 5 ms 30 nm 165
22
citrate-coated medium filtration (1 µm
23
24 Ag NPs, Ag- (remobilization pore size) or no
25 containing from a model filtration
26
aggregates sediment)
27
28 2018 40, 70, 100 nm Spiked river and Dilution Reference to Reference to Q 47 Ti+ 0.1 ms 25 nm Ag, 166
29 citrate-coated lake waters with previous studies previous 30 nm Au,
30
Ag; 50, 80, alum, ferric oxides, studies 70 nm TiO2,
31
32 100 nm citrate- or ferric sulfate 23 nm CeO2,
33 coated Au; 44 nm ZnO
34
100 nm TiO2;
35
36 30-50 nm CeO2;
37 80-200 nm ZnO
38
NPs
39
40
41
42
43 76
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2018 25 nm PVP- Effluent of a lab- Sonication, n/s n/s Q 107 Ag+ 3 ms n/s 167
9 coated Ag NPs, scale WWTP dilution
10
5 nm TiO2 NPs
11
12 2018 30, 50, 80, Spiked tap, river Spiking, Ag+ n/s RF power Q 107 Ag+ 3 ms 20 nm 168
13 100 nm citrate- waters, waste was adsorbed 1550 W,
14
coated and 60, water influent by magnetic cooling gas
15
16 100 nm PVP- reduced 15 L min-1
17 coated Ag NPs graphene oxide
18
2018 30-50 nm PVP- Spiked surface Lake spiking Reference to Reference to SF 107 Ag+ 50 µs 12 nm 169
19
20 coated Ag NPs water of a boreal previous studies previous
21 oligotrophic lake studies
22
2018 30-50 nm PVP- Spiked surface Lake spiking Glass conical RF power Q 107 Ag+ 5 ms 45±5 nm 170
23
24 coated Ag NPs water of a boreal nebulizer 1450 W,
25 oligotrophic lake cooling gas
26
15 L min-1
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43 77
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2018 50 nm zero- Spiked Milli-Q Spiking, Scott spray RF power TQ 56 Fe ,
+ 111 Cd+ 3 ms 36 nm H2 was used as a 171
9 valent iron NPs, water, synthetic shaking chamber 1550 W, reaction gas
10
Cd2+ sorbed to and effluent waste cooling gas
11
12 the NPs waters 15.0 L min-1,
13 auxiliary gas
14
0.90 L min-1,
15
16 nebulizer
17 gas
18
1.09 L min-1,
19
20 sampling
21 position
22
8 mm
23
24 2019 20,40, 60 nm Spiked Milli-Q CPE PFA Microflow RF power Q 107 Ag+ 0.1 ms >20 nm Optimization of 172
25 citrate-coated water, spiked nebulizer, 1600 W, CPE was
26
Ag NPs wastewater cyclonic spray cooling gas performed
27
28 chamber 18.0 L min ,-1
29 auxiliary gas
30
1.2 L min-1,
31
32 nebulizer
33 gas
34
0.83 L min-1
35
36
37
38
39
40
41
42
43 78
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 Environmental Aqueous Samples
9
10 2014 TiO2 NPs Suspended Dilution n/s n/s Q 47 Ti+ 10 ms 130 nm Interference of 173
11 released from particulate matter 48 Ti+ with 48Ca+
12
sunscreen of Old Danube
13
14 products Lake, Vienna,
15 Austria
16
2015 50 nm ZnO NPs Spiked and Spiking, Type C0.5 n/s Q n/s 0.5 ms 32 nm for 174
17
18 and Zn- unspiked surface dilution or IEC concentric glass Milli-Q
19 containing NPs water, effluent (Chelex 100) nebulizer, water,
20
waste water (Des cyclonic spray 70 nm for
21
22 Prairies River, chamber river water,
23 Montreal WWTP, 126 nm for
24
Canada) waste water
25
26 2016 Ag-containing WWTP and surface CPE, dilution n/s n/s Q 107 Ag + 3 ms 14 nm 175
27 NPs waters from the
28
River Isar,
29
30 Germany; pre-
31 alpine lakes water,
32
Germany
33
34
35
36
37
38
39
40
41
42
43 79
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2016 Citrate-coated Spiked filtered Filtration with MicroMist RF power Q 107 Ag , + 3 ms 20 nm Ag, 103
9 Ag NPs, tannic natural and waste nylon nebulizer 1550 W, 197 Au + 19 nm Au
10
acid-coated Au waters, unspiked membrane auxiliary gas
11
12 NPs, Ag- and natural water (0.45 and 0.1 L min-1,
13 Au-containing (Guiyu and 0.22 µm pore nebulizer
14
NPs Xiangjiang Rivers size) before gas
15
16 and Chendian spiking; dilution 1.05 L min-1,
17 Lake, China) and for unspiked sampling
18
waste water samples position
19
20 (HuNan University, 8 mm
21 China)
22
2017 71 and 145 nm Influent sewage, Microwave n/s RF power n/s 47 Ti+ 3 and n/s 176
23
24 TiO2 NPs aeration tank digestion 1550 W, 10 ms
25 contents of WWTP (HNO3 and nebulizer
26
(Hyderabad, India) H2O2), filtration gas
27
28 with cellulose 1.05 L min-1,
29 acetate
30
membrane
31
32 (0.22 µm pore
33 size), sonication
34
