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Commonly used sample introduction systems for inductively coupled plasma mass spectrometry (ICP-MS) are generally not well-suited for single particle ICP-MS (spICP-MS) applications due to their high sample requirements and low efficiency. In this study, the first completely 3D-printed, polymer SIS was developed to facilitate spICP-MS analysis. The system is based on a microconcentric pneumatic nebulizer and a single-pass spray chamber with an additional sheath gas flow to further facilitate the transport of larger droplets or particles. The geometry of the system was optimized using numerical simulations. Its aerosol characteristics and operational conditions were studied via optical particle counting and a course of spICP-MS measurements, involving nanodispersions and cell suspensions. In a comparison of the performance of the new and the standard (quartz microconcentric nebulizer plus a double-pass spray chamber) systems, it was found that the new sample introduction system has four times higher particle detection efficiency, significantly better signal-to-noise ratio, provides ca. 20% lower size detection limit, and allows an extension of the upper limit of transportable particle diameters to about 25 µm. [ABSTRACT FROM AUTHOR]

Knowledge of dissolution, aggregation, and stability of nanoagrochemicals in root exudates (RE) and soil leachate will contribute to improving delivery mechanisms, transport in plants, and bioavailability. We characterized aggregation, stability, and dissolution of four nanoparticles (NPs) in soybean RE and soil leachate: nano-CeO2, nano-Mn3O4, nano-Cu(OH)2, and nano-MoO3. Aggregation differed considerably in different media. In RE, nano-Cu(OH)2, and nano-MoO3 increased their aggregate size for 5 days; their mean sizes increased from 518 ± 43 nm to 938 ± 32 nm, and from 372 ± 14 nm to 690 ± 65 nm, respectively. Conversely, nano-CeO2 and nano-Mn3O4 disaggregated in RE with time, decreasing from 289 ± 5 nm to 129 ± 10 nm, and from 761 ± 58 nm to 143 ± 18 nm, respectively. Organic acids in RE and soil leachate can be adsorbed onto particle surfaces, influencing aggregation. Charge of the four NPs was negative in contact with RE and soil leachate, due to organic matter present in RE and soil leachate. Dissolution in RE after 6 days was 38%, 1.2%, 0.5%, and

Due to enhanced properties at the nanoscale, nanomaterials (NMs) have been incorporated into foods, food additives, and food packaging materials. Knowledge gaps related to (but not limited to) fate, transport, bioaccumulation, and toxicity of nanomaterials have led to an expedient need to expand research efforts in the food research field. While classical techniques can provide information on dilute suspensions, these techniques sample a low throughput of nanoparticles (NPs) in the suspension and are limited in the range of the measurement metrics so orthogonal techniques must be used in tandem to fill in measurement gaps. New and innovative characterization techniques have been developed and optimized for employment in food nano-characterization. Single particle inductively coupled plasma mass spectrometry, a high-throughput nanoparticle characterization technique capable of providing vital measurands of NP-containing samples such as size distribution, number concentration, and NP evolution has been employed as a characterization technique in food research since its inception. Here, we offer a short, critical review highlighting existing studies that employ spICP-MS in food research with a particular focus on method validation and trends in sample preparation and spICP-MS methodology. Importantly, we identify and address areas in research as well as offer insights into yet to be addressed knowledge gaps in methodology. [ABSTRACT FROM AUTHOR]

Single particle inductively coupled plasma mass spectrometry has been used for size measurements of individual nanoparticles (NPs). Here, uncertainties in size analysis based upon two calibration approaches were evaluated: (i) the use of particle size standard and (ii) the use of ion standard solution. For particle size standard approach, the source of uncertainty to determine the target NP diameter was related to the variation in the signal intensities of both target NPs and particle size standard, and the size distribution of the particle size standard. The relative uncertainties of the 50 nm silver NP as the target were 15.0%, 9.9%, and 10.8% when particle size standards of 30 nm, 60 nm, and 100 nm silver NPs were used, respectively. As for the ion standard solution approach, the sources of uncertainty were the concentration of working standard solution, sample flow rate, transport efficiency, slope of calibration curve, and variation in the signal intensity of the ion standard solution and of the target NPs. The relative uncertainties for the 50 nm silver NP were 18.5% for 1 ng/g, 7.6% for 10 ng/g, and 4.7% for 100 ng/g solutions. The lower uncertainty obtained with a high concentration working standard solution is recommended to improve precision on particle size determinations by spICP-MS. [ABSTRACT FROM AUTHOR]

This paper proposes a novel approach to implement an internal standard (IS) correction in single particle inductively coupled plasma mass spectrometry (SP ICP-MS), as exemplified for the characterization of Au nanoparticles (NPs) in complex matrices. This approach is based on the use of the mass spectrometer (quadrupole) in bandpass mode, enhancing the sensitivity for the monitoring of AuNPs while also allowing for the detection of PtNPs in the same measurement run, such that they can serve as an internal standard. The performance of the method developed was proved for three different matrices: pure water, a 5 g L−1 NaCl water solution, and another water solution containing 2.5% (m/v) tetramethylammonium hydroxide (TMAH)/0.1% Triton X-100. It was observed that matrix-effects impacted both the sensitivity of the NPs and their transport efficiencies. To circumvent this problem, two methods were used to determine the TE: the particle size method for sizing and the dynamic mass flow method for the determination of the particle number concentration (PNC). This fact, together with the use of the IS, enabled us to attain accurate results in all cases, both for sizing and for the PNC determination. Additionally, the use of the bandpass mode provides additional flexibility for this characterization, as it is possible to easily tune the sensitivity achieved for each NP type to ensure that their distributions are sufficiently resolved. [ABSTRACT FROM AUTHOR]

The regulation and characterization of nanomaterials in foods are of great interest due to the potential risks associated with their exposure and the increasing number of applications where they are used within the food industry. One factor limiting the scientifically rigorous regulation of nanoparticles in foods is the lack of standardized procedures for the extraction of nanoparticles (NPs) from complex matrices without alteration of their physico-chemical properties. To this end, we tested and optimized two sample preparation approaches (enzymatic- and alkaline-based hydrolyses) in order to extract 40 nm of Ag NP, following their equilibration with a fatty ground beef matrix. NPs were characterized using single particle inductively coupled plasma mass spectrometry (SP-ICP-MS). Fast sample processing times (<20 min) were achieved using ultrasonication to accelerate the matrix degradation. NP losses during the sample preparation were minimized by optimizing the choice of enzymes/chemicals, the use of surfactants, and the product concentration and sonication. The alkaline approach using TMAH (tetramethylammonium hydroxide) was found to have the highest recoveries (over 90%); however, processed samples were found to be less stable than the samples processed using an enzymatic digestion based upon pork pancreatin and lipase (≈60 % recovery). Low method detection limits (MDLs) of 4.8 × 106 particles g−1 with a size detection limit (SDL) of 10.9 nm were achieved for the enzymatic extraction whereas an MDL of 5.7 × 107 particles g−1 and an SDL of 10.5 nm were obtained for the alkaline hydrolysis. [ABSTRACT FROM AUTHOR]

The concentration of silver nanoparticles (nano-Ag) in aqueous media influences the kinetics of ion release; hence, the transformation and stability of nano-Ag are also influenced. The stability, dissolution and further transformation of nano-Ag in aqueous media at predicted environmental concentrations (PECs) ≤ μg/L may differ from that reported at higher concentrations. Analytical techniques characterizing nanoparticles (NPs) at μg/L have advantages and limitations, including an inherent bias based on theoretical and analytical considerations, as well as the matrix effects. In this work, we applied nanoparticle tracking analysis (NTA), single particle ICP-MS (sp-ICP-MS), and localized surface plasmon resonance (LSPR) analysis to study the stability and dissolution of nano-Ag with different nominal sizes (20, 40, 80 and 100 nm) at PECs in synthetic wastewater (SWW). The influence of the main wastewater constituents, such as organic matter, Cl-, S2-, PO43- and NH4+, on the stability and dissolution of nano-Ag (40 nm) at PECs was also determined. Diagrams of the predominant species of silver exposed to major ligands were generated using MINTEQ. After 5 h in SWW, 20 nm nano-Ag dissolved 19.27% and 40 nm nano-Ag dissolved 14.8%. Aggregates of Ag particles were clearly noted for 80 and 100 nm nano-Ag after 5 h of exposure to SWW. Aggregates size also ranged very similar for both techniques, NTA and sp-ICP-MS, 29-211 nm and 38-241 for NTA and 48-210 and 50-220 nm, for sp-ICP-MS, respectively. Monodispersed size distribution (22-85 nm) and low dissolution (up to 5.1%) of nano-Ag at PECs were observed in presence of organic matter (5-800 μg/L) and PO43- (9.5-47.5 mg/L), while precipitation and higher dissolution (up to 74.9%) were observed in media containing either Cl- (0.07-10.64 g/L), S2- (0.32-32.1 mg/L) or NH4+ (36-90 mg/L), respectively. Speciation diagrams predict the formation of Ag2S(s) and AgCl(s), and soluble species such as AgClx(x-1)-, AgNH3+ and Ag(NH3)2+ when Ag+ at PECs in wastewater. The NTA and sp-ICP-MS were suitable techniques for sizing nano-Ag in wastewater at PECs at experimented nominal sizes. sp-ICP-MS was also useful to quantify the coexistence of Ag+ and nano-Ag. The LSPR analysis served to determine the relative persistence of original nano-Ag at PECs in the wastewater during the first 5 h after spiking.