2017 Ti-containing Surface water of n/s n/s n/s Q, SF 49 Ti+ at 3 ms 79 nm TiO2 SF 177
35
36 NPs Clear Creek in quadrupole for Q, 42 nm measurements
37 Golden, Colorado, , Ti at SF
48 + TiO2 for SF were presented
38
USA as a proof of
39
40 concept
41
42
43 80
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2018 Ti-containing Water samples Sonication, n/s n/s TQ, TOF 63 TiNH + for 4 ms for 81 nm TiO2 NH3 and He were 73
9 natural NPs and from Old Danube centrifugation TQ, MA for TQ, for TQ used as
10
engineered Lake, Vienna, for TQ; TOF 3 ms for reaction/collision
11
12 TiO2 NPs Austria sonication, TOF gases
13 dialysis for TOF
14
2018 Ag-containing Water from Vltava, 1% (w/w) PTFE concentric RF power Q 107 Ag+ 0.1 ms 15 nm 178
15
16 NPs Prague, Czech gelatin for nebulizer, 1100 W,
17 Republic stabilization cyclonic spray cooling gas
18
chamber 11 L min-1,
19
20 auxiliary gas
21 1.0 L min-1,
22
nebulizer
23
24 gas
25 0.85 L min-1
26
2018 Ag-containing Bottom sediments Sonication with Reference to Reference to SF mass 107 Ag+ 50 µs 16 nm 179
27
28 NPs and labile water, previous studies previous analyzer
29 sediments from centrifugation, studies was used
30
Lake Ontario, filtration in low
31
32 Canada, freeze- (0.45 µm pore resolutio
33 dried samples size) n mode
34
35
36
37
38
39
40
41
42
43 81
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2018 Ag, CeO2, TiO2 Surface water of Sonication MicroFlow PFA RF power Q 107 Ag , + 3 ms 14 nm Ag, MA was used 180
9 NPs Meuse and Ijssel nebulizer, 1550 W, 140 Ce , Ti ,
+ 48 + 10 nm CeO2, with 100 µs dwell
10
Rivers, the cyclonic spray cooling gas 139 La + 100 nm TiO2 time to detect
11
12 Netherlands chamber 14 L min ,-1 140 Ce+ and 139La+
13 auxiliary gas
14
0.8 L min-1,
15
16 nebulizer
17 gas
18
1.1 L min-1
19
20 2018 Ti-containing Water from Salt Filtration n/s n/s Q 49 Ti+ 10 ms 148 ± 3 nm 181
21 NPs River, pools, (0.7 µm pore for river
22
Arizona, USA size) water,
23
24 173 ± 15 n
25 m for pool
26
water
27
28 2018 Ag-containing Water from Lake CPE, dilution n/s n/s Q 107 Ag + 0.1 ms 10 nm 182
29 NPs Königssee and
30
Lake Waginger
31
32 See, Bavaria,
33 Germany
34
35
36
37
38
39
40
41
42
43 82
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2018 Pb-, Fe-, Sn-, Tap water from n/s n/s Q with 208 Pb , + 10 ms 11.3 nm Pb, No Ti- and Ag- 183
9 Cu-, Ag-, Ti- Phoenix, Arizona, KED for 56 Fe ,
+ 55 nm Fe, containing NPs
10
containing USA 56 Fe + 118 Sn ,+ 26 nm Sn, were discovered
11
12 particles 107 Ag , + 40 nm Cu,
13 65 Cu , Ti
+ 49 + 75 nm Ti,
14
13 nm Ag
15
16 2019 Engineered Sanitary sewage Tetrasodium n/s n/s TOF 48 Ti , MA
+ 1.8 ms 40 nm TiO2 Split-particle 184
17 TiO2 NPs spills pyrophosphate events were
18
treatment, summed up
19
20 stirring,
21 sonication,
22
centrifugation,
23
24 dilution
25
Model Food Samples
26
27 2014 20, 40, 100 nm Food simulants Dilution Varied among Varied n/s n/s 3 ms Varied Interlaboratory 83
28
PVP-coated Ag (distilled water, the participants among the among the method
29
30 NPs 10% ethanol) participants participants performance
31 study with over
32
23 laboratories
33
34
35
36
37
38
39
40
41
42
43 83
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2014 30, 60 nm Spiked Milli-Q Dilution Varied among Varied n/s 107 Ag , + 3 ms Varied Interlaboratory 185
9 citrate-coated water, chicken the participants among the 197 Au+ among the method
10
Au NPs, 60 nm digest (enzymatic participants participants performance
11
12 citrate-coated digestion) study with over 9
13 Ag NPs laboratories, 3 of
14
which used SP-
15
16 ICP-MS
17 2016 60 nm PVP- Food simulants Dilution MicroMist RF power Q 107 Ag + 3 ms n/s 186
18
coated Ag NPs (water, 10% nebulizer 1550 W,
19
20 ethanol, 3% acetic cooling gas
21 acid) 15 L min-1
22
2016 10, 30, 50, 60, Spiked water, Dilution n/s n/s Q 107 Ag+, 50 µs 31-34 nm The coatings 187
23
24 100 nm Ag NPs, orange juice, apple 197 Au+ were not
25 10, 20, 30, 50, juice specified for each
26
60, 70, 80 nm size of the NPs.
27
28 Au NPs Citrate-, PVP-
29 coated Ag NPs;
30
citrate-,
31
32 carboxylic acid-
33 coated, PBS-
34
buffered Au NPs
35
36 were used.