Commonly used sample introduction systems for inductively coupled plasma mass spectrometry (ICP-MS) are generally not well-suited for single particle ICP-MS (spICP-MS) applications due to their high sample requirements and low efficiency. In this study, the first completely 3D-printed, polymer SIS was developed to facilitate spICP-MS analysis. The system is based on a microconcentric pneumatic nebulizer and a single-pass spray chamber with an additional sheath gas flow to further facilitate the transport of larger droplets or particles. The geometry of the system was optimized using numerical simulations. Its aerosol characteristics and operational conditions were studied via optical particle counting and a course of spICP-MS measurements, involving nanodispersions and cell suspensions. In a comparison of the performance of the new and the standard (quartz microconcentric nebulizer plus a double-pass spray chamber) systems, it was found that the new sample introduction system has four times higher particle detection efficiency, significantly better signal-to-noise ratio, provides ca. 20% lower size detection limit, and allows an extension of the upper limit of transportable particle diameters to about 25 µm.

While the predicted or observed concentrations of Ag NPs in wastewater treatment plants (WWTPs) have ranged from μg/L to ng/L, there is still uncertainty with regards to the realistic concentration range of Ag NPs in WWTPs. In addition, the persistence, removal, and size of Ag NPs throughout WWTP process is also not well investigated, particularly in real operating conditions. In this study, the incidence and persistence of Ag NPs in the wastewater process were studied by using single particle inductively coupled plasma mass spectrometry (sp-ICP-MS). The incidence of Ag NPs was determined in samples collected at the influent and effluent of the conventional process, as well as reclaimed and backwash waters of the ultrafiltration (UF) system in a WWTP (Santa Barbara, CA), showing a concentration of 13.5, 3.2, 0.5 and 9.8 ng/L, respectively, with relative standard deviations (RSDs)  Effluent > Reclaimed > SWW. Partial dissolution of NPs in all waters was observed from time 0 h. Although the current concentrations in the outlet flows from WWTP (effluent and reclaimed waters) were low, the presence of small and stable Ag NPs may raise ecotoxicological concerns via bioaccumulation.

We discuss the features involved in determining the titanium dioxide nanoparticle (TiO2NP) sizes in cosmetic samples via single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) in the millisecond-time resolution mode, and methods for considering the background signal. In the SP-ICP-MS determination of TiO2NPs in cosmetics, the background signal was recorded in each dwell time interval due to the signal of the Ti dissolved form in deionized water, and the background signal of the cosmetic matrix was compensated by dilution. A correction procedure for the frequency and intensity of the background signal is proposed, which differs from the known procedures due to its correction by the standard deviation above the background signal. Background signals were removed from the sample signal distribution using the deionized water signal distribution. Data processing was carried out using Microsoft Office Excel and SPCal software. The distributions of NP signals in cosmetic product samples were studied in the dwell time range of 4–20 ms. The limit of detection of the NP size (LODsize) with the proposed background signal correction procedure was 71 nm. For the studied samples, the LODsize did not depend on the threshold of the background signal and was determined by the sensitivity of the mass spectrometer. [ABSTRACT FROM AUTHOR]

Due to enhanced properties at the nanoscale, nanomaterials (NMs) have been incorporated into foods, food additives, and food packaging materials. Knowledge gaps related to (but not limited to) fate, transport, bioaccumulation, and toxicity of nanomaterials have led to an expedient need to expand research efforts in the food research field. While classical techniques can provide information on dilute suspensions, these techniques sample a low throughput of nanoparticles (NPs) in the suspension and are limited in the range of the measurement metrics so orthogonal techniques must be used in tandem to fill in measurement gaps. New and innovative characterization techniques have been developed and optimized for employment in food nano-characterization. Single particle inductively coupled plasma mass spectrometry, a high-throughput nanoparticle characterization technique capable of providing vital measurands of NP-containing samples such as size distribution, number concentration, and NP evolution has been employed as a characterization technique in food research since its inception. Here, we offer a short, critical review highlighting existing studies that employ spICP-MS in food research with a particular focus on method validation and trends in sample preparation and spICP-MS methodology. Importantly, we identify and address areas in research as well as offer insights into yet to be addressed knowledge gaps in methodology.

Ageing processes of vehicle catalytic converters inevitably lead to the release of Pt and Pd into the environment, road dust being the main sink. Though Pt and Pd are contained in catalytic converters in nanoparticulate metallic form, under environmental conditions, they can be transformed into toxic dissolved species. In the present work, the distribution of Pt and Pd between dissolved, nanoparticulate, and microparticulate fractions of Moscow road dust is assessed. The total concentrations of Pt and Pd in dust vary in the ranges 9–142 ng (mean 35) and 155–456 (mean 235) ng g−1, respectively. The nanoparticulate and dissolved species of Pt and Pd in dust were studied using single particle inductively coupled plasma mass spectrometry. The median sizes of nanoparticulate Pt and Pd were 7 and 13 nm, respectively. The nanoparticulate fraction of Pt and Pd in Moscow dust is only about 1.6–1.8%. The average contents of dissolved fraction of Pt and Pd are 10.4% and 4.1%, respectively. The major fractions of Pt and Pd (88–94%) in road dust are associated with microparticles. Although the microparticulate fractions of Pt and Pd are relatively stable, they may become dissolved under changing environmental conditions and, hence, transformed into toxic species. [ABSTRACT FROM AUTHOR]

The goal of the current study was to quantify the trophic transfer of copper nanoparticles (CuNPs) in a food chain consisting of the microalga Pseudokirchneriella subcapitata as the representative of primary producer, the grazer Daphnia magna, and the omnivorous mysid Limnomysis benedeni. To quantify the size and number concentration of CuNPs in the biota, tissue extraction with tetramethylammonium hydroxide (TMAH) was performed and quantification was done by single particle inductively coupled plasma mass spectrometry (sp-ICP-MS). The bioconcentration factor (BCF) of the test species for CuNPs varied between 102 – 103 L/kg dry weight when expressing the internal concentration on a mass basis, which was lower than BCF values reported for Cu2+ (103 – 104 L/kg dry weight). The particle size of CuNPs determined by sp-ICP-MS ranged from 22 to 40 nm in the species. No significant changes in the particle size were measured throughout the food chain. Moreover, the measured number of CuNPs in each trophic level was in the order of 1013 particles/kg wet weight. The calculated trophic transfer factor (mass concentration basis) was > 1. This indicates biomagnification of particulate Cu from P. subcapitata to L. benedeni. It was also found that the uptake of particulate Cu (based on the particle number concentration) was mainly from the dietary route rather than from direct aqueous exposure. Furthermore, dietary exposure to CuNPs had a significant effect on the feeding rate of mysid during their transfer from daphnia to mysid and from alga through daphnia to mysid. This work emphasizes the importance of tracing the particulate fraction of metal-based engineered nanoparticles when studying their uptake and trophic transfer.

Single particle inductively coupled plasma mass spectrometry has been used for size measurements of individual nanoparticles (NPs). Here, uncertainties in size analysis based upon two calibration approaches were evaluated: (i) the use of particle size standard and (ii) the use of ion standard solution. For particle size standard approach, the source of uncertainty to determine the target NP diameter was related to the variation in the signal intensities of both target NPs and particle size standard, and the size distribution of the particle size standard. The relative uncertainties of the 50 nm silver NP as the target were 15.0%, 9.9%, and 10.8% when particle size standards of 30 nm, 60 nm, and 100 nm silver NPs were used, respectively. As for the ion standard solution approach, the sources of uncertainty were the concentration of working standard solution, sample flow rate, transport efficiency, slope of calibration curve, and variation in the signal intensity of the ion standard solution and of the target NPs. The relative uncertainties for the 50 nm silver NP were 18.5% for 1 ng/g, 7.6% for 10 ng/g, and 4.7% for 100 ng/g solutions. The lower uncertainty obtained with a high concentration working standard solution is recommended to improve precision on particle size determinations by spICP-MS.

This paper proposes a novel approach to implement an internal standard (IS) correction in single particle inductively coupled plasma mass spectrometry (SP ICP-MS), as exemplified for the characterization of Au nanoparticles (NPs) in complex matrices. This approach is based on the use of the mass spectrometer (quadrupole) in bandpass mode, enhancing the sensitivity for the monitoring of AuNPs while also allowing for the detection of PtNPs in the same measurement run, such that they can serve as an internal standard. The performance of the method developed was proved for three different matrices: pure water, a 5 g L−1 NaCl water solution, and another water solution containing 2.5% (m/v) tetramethylammonium hydroxide (TMAH)/0.1% Triton X-100. It was observed that matrix-effects impacted both the sensitivity of the NPs and their transport efficiencies. To circumvent this problem, two methods were used to determine the TE: the particle size method for sizing and the dynamic mass flow method for the determination of the particle number concentration (PNC). This fact, together with the use of the IS, enabled us to attain accurate results in all cases, both for sizing and for the PNC determination. Additionally, the use of the bandpass mode provides additional flexibility for this characterization, as it is possible to easily tune the sensitivity achieved for each NP type to ensure that their distributions are sufficiently resolved.

The regulation and characterization of nanomaterials in foods are of great interest due to the potential risks associated with their exposure and the increasing number of applications where they are used within the food industry. One factor limiting the scientifically rigorous regulation of nanoparticles in foods is the lack of standardized procedures for the extraction of nanoparticles (NPs) from complex matrices without alteration of their physico-chemical properties. To this end, we tested and optimized two sample preparation approaches (enzymatic- and alkaline-based hydrolyses) in order to extract 40 nm of Ag NP, following their equilibration with a fatty ground beef matrix. NPs were characterized using single particle inductively coupled plasma mass spectrometry (SP-ICP-MS). Fast sample processing times (6 particles g−1 with a size detection limit (SDL) of 10.9 nm were achieved for the enzymatic extraction whereas an MDL of 5.7 × 107 particles g−1 and an SDL of 10.5 nm were obtained for the alkaline hydrolysis.