37
38
39
40
41
42
43 84
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2018 40 nm PEG-, Food simulants Dilution, Triton Low-flow RF power Q 107 Ag + 3 ms 10-20 nm 188
9 citrate-coated (10%, 20%, 50% X-100 was used concentric 1550 W,
10
Ag NPs ethanol; 3% acetic to create olive nebulizer, cooling gas
11
12 acid, olive oil), low oil emulsion in cyclonic spray 14 L min-1,
13 fat cow milk, 2% water chamber auxiliary gas
14
NaCl 0.80 L min-1,
15
16 nebulizer
17 gas
18
0.96 L min-1
19
20 Food
21
22 2014 TiO2 NPs Food grade TiO2 Food grade Conical glass RF power Q 48 Ti+ 3 ms 50 nm 189
23 (E171), food and TiO2 suspension concentric 1400 W
24
personal care in BSA, heating nebulizer
25
26 products with H2O2 and
27 resuspension in
28
BSA for other
29
30 products
31 2015 Ag NPs Decoration of Dissolution in MicroMist n/s Q 107 Ag+ 3 ms 13 nm 190
32
pastry (“pearls”) water, dilution nebulizer
33
34
35
36
37
38
39
40
41
42
43 85
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2018 TiO2 NPs Candy products Sonication in MicroMist RF power TQ 48 Ti + with 10 ms 26 nm Optimization of 57
9 water, dilution nebulizer, 1550 W, O2 gas had TQ detection was
10
cyclonic spray cooling gas the highest performed with
11
12 chamber 14 L min ,-1 sensitivity different gases
13 auxiliary gas
14
0.8 L min-1,
15
16 nebulizer
17 gas
18
1.03 L min-1
19
20 2018 TiO2, Cu, Ag Drinks and food Sample Meinhard n/s Q 107 Ag+, 0.1 µs 32 nm TiO2, 191
21 NPs preparation nebulizer, 63 Cu , Ti
+ 48 + 30 nm Ag
22
varied cyclonic spray
23
24 depending on chamber
25 the product
26
2018 Al-containing Chinese noodles Enzymatic Low-low RF power Q 27 Al+ 3 ms 54-83 nm 192
27
28 NPs digestion with concentric 1550 W, Al2O3
29 α-amylase nebulizer, cooling gas
30
cyclonic spray 13.9 L min-1,
31
32 chamber auxiliary gas
33 0.79 L min-1,
34
nebulizer
35
36 gas
37 1.07 L min-1
38
39
40
41
42
43 86
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2019 TiO2 NPs Surimi (crab sticks) Enzymatic n/s RF power Q 49 Ti + 0.1 ms 31.3- 193
9 digestion with 1600 W, 37.1 nm
10
pancreatin and cooling gas
11
12 lipase, dilution 16 L min-1,
13 with 1% auxiliary gas
14
glycerol, 1.2 L min-1,
15
16 sonication nebulizer
17 gas
18
0.95 L min-1
19
20 Plants exposure
21
22 2015 40 nm PVP- Tomato plants Enzymatic Meinhard RF power Q 197 Au+ 0.1 ms 20 nm 194
23 coated; 10, 12, digestion with nebulizer, 1600 W,
24
15, 20, 30, 40, Macerozyme R- cyclonic spray cooling gas
25
26 50, 80, 100 nm 10, dilution chamber 18 L min-1,
27 citrate-coated auxiliary gas
28
Au NPs 1.2 L min-1,
29
30 nebulizer
31 gas
32
1.08 L min-1
33
34 2016 10 nm citrate- Arabidopsis Enzymatic n/s n/s Q 107 Ag+ 0.05 ms 10 nm 195
35 coated Ag NPs thaliana plants´ digestion with
36
roots and shoots Macerozyme R-
37
38 10, dilution
39
40
41
42
43 87
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2016 30-50 nm, 50- Shoots of Enzymatic Meinhard RF power Q 140 Ce + 0.1 ms 23-25 nm 196
9 100 nm CeO2 cucumber (C. digestion with nebulizer, 1600 W,
10
NPs sativus), tomato (S. Macerozyme R- cyclonic spray cooling gas
11
12 lycopersicum L.), 10 chamber 18 L min-1,
13 soybean (Glycine auxiliary gas
14
max), pumpkin 1.2 L min-1,
15
16 (Cucurbita pepo) nebulizer
17 gas
18
1.06 L min-1
19
20 2016 70 nm citrate- Lepidium sativum, Enzymatic Meinhard glass RF power Q 195 Pt+ 0.1 ms n/s 197
21 coated Pt NPs Sinapis alba plants digestion with microconcentric 1450 W,
22
Macerozyme R- nebulizer, cooling gas
23
24 10, filtration cyclonic spray 15.0 L min-1,
25 (0.45 µm pore chamber auxiliary gas
26
size), dilution 1.0 L min-1,
27
28 nebulizer
29 gas
30
0.98 L min-1
31
32 2017 Cu-containing Vine leaves Rainfall n/s n/s Q 63 Cu+ 0.1 ms 8-60 nm Cu 198
33 NPs from washoff,
34
fungicide through fall
35
36 residues sampling,
37 (copper filtration
38
oxychloride) (0.45 µm pore
39
40 size), dilution
41
42
43 88
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2017 17 nm PVP- Soybean, rice (root Enzymatic Meinhard n/s Q 107 Ag+ 0.05 ms 14 nm 199
9 coated Ag NPs and foliar digestion with nebulizer,
10
exposures) Macerozyme R- cyclonic spray
11
12 10, dilution chamber
13 2017 PVP-coated Dicotyledonous Enzymatic n/s n/s TQ 107 Ag+ 3 ms 20-25 nm 200
14
Ag2S cucumber digestion with
15
16 (Cucumis sativus), Macerozyme R-
17 monocotyladonou 10, dilution
18
s wheat (Triticum
19
20 aestivum L.)
21 2018 20-100 nm CuO Leaves of Exposure to Glass concentric RF power Q 63 Cu+ 0.1 ms n/s 201
22
NPs vegetables, kale NPs, rinsing nebulizer 1550 W,
23
24 (Brassica oleracea, with ultrapure nebulizer
25 var. Acephala water or gas
26
Lacinato), lettuce enzymatic 0.67 L min-1,
27
28 (Lactuca sativa var. digestion with sampling
29 green leaf cultivar), Macerozyme R- position
30
collard green 10, dilution 8.0 mm
31
32 (Brassica oleracea,
33 var. Acephala)
34
35
36
37
38
39
40
41
42
43 89
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2018 Pd NPs Sinapis alba leaves, Enzymatic Meinhard glass RF power Q 105 Pd+ 0.1 ms 25-30 nm 202
9 stems, roots digestion with microconcentric 1450 W,
10
Macerozyme R- nebulizer, cooling gas
11
12 10, filtration cyclonic spray 15.0 L min-1,
13 (0.45 µm pore chamber auxiliary gas
14
size), dilution 0.9 L min-1,
15
16 nebulizer
17 gas
18
1.10 L min-1
19
20 2018 “Green Leaf sap extract AgNO3 addition Concentric RF power Q 107 Ag+ 5 ms n/s 203
21 synthesis” of Ag from Aloe to the leaf sap quartz 1500 W,
22
NPs arborescens extract induces nebulizer, cooling gas
23
24 the formation baffle-type 17 L min-1,
25 of Ag NPs cyclonic spray auxiliary gas
26
under sunlight, chamber 1.4 L min-1,
27
28 centrifugation, nebulizer
29 dilution gas
30
0.8 L min-1
31
32 2018 Isotopically Arabidopsis Macerozyme R- MicroMist Cooling gas Q 107 Ag+, 3 ms n/s Cu, ZnO NPs 204
33 labelled Ag, Cu, thaliana shoot and 10, filtration nebulizer 15 L min ,-1 65 Cu , Zn
+ 70 + were not
34
ZnO NPs roots (0.22 µm pore auxiliary gas detected in
35
36 size), dilution 1.0 L min ,
-1 shoots or roots
37 nebulizer because of the
38
gas high background
39
40 1.05 L min -1
41
42
43 90
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2019 “Green Cucumber leaf AgNO3 addition n/s RF power Q 107 Ag + 0.1 ms n/s 205
9 synthesis” of Ag extract to the leaf 1550 W,
10
NPs extract, pH 10.0, nebulizer
11
12 4 h at 80 °C gas
13 0.67 L min-1,
14
sampling
15
16 position
17 8.0 mm
18
2019 80-200 nm ZnO Lettuce Lactuca Dilution, n/s n/s Q 66 Zn+ 0.1 ms n/s 206
19
20 NPs sativa L. growth Macerozyme R-
21 medium, roots and 10 for roots and
22
leaves leaves
23
24
25
26
27
28
29
Model Soil Samples
30
31 2014 25 nm PVA- Soil spiked with Spiking, water n/s n/s Q n/s 10 ms 18 nm Ag, 207
32
coated Ag NPs, biosolids that were extraction, 70-80 nm
33
34 30 nm ZnO enriched with NPs centrifugation, TiO2, 10 nm
35 NPs, 42 nm filtration CeO2
36
TiO2 NPs, (0.45 µm pore
37
38 35 nm CeO2 size)
39 NPs
40
41
42
43 91
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2015 CuO NPs Spiked topsoil Extraction, MicroMist RF power Q with 63 Cu+ 5 ms or 15±10 nm 208
9 colloid extracts dilution, spiking nebulizer 1550 W, KED (He) 0.1 ms
10
cooling gas
11
12 15 L min-1,
13 auxiliary gas
14
0.15 L min-1,
15
16 nebulizer
17 gas
18
0.98 L min-1
19
20 2017 10, 30, 60 nm Spiked soil colloid Water Concentric n/s Q 197 Au+ 10 ms n/s 209
21 citrate-coated extracts extraction, MicroMist
22
Au NPs, 30 nm centrifugation, nebulizer, Scott
23
24 BPEI- and PVP- filtration spray chamber
25 coated Au NPs (0.45 µm pore
26
size), spiking,
27
28 CPE
29 2017 40 nm PVP- Natural sandy Spiking, TSPP Low pressure RF power Q 107 Ag+ 0.05 µs 20 nm 210
30
coated Ag NPs loam soil spiked extraction, PFA nebulizer 1600 W,
31
32 with biosolids that gravimetric nebulizer
33 were enriched with sedimentation, gas
34
NPs dilution 1.04 L min-1
35
36
37
38
39
40
41
42
43 92
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2017 40 nm PVP- Nanopure water KNO3 Low pressure RF power Q 107 Ag + 0.05 µs 19 nm 211
9 coated Ag NPs with NaNO3 and extraction, PFA nebulizer, 1600 W,
10
KNO3, filtered centrifugation, cyclonic spray nebulizer
11
12 sandy loam soil filtration chamber gas
13 extracts with (0.45 µm and 1.04 L min-1
14
NaNO3 and KNO3 0.22 µm pore
15
16 size), spiking,
17 dilution
18
2017 25, 40 nm PVP- Spiked sandy loam Spiking, TSPP Low pressure RF power Q 107 Ag+ 0.05 µs 19 nm Optimization of 212
19
20 coated Ag NPs soils and biosolids extraction, PFA nebulizer, 1600 W, the NPs
21 extracts sonication, cyclonic spray nebulizer extraction
22
filtration chamber gas conditions from
23