In single particle inductively coupled plasma mass spectrometry (spICP-MS), the transport efficiency is fundamental for the correct determination of both particle number concentration and size. In the present study, transport efficiency was systematically determined on three different days with six carefully characterised gold nanoparticle (AuNP) suspensions and in seven European and US expert laboratories using different ICP-MS instruments and spICP-MS software. Both particle size—(TES)—and particle frequency—(TEF)—methods were applied. The resulting transport efficiencies did not deviate much under ideal conditions. The TEF method however systematically resulted in lower transport efficiencies. The extent of this difference (0–300% rel. difference) depended largely on the choice and storage conditions of the nanoparticle suspensions used for the determination. The TES method is recommended when the principal measurement objective is particle size. If the main aim of the measurement is the determination of the particle number concentration, the TEF approach could be preferred as it might better account for particle losses in the sample introduction system. [ABSTRACT FROM AUTHOR]

It has been well known that the free ion concentration of metals plays a vital role in metal bioavailability. However, measurement of this fraction is still not easy over years of development. Nowadays, rare earth elements (REEs) are drawing more attentions as an emerging contaminant due to their wide applications in our daily life. To analyze the free ion concentration of neodymium (Nd), we adopted ion-exchange technique (IET) to investigate the changes on Nd free ion concentration in the presence of fulvic acid (FA). With the dynamic mode of IET analysis, the concentrations of Nd free ion were in the range of 0.85–36.8 × 10–8 M at the total Nd concentration of 5 × 10–7 M when FA varied from 0.4 to 10 M. However, these concentrations were 3–58 times higher than the one calculated by WHAM 7.0, which may be due to the particulate Nd spontaneously formed in solution. With single particle ICP-MS analysis, we found 0.25%–2.36% of Nd was in the form of colloids when the total Nd concentrations varied from 8.5 × 10–9 to 4.7 × 10–7 M, with the average particle sizes in the range of 26.5–39.2 nm. The presence of FA significantly decreased the number of Nd colloids, but increased the average particle size. Under the TEM, we found that Nd colloids were amorphous, with the size less than 200 nm. The present study provided a relatively new perspective on REE speciation in water. The natural organic matters not only affect the free ion concentration of Nd, but also influenced the size and numbers of Nd colloids in solution. [ABSTRACT FROM AUTHOR]

Transport efficiency has become a critical parameter in single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) since it is involved in the calibrations to determine different measurands (element mass per particle, particle size and particle number concentration). Specific methods for its determination based on the use of particle standards have been developed and widely applied (particle frequency and particle size methods). A refined indirect method not relying on particle standards is also available (dynamic mass flow method). A number of discrepancies on the accuracy of these methods and their adequacy have become evident, making a revision of the topic pertinent. In fact, the application of the particle frequency and particle size methods determine the transport efficiencies corresponding to the particles or the dissolved element respectively, whereas the solvent transport efficiency is actually measured by the dynamic mass flow method. The use of each of these methods requires assuming different conditions that must be considered. These conditions, together with the sources of bias associated to each method are critically discussed to provide a holistic and harmonized view of transport efficiency in the context of SP-ICP-MS metrology. [Display omitted] • Transport efficiency is a critical parameter in SP-ICP-MS. • Particle, dissolved element or solvent transport efficiencies are determined by current available methods. • A number of conditions are assumed when applying the different transport efficiencies. • A harmonized view of transport efficiency in SP-ICP-MS metrology is provided. [ABSTRACT FROM AUTHOR]