24 (0.45 µm and 1.04 L min -1 soil, only the
25 0.22 µm pore most efficient
26
size), dilution conditions were
27
28 mentioned
29 2018 30 nm citrate-, Standard soils Spiking, Concentric n/s Q 197 Au+ 10 ms n/s 213
30
BPEI-, PVP-, water extracts, moderately nebulizer, Scott
31
32 PEG-, NOM- estuarine sediment hard water spray chamber
33 coated Au NPs in moderately hard extraction,
34
water centrifugation,
35
36 dilution
37
38
39
40
41
42
43 93
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2018 40, 100 nm Consumer product Spiking, Milli-Q n/s RF power Q 107 Ag + 10 ms n/s 214
9 citrate-coated; (band aid) water water 1500 W,
10
75, 100 nm extracts, spiked extraction, cooling gas
11
12 PVP- and PEG- soil water extracts filtration 15 L min-1
13 coated Ag NPs (0.45 µm pore
14
size)
15
16
17
18
19
20
21
Solid Environmental Samples
22
23 2016 As-containing Leachate from Leaching with Glass concentric RF power Q 75 As+ 5 ms 117 nm Settling time of 215
24
NPs mine wastes 1 mM KCl, slurry nebulizer, 1200 W, Fe As O4
III V · 3 ms
25
26 centrifugation cyclonic spray cooling gas 2H2O
27 chamber 15 L min-1,
28
auxiliary gas
29
30 1.2 L min-1,
31 nebulizer
32
gas
33
34 1.0 L min-1
35 2017 Zn-, Fe-, Ti- Sewage sludge Acetic acid n/s n/s Q with 47 Ti+, 66 Zn+, 0.1 ms 15-20 nm Ti, 216
36
containing NPs extraction, KED for 56 Fe + 15-16 nm
37
38 dilution 56 Fe + Zn, 12-
39 17 nm Fe
40
41
42
43 94
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2017 Ce-containing Spiked topsoil Spiking, Pneumatic RF power TOF at MA for TOF; n/a for 0.10-0.17 fg Natural and 72
9 natural NPs and samples shaking, wet- nebulizer, 1400 W, 33 kHz 140 Ce + and TOF, Ce, 0.13 fg engineered NPs
10
<50 nm CeO2 sieving (32 µm cyclonic spray cooling gas complete 139 La for Q
+ 5 ms for La for TOF; were identified
11
12 NPs pore size), chamber for 16 L min ,-1 mass Q 0.13-0.57 fg with
13 freeze-drying, TOF; Miramist auxiliary gas spectrum Ce, 0.21- multielement
14
aqueous colloid nebulizer for Q 1.1 L min ,
-1 in 300 µs, 0.34 fg La fingerprinting
15
16 extraction, nebulizer Q for Q
17 dilution gas
18
1.2 L min-1
19
20 for TOF; RF
21 power
22
1550 W,
23
24 cooling gas
25 15 L min-1,
26
auxiliary gas
27
28 0.4 L min-1,
29 nebulizer
30
gas
31
32 0.8 L min-1
33 for Q
34
35
36
37
38
39
40
41
42
43 95
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2018 Pt NPs Road dust Ultrasonic Quartz n/s Q 195 Pt+ 5 ms 7.4 nm 217
9 leachate, catalyst extraction with nebulizer
10
material stormwater
11
12 runoff, filtration
13 (0.45 µm pore
14
size)
15
16 2019 Th, U- Leachates of Leaching with n/s RF power SF 232 Th+, 238U+ 0.05 ms 3 nm U, Th 218
17 containing NPs tailings of a different 1300 W,
18
Niobium mine solutions of 2- cooling gas
19
20 10 pH; Ca, Mg, 13 L min-1,
21 Na of 0- auxiliary gas
22
13 mmol L ; -1 1.2 L min-1,
23
24 fulvic acid of 0- nebulizer
25 20 ng L ;
-1 gas 0.7 -
26
centrifugation 1.0 L min -1
27
28 Model Water Samples
29
30 2013 1-10 nm NPs water Dilution n/s n/s Q n/s 3 ms 20 nm 219
31 sodium suspensions
32
polyacrylate-
33
34 coated; 20, 40,
35 80 Ag NPs
36
37
38
39
40
41
42
43 96
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2015 100 nm citrate- Spiked water with Spiking, Type-C n/s Q n/s 3 ms 30 nm Ag 220
9 coated Ag NPs; laundry detergents filtration or no MiraMist
10
60, 100 nm Au filtration, nebulizer,
11
12 NPs; Au/Ag dilution cyclonic spray
13 48 nm core/ chamber
14
15 nm shell
15
16 2015 252 nm Spiked ultrapure Dilution Quartz RF power SF 28 Si+ 5 ms n/s 221
17 DNA/SiO2 NPs, and drinking MicroMist 950 W,
18
350 nm SiO2 waters nebulizer, cooling gas
19
20 NPs cyclonic spray 16 L min-1,
21 chamber auxiliary gas
22
0.6 L min-1,
23
24 nebulizer
25 gas
26
1.2 L min-1
27
28 2017 60, 100 nm NaNO3 or NaNO3 Dilution or MicroMist RF power Q n/s 10 ms n/s 222
29 citrate- and and Ca(NO3)2 dialysis nebulizer 1400 W,
30
PVP-coated Ag cooling gas
31
32 NPs and their 18.0 L min-1,
33 aggregates auxiliary gas
34
1.30 L min-1,
35
36 nebulizer
37 gas
38
1.44 L min-1
39
40 Other Applications
41
42
43 97
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2016 Cu2O NPs Antifouling paint Dilution, n/s n/s Q n/s 0.1 ms n/s 223
9 sonication
10
2016 Ag NPs Release from Incubation n/s Sampling n/s n/s 3 ms n/s 224
11
12 plastic food position
13 containers into 7 mm
14
food simulants
15
16 (Milli-Q water, 10%
17 ethanol, 3% acetic
18
acid)
19
20 2016 Ag NPs Release from Incubation, MicroMist RF power Q 107 Ag+ 10 ms n/s 225
21 plastic food sonication, Nebulizer, Scott 1550 W,
22
containers and evaporation of spray chamber cooling gas
23
24 baby feeding ethanol and 15 L min-1,
25 bottle into food reconstitution auxiliary gas
26
simulants (Milli-Q in Milli-Q water 1.2 L min-1,
27
28 water, 10% and nebulizer
29 90% ethanol, 3% gas 1 L min-1
30
acetic acid)
31
32 2016 Ag NPs Release from Ink dilution n/s n/s Q n/s 0.1 ms n/s 226
33 nanosilver
34
conductive ink, ink
35
36 itself
37
38
39
40
41
42
43 98
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2017 Ag NPs Glass slides coated Ultrapure water Glass concentric RF power Q 107 Ag + and 5 ms 24 to 40 nm 227
9 with Ag NPs, extraction and slurry nebulizer, 1200 W, 109 Ag +
10
structured SiO2- dilution for cyclonic spray cooling gas
11
12 based glass slides; chamber 15 L min-1,
13 nanocomposites MOPS auxiliary gas
14
with a single layer extraction, 1.2 L min-1,
15
16 of Ag NPs algae nebulizer
17 treatment, gas
18
centrifugation, 1.0 L min-1
19
20 dilution for
21 nanocomposite
22
s
23
24 2017 Ag NPs Toothbrushes Release of NPs n/s Sampling n/s n/s 3 ms 35 nm 228
25 to tap water position
26
7 mm
27
28 2017 TiO2 NPs Textiles (table Release of NPs n/s n/s n/s 48 Ti+, 44Ca+ 0.1 ms 27-33 nm 229
29 placemats, wet to deionized
30
wipes, microfiber water,
31
32 cloths, baby sonication,
33 bodysuits) shaking,
34
dilution and
35
36 addition of
37 Triton-X
38
39
40
41
42
43 99
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2017 Iron based Nanopigments in Rotation end MicroMist RF power Q with 56 Fe + 5 ms n/s 230
9 Fe2O3 polymer matrix: over end nebulizer 1550 W, KED (H2)
10
nanopigment release from cryo- cooling gas
11
12 milled debris into 15 L min-1,
13 Milli-Q water, auxiliary gas
14
moderately hard 0.19 L min-1,
15
16 water, water with a nebulizer
17 humic acid gas
18
0.98 L min-1
19
20 2017 Ag NPs Release from Milli-Q water n/s n/s Q 107 Ag+ 0.05 ms n/s 231
21 antibacterial extraction
22
leather and
23
24 leatherette into
25 Milli-Q water
26
2017 TiO2, Al2O3, Cu- Tattoo inks Dilution PFA-ST RF power Q with 27 Al+, 63 Cu+, 5 ms n/s 232
27
28 phthalocyanine, nebulizer 1400 W, KED (He) 47 Ti +
29 CuO NPs cooling gas

30
15 L min-1,
31
32 auxiliary gas
33 1.2 L min-1,
34
nebulizer
35
36 gas
37 1.05 L min-1
38
39
40
41
42
43 100
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2017 Mo-, Fe- Asphaltene Dilution with o- Concentric RF power TQ 51 + V , 56 Fe ,
+ 0.1 ms n/s 233
9 containing NPs solutions xylene, glass nebulizer 1600 W, 60 Ni , Mo
+ 95 +
10
sonication nebulizer
11
12 gas
13 0.35 L min-1,
14
option gas
15
16 0.35 L min-1
17 (Ar, 80%; O2,
18
20%),
19
20 sampling
21 position
22
10 mm
23
24 2017 Pt/SiO2 Pt/SiO2 Dilution MicroMist RF power Q with 195 Pt+ 10 ms 17.2 nm Pt 234
25 nanocomposite nanocomposite pneumatic 1500 W, KED (He)
26
with ultra small nebulizer, nebulizer
27
28 Pt NPs Scott-type gas
29 spray chamber 1.05 L min-1,
30
sampling
31
32 position
33 8.0 mm
34
2018 Al-, Si-, Ti- Release from Wash with MicroMist n/s TQ 27 Al+, 28 Si+, 3 ms n/s H2 was used as a 235
35
36 containing NPs ceramic cookware Liquinox, nebulizer 48 Ti + reaction gas
37 during simulated release to 3%
38
linear abrasion acetic acid,
39
40 dilution
41
42
43 101
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2018 Ag NPs Consumer sprays Dilution n/s n/s Q n/s 10 ms 17.3- 236
9 35.3 nm
10
2018 Sb-, Pb-, Ba- Gunshot residue Wash with n/s n/s Q 121 Sb ,
+ 29 µs, n/s Single and dual 237
11
12 containing NPs wash from ultrapure water 137 Ba ,
+ 30 µs element modes
13 shooters' hands with 0.2% 208 Pb ,
+ for lead were used. Two
14
formaldehyde 121 Sb and
+ isotope isotopes
15
16 or hand 137 Ba ,
+ s monitoring with
17 swabbing with 121 Sb and
+ 145 µs settling
18
cotton swabs 208 Pb ,
+ time, 150 µs
19
20 and sonication 137 Ba and
+ settling time for
21 208 Pb ,
+ lead isotopes
22 206 Pb and
+
23
24 208 Pb+,
25 207 Pb+ and
26 208 Pb+,
27