This paper provides a rebuttal to the comments on our original research article entitled "Comparison of Direct and Indirect Measures of Transport Efficiency in Single Particle ICP-MS" recently published by Goenaga-Infante in Spectrochimica Acta Part B: Atomic Spectroscopy. The intent of our study is not to condemn the dynamic mass flow (DMF) method but rather to explore the use parameters under which it can and cannot be applied. As explained in the original paper, the goal of this study is to evaluate the ranges of use conditions under which measures of transport efficiency (TE) yield accurate and reproducible results for spICP-MS measurements of particle number concentration (PNC) and particle size (diameter, PS) of various gold nanoparticle (AuNP) suspensions. The evaluation was performed through a systematic comparison of three methods for the measurement of TE: the particle frequency (TEF), particle size (TES), and DMF methods using three types of spray chambers operated at cooled and ambient temperature conditions and employing different ICP-MS platforms. While we appreciate thorough critical and constructive comments on our paper, we strongly disagree that the conclusions and highlights are not supported by the content and findings about the features and benefits of the DMF method. The discussion of three additional independent studies in this field by other spICP-MS expert groups that have been published after the submission of our manuscript is included in this paper. While the DMF approach has been used in two interlaboratory comparisons for TE determination in spICP-MS measurements of PNC, only one laboratory, namely the laboratory led by Goenaga-Infante, provided results using the DMF method in both projects. A method cannot be considered validated if successful results have only been demonstrated within one laboratory. The paper by Goenaga-Infante claims that the main use of DMF, the assignment of a SI traceable PNC value to new commercial nanomaterials (NMs), has not been highlighted explicitly in our original paper. The advantages and disadvantages of the DMF, TES, and TEF methods to measure TE were presented throughout the manuscript and are clearly summarized in the conclusion. The assignment of PNC that is metrologically traceable to the SI implies that all known or suspected uncertainty components including bias are taken into account. Our research shows that under some use conditions, the biases inherent to the DMF method are not yet fully understood and cannot be accounted for. While Cuello-Nuñez et al. Journal of Analytical Atomic Spectrometry, 2020, DOI: https://doi.org/10.1039/c9ja00415g state that cooled conditions (2 °C) were used in their work, they do not define the level of bias that can be expected if different spray chamber temperatures are used, and they do not provide recommendations on the optimal use conditions that define the field of applicability of the DMF method. Furthermore, besides the use of a Scott-type spray chamber cooled to 2 °C, neither the composition material of the spray chamber nor the volume of the Scott-type spray chamber were specified. It is important to note that in our original research, fifteen of the nineteen experiments were conducted using a cooled spray chamber. Also, the four different ICP-MS platforms were used in the standard configuration and with additional spray chamber options encountered in common ICP-MS usage. The value of our work is that it extends the study of Cuello-Nuñez et al. to a wide variety of use conditions routinely encountered in spICP-MS analysis. [Display omitted] • The intent of our original study is not to condemn the dynamic mass flow (DMF) method but rather to explore the use parameters for its applications. • The goal of our original study is to evaluate the ranges of use conditions under which measures of transport efficiency (TE) yield accurate and reproducible results for spICP-MS measurements of particle number concentration (PNC) and particle size (diameter, PS) of various gold nanoparticle (AuNP) suspensions. • The evaluation is performed through a systematic comparison of three methods for the measurement of TE: the particle frequency (TEF), particle size (TES), and DMF methods using three types of spray chambers operated at cooled and ambient temperature conditions and employing different ICP-MS platforms commonly used in spICP-MS analysis. • In our original research, fifteen of the nineteen experiments were conducted using a cooled spray chamber. In contrast to the experimental setup used by Cuello-Nuñez et al, we found that a cyclonic spray chamber cooled to 2 °C, rather than a Scott-type spray chamber gave satisfactory results for the DMF method as well as the TEF and TES methods. • The assignment of PNC that is metrologically traceable to the SI implies that all known or suspected uncertainty components including bias are taken into account. Our research shows that under some use conditions, the biases inherent to the DMF method are not yet fully understood and cannot be accounted for. [ABSTRACT FROM AUTHOR]

This paper provides critical and constructive comments on the paper "Comparison of direct and indirect measures of transport efficiency in single particle inductively coupled plasma mass spectrometry" by K. E. Murphy, A. R. Montoro Bustos, L. L. Yu, M. E. Johnson, M. R. Winchester, which has been recently published in Spectrochimica Acta Part B. It details the author's reservations about the discussions and message of this paper. It calls the reader's attention to the paper conclusions and highlights which are not supported by the paper content/findings but they only mislead the reader with regards to the features and benefits of the dynamic mass flow (DMF) method reported for the first time by Cuello et al., Journal of Analytical Atomic Spectrometry, 2020, DOI: https://doi.org/10.1039/c9ja00415g and used by other groups and in interlaboratory comparisons at the metrological level for transport efficiency determination in spICP-MS measurements of particle number concentration. The paper by Murphy et al. misses the key fact that DMF is not intended for use with any set up or condition but, if used under specified optimal operating set up and conditions (e.g. use of an ICP-MS system in equilibrium, a cooled spray chamber as reported by Cuello et al.) the method is invaluable for applications where use of the TEF and TES methods to determine transport efficiency is constrained by their reliance on reference materials which are limited or unavailable. The main use of DMF is the assignment of a SI traceable number concentration value to new, commercial nanomaterials and use those as quality control materials in spICP-MS experiments. This has not been highlighted explicitly in the paper under discussion. Instead, the findings rely heavily on data acquired by the DMF method using nineteen different conditions of which only one complies with the published recommendations and, unsurprisingly, for which the authors found the DMF to work. Indeed, some of the chosen operating conditions are unjustifiable given any knowledge of common ICP-MS usage. Yet this is used to justify condemning the DMF method and ignores the fact that close control of operating conditions is essential for many methods, particularly when striving for small uncertainty. • The dynamic mass flow approach (DMF) is not intended for use with any set up or condition but, like many metrological methods, requires careful optimisation. • The main use of DMF is the assignment of SI traceable number concentration values to new, commercial nanomaterials which are then available as quality control materials in spICP-MS experiments. This aspect has not been highlighted explicitly in the paper under discussion. • Instead, the findings rely heavily on data acquired by the DMF method using nineteen different conditions of which only one complies with the published recommendations and, unsurprisingly, for which the authors found the DMF to work. [ABSTRACT FROM AUTHOR]

Titanium dioxide nanoparticles (TiO2NPs) are widely produced and used NPs in different applications. To evaluate the risk from anthropogenic TiO2NPs, more information is needed on their occurrence in the environment. For the first time, this study reports the levels of TiO2NPs in waters and sediments at selected sampling sites along the Sava River using inductively coupled plasma mass spectrometry in single particle mode (spICP-MS). The highest concentrations of TiO2NPs were determined in river water at Vrhovo (VRH), Jasenovac (JAS), and Slavonski Brod (SLB) sampling locations impacted by urban, agricultural, and/or industrial activities, suggesting that these NPs are likely of anthropogenic origin. The results further showed that hydrological conditions and sediment composition significantly influence the levels of TiO2NPs in river water at most locations. Moreover, the Ti/Al elemental concentration ratios of NPs in water and sediments at JAS were higher than the natural background ratios, further confirming their anthropogenic origin. The outcome of this study provides first information on the presence of (anthropogenic) TiO2NPs in different environmental compartments of the Sava River, contributing to more reliable risk assessments and better regulation of TiO2NPs emissions in the future. [ABSTRACT FROM AUTHOR]

Plastics have long been an environmental contaminant of concern as both large-scale plastic debris and as micro- and nano-plastics with demonstrated wide-scale ubiquity. Research in the past decade has focused on the potential toxicological risks posed by microplastics, as well as their unique fate and transport brought on by their colloidal nature. These efforts have been slowed by the lack of analytical techniques with sufficient sensitivity and selectivity to adequately detect and characterize these contaminants in environmental and biological matrices. To improve analytical analyses, microplastic tracers are developed with recognizable isotopic, metallic, or fluorescent signatures capable of being identified amidst a complex background. Here we describe the synthesis, characterization, and application of a novel synthetic copolymer nanoplastic based on polystyrene (PS) and poly(2-vinylpyridine) (P2VP) intercalated with gold, platinum or palladium nanoparticles that can be capped with different polymeric shells meant to mimic the intended microplastic. In this work, particles with PS and polymethylmethacrylate (PMMA) shells are used to examine the behavior of microplastic particles in estuarine sediment and coastal waters. The micro- and nanoplastic tracers, with sizes between 300 and 500 nm in diameter, were characterized using multiple physical, chemical, and colloidal analysis techniques. The metallic signatures of the tracers allow for quantification by both bulk and single-particle inductively-coupled plasma mass spectrometry (ICP-MS and spICP-MS, respectively). As a demonstration of environmental applicability, the tracers were equilibrated with sediment collected from Bellingham Bay, WA, United States to determine the degree to which microplastics bind and sink in an estuary based of grain size and organic carbon parameters. In these experiments, between 80 and 95% of particles were found to associate with the sediment, demonstrative of estuaries being a major anticipated sink for these contaminants. These materials show considerable promise in their versatility, potential for multiplexing, and utility in studying micro- and nano-plastic transport in real-world environments.

The development of engineered nanotechnology has necessitated a commensurate maturation of nanoanalysis capabilities. Building off a legacy established by electron microscopy and light-scattering, environmental nanoanalysis has now benefited from ongoing advancements in instrumentation and data analysis, which enable a deeper understanding of nanomaterial properties, behavior, and impacts. Where once environmental nanoparticles and colloids were grouped into broad 'dissolved or particulate' classes that are dependent on a filter size cut-off, now size distributions of submicron particles can be separated and characterized providing a more comprehensive examination of the nanoscale. Inductively coupled plasma-quadrupole mass spectrometry (ICP-QMS), directly coupled to field flow fractionation (FFF-ICP-QMS) or operated in single particle mode (spICP-MS) have spearheaded a revolution in nanoanalysis, enabling research into nanomaterial behavior in environmental and biological systems at expected release concentrations. However, the complexity of the nanoparticle population drives a need to characterize and quantify the multi-element composition of nanoparticles, which has begun to be realized through the application of time-of-flight MS (spICP-TOFMS). Despite its relative infancy, this technique has begun to make significant strides in more fully characterizing particulate systems and expanding our understanding of nanoparticle behavior. Though there is still more work to be done with regards to improving instrumentation and data processing, it is possible we are on the cusp of a new nanoanalysis revolution, capable of broadening our understanding of the size regime between dissolved and bulk particulate compartments of the environment., Competing Interests: Declaration of competing interest None., (Copyright © 2023. Published by Elsevier B.V.)