28 206 Pb+ and
29 207 Pb+
30
2018 As-containing Cigarette smoke Smoke Dual-port spray n/s Q 75 As+ 0.1 ms n/s No As- 238
31
32 NPs collection with chamber containing NPs
33 electrostatic were found
34
trapping, wash
35
36 with methanol,
37 dilution with
38
deionized water
39
40
41
42
43 102
44
45
46
47
1
2
3
4
Table 1: Continued.
6

7
8 2018 Biogenic Se Se-rich yeast Enzymatic Concentric RF power Q with 78 Se , Se
+ 80 + 5 ms, 18 nm 239
9 NPs; 50, 100 nm digestion with nebulizer, 1550 W, KED (H2) 0.1 ms
10
Se NPs Driselase, cyclonic spray cooling gas
11
12 protease chamber 15 L min-1,
13 auxiliary gas
14
0.9 L min-1,
15
16 nebulizer
17 gas
18
1.10 L min-1
19
20 2018 Cu NPs Cuprum n/s n/s n/s Q n/s n/s 45 nm Cu, 240
21 metallicum, 52 nm Cu2O
22
Gelsemium
23
24 sempervirens
25 homeopathy
26
medicines
27
28 2019 Niobium and Microalloyed steel Etching in Pneumatic n/s TOF at MA, 48 Ti+, n/a 27.5 nm 241
29 titanium H2SO4 and nebulizer, 555 Hz 93 Nb+ NbCN,
30
carbonitride Disperbyk- cyclonic spray 50.5 nm
31
32 particles 2012, chamber TiNbCN
33 centrifugation
34
to remove
35
36 dissolved iron,
37 dilution
38
39
40
41
42
43 103
44
45
46
47
1
2
3
4
1 Note that the entries are grouped by the sample matrix that is the main focus of each study. Papers that report solely on
5
6 2 spICP-MS method development are not included.

7
8
9
10 3
11
12
13
4
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43 104
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45
46
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DOI: 10.1039/C9JA00206E
1
2
3
4
1 4 CONCLUSION
5
6
7 2 The past two decades have witnessed the commercial realization of new and

8
9
10 3 powerful ICP-MS instrumentation and methods, including instruments with faster data
11
12
4 acquisition, enhanced detection power, alternative mass analyzers, off-the-shelf interfaces
13
14
15 5 to couple liquid chromatography, CE, etc. to ICP-MS, and novel separation and
16
17
18 6 fractionation methods. While these instruments were successfully used for nanomaterials
19
20
7 characterization and the number of published studies of spICP-MS is steadily increasing,
21
22
23 8 there are some remaining challenges that need to be addressed to ultimately reach the
24
25
26 9 top of the nanoparticle peak.
27
28
29
30
31 10 Total consumption microflow nebulizers or droplet generators are attractive due
32
33
34
11 to a high particle transport efficiency. However, microflow nebulizers sometimes suffer
35
36 12 from clogging (in the presence of agglomerates or organic matter) and commercially
37
38
39 13 available droplet generators reportedly suffer from a limited day-to-day reproducibility
40
41
14 and cannot be coupled to autosamplers in the state in which they are available today.
42
43
44 15 Future research in the area of sample introduction for both stand-alone spICP-MS and
45
46
47 16 when interfaced with separation methods (e.g. CE-spICP-MS) is encouraged to address
48
49
17 these and other challenges with the ultimate goal of a high-throughput and robust
50
51
52 18 sample introduction system for single particle (and single-cell) ICP-MS. While sample
53
54
55 19 introduction is a potential source of error, sample preparation is often overlooked but
56
57
58 105
59
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1
2
3
4
1 may play an even bigger role, especially when particle number concentrations are to be
5
determined. Here, more fundamental studies on potential analyte losses and species
6 2
7

8
9 3 transformation (oxidation, release of ions, change of size, agglomeration) during
10
11
4 sampling, storage, and sample preparation are required. For example, a common sample
12
13
14 5 preparation step is filtration to remove unwanted organic matter and larger particle
15
16
17 6 fractions. However, particle losses might occur depending on the particle size and surface
18
19
7 coating interaction with the filter material and are often overlooked when particle number
20
21
22 8 concentrations are reported. Similarly to conventional analytical methods, the analyte
23
24
25 9 (particle) recovery should become a parameter that is always reported in future spICP-MS
26
27
10 studies.
28
29
30
31
32
33
11 Based on the publications discussed in this review and from our own findings, we
34
35 12 would like to stress that a careful optimization of the plasma conditions and dwell time is
36
37
38 13 required to achieve better NP size detection limits and accurate particle size and number
39
40
14 information respectively. In addition, instrumental developments to improve the ion
41
42
43 15 sampling/transfer efficiency in ICP-MS would help to further decrease the size detection
44
45
46 16 limits for single particles and also to gain access to information on NPs of mixed elemental
47
48
17 composition and core/shell materials.
49
50
51
52
53
54
55
56
57
58 106
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2
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4
1 While quadrupole-based ICP-MS systems were widely used in past spICP-MS
5
studies, we assume that mass analyzers that provide fast time-resolved and multielement
6 2
7

8
9 3 detection such as ICP-TOF-MS will play an important role in this field in the future.
10
11
4 However, even the best instrument is worthless if it cannot be calibrated properly, and
12
13
14 5 there is still the lack of appropriate reference materials for calibration. In the future, the
15
16
17 6 field would benefit from more well-characterized and certified nanomaterials to assure
18
19
7 accurate and precise quantification.
20
21
22
23
24
25
8 It can be concluded that spICP-MS is a very useful method for NPs analysis today but
26
27 9 there is still room for fundamental studies, instrumental improvements, and
28
29
30 10 methodological advances to come closer to what would be the ideal method for
31
32
33
11 nanomaterials characterization.
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
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3 1 CONFLICTS OF INTEREST
4
5
2 There are no conflicts to declare. The manuscript was written through contributions of all
6
7

8 3 authors. All authors have given approval to the final version of the manuscript. The authors declare
9
10 4 no competing financial interest.
11
12
13 5 ACKNOWLEDGMENT
14
15
16 6 We acknowledge the House of Young Talents of the University of Siegen for
17
18
19
7 providing funding for Darya Mozhayeva.
20
21
22 8
23
24
25 9 5 LIST OF ABBREVIATIONS
26
27
28 10
29
30 11 AF4 asymmetrical flow field-flow fractionation
31
32 12 BPEI branched polyethyleneimine
33
34
35 13 BSA bovine serum albumin
36
37 14 CAPS 3-cyclohexylamoniuopropanesulfonic acid
38
39 15 CE capillary electrophoresis
40
41
42 16 CIGS copper indium gallium selenide cells
43
44 17 CNT carbon nanotube
45
46 18 CPE cloud point extraction
47
48
49 19 CTAB cetyltrimethylammonium bromide
50
51 20 DAQ data acquisition
52
53 21 DMEM Dulbecco’s modified eagle medium
54
55
56 22 EPA Environmental Protection Agency
57
58 108
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4
1 ESD equivalent spherical diameter
5
2 ES-DMA electrospray-differential mobility analysis
6
7

8 3 FFF field flow fractionation
9
10
11
4 HDC hydrodynamic chromatography
12
5 HR-SEM high-resolution scanning electron microscopy
13
14
15 6 ICP-Q-MS single quadrupole ICP-MS
16
17
7 IEC ion-exchange column
18
19
20 8 KED kinetic energy discrimination
21
22 9 LA laser ablation
23
24
10 LDR linear dynamic range
25
26
27 11 LOD detection limit
28
29 12 m/z mass-to-charge ratio
30
31
13 MA multielement analysis
32
33
34 14 MC multi-collector
35
36 15 MDG microdroplet generator
37
38
16 MOPS 3-morpholinopropane-1-sulfonic acid
39
40
41 17 n/a not applicable
42
43 18 n/s not specified
44
45
19 NOM natural organic matter
46
47
48 20 NP nanoparticle
49
50 21 OECD The Organization for Economic Co-operation and Development
51
52
22 OES optical emission spectrometry
53
54
55 23 OPV organic photovoltaic cells
56
57
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2
3
4
1 PBS phosphate buffered saline
5
2 PEG polyethylene glycol
6
7

8 3 PFA perfluoroalkoxy alkane
9
10
11
4 PNC particle number concentration
12
5 PTFE polytetrafluoroethylene
13
14
15 6 PVA polyvinyl alcohol
16
17
7 PVP polyvinylpyrrolidone
18
19
20 8 Q quadrupole
21
22 9 QQQ triple quadrupole
23
24
10 RF radio frequency
25
26
27 11 SD standard deviation
28
29 12 SDS sodium dodecyl sulfate
30
31
13 SEM secondary electron multiplier
32
33
34 14 SF sector field
35
36 15 spICP-MS single particle inductively coupled plasma mass spectrometry
37
38
16 TAP tris-acetate-phosphate
39
40
41 17 TMAH tetramethylammonium hydroxide
42
43 18 TOF time-of-flight
44
45
19 TQ triple quadrupole
46
47
48 20 TSPP tetrasodium pyrophosphate
49
50 21 WWTP waste water treatment plant
51
52
22
53
54
55
56 23
57
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2
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