We discuss the features involved in determining the titanium dioxide nanoparticle (TiO2NP) sizes in cosmetic samples via single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) in the millisecond-time resolution mode, and methods for considering the background signal. In the SP-ICP-MS determination of TiO2NPs in cosmetics, the background signal was recorded in each dwell time interval due to the signal of the Ti dissolved form in deionized water, and the background signal of the cosmetic matrix was compensated by dilution. A correction procedure for the frequency and intensity of the background signal is proposed, which differs from the known procedures due to its correction by the standard deviation above the background signal. Background signals were removed from the sample signal distribution using the deionized water signal distribution. Data processing was carried out using Microsoft Office Excel and SPCal software. The distributions of NP signals in cosmetic product samples were studied in the dwell time range of 4–20 ms. The limit of detection of the NP size (LODsize) with the proposed background signal correction procedure was 71 nm. For the studied samples, the LODsize did not depend on the threshold of the background signal and was determined by the sensitivity of the mass spectrometer.

The presence of metal salts has become one of the major limitations for measuring metallic nanoparticles (NPs) in single particle inductively coupled plasma mass spectrometry (spICP-MS). Their presence generates a background signal in spICP-MS that can be overlapped with the signal intensity of small particles, leading to inaccurate NP size distributions. To overcome this analytical problem, sample pretreatment methods (e.g. dilution or fractionation) have been applied to liquid samples before spICP-MS measurements to minimize the ionic interference. However, the number of studies focused on reducing the presence of metal salts in aerosol characterization is limited. In this contribution, we investigated three different technologies coupled to an ICP-MS for online separating metallic NPs signals from ionic interference signals of metal salts in the aerosol. A rotating disk diluter (RDD) was used for the online dilution of the aerosol, while a differential mobility analyzer (DMA) and a centrifugal particle mass analyzer (CPMA) were used for the online fractionation of specific-sized NPs in the aerosol. The results from the analysis of 100 nm gold NPs (AuNPs) mixed with gold salts (Au3+, mass ratio 1:25) showed the particle size limit of detection decreased from 78 nm to 61, 50, and 33 nm by using RDD, CPMA, and DMA respectively. In addition, it was found that the separation performance of AuNPs was in the order of DMA > RDD > CPMA. The methods used in this study based on spICP-MS have the potential to characterize directly NPs in complex aerosols containing metal salts. [Display omitted] • Effect of ionic interference in spICP-MS aerosol mode was compared to liquid mode. • RDD, DMA, and CPMA were investigated for reducing the ionic interference effect. • Separation based on electrical mobility was more effective than dilution. [ABSTRACT FROM AUTHOR]

Inorganic gunshot residue (IGSR) has certain environmental and occupational interferent-particle sources known to display similar morphologies and elemental compositions to IGSR. These interferences can make detecting and identifying IGSR particles difficult, especially when IGSR particle number concentrations are low. Here, single-particle inductively coupled plasma time-of-flight mass spectrometry (spICP-TOFMS) is used to explore the particle types measured from IGSR and three important interferent-particle sources: brake pads, fireworks, and mineral sunscreen. spICP-TOFMS offers results in as little as 2 min per sample. With spICP-TOFMS, the mass of most elements, down to the 10s of attograms, can be detected and quantified in individual particles with diameters from 10s to 100s of nm. At this size range, almost all interferent sources produce particles with elemental compositions that overlap with ASTM-defined particle compositions used for identifying leaded and lead-free IGSR. We establish probabilities for detecting IGSR-like particles from interference sources through the analysis of thousands of particles from each interference. Based on this analysis, robust sample-specific 'characteristic' particle types can be used to classify leaded and unleaded IGSR particles, even in the presence of interferent particles. Of the interference sources studied, particles from brake pads and fireworks are most similar to leaded IGSR; however, IGSR particles could be unequivocally classified based on detection of lead and antimony. Particles from mineral sunscreen are most similar to those from lead-free IGSR; however, lead-free IGSR particles exhibit a unique titanium-zinc-copper elemental fingerprint that is not detected in mineral sunscreen particles. Within mixtures of interference particles and IGSR, IGSR is accurately identified with limited false positives, even when the number of interference particles is over 200-times greater than that of IGSR. Our results suggest that spICP-TOFMS is a useful approach for rapid and accurate IGSR identification even in samples with high concentrations of interferent background particles. [Display omitted] • Leaded and lead-free inorganic gunshot residue (IGSR) analysis via spICP-TOFMS. • Characterization of particles from fireworks, brake pads, and mineral sunscreen. • Probability of finding IGSR-like particles, as defined by ASTM, in interferences. • Signature particle compositions (Pb–Sb) found to identify IGSR from interferences. • Accurate classification of IGSR in various interfering particle concentrations. [ABSTRACT FROM AUTHOR]

Accurate calibration of the fraction of introduced sample that is transported to the plasma, termed "transport efficiency" (TE), is required for particle sizing and number concentration determination by single particle inductively coupled plasma mass spectrometry (spICP-MS). In this study, we systematically compare three methods for the measurement of TE: the particle frequency (TEF), particle size (TES), and dynamic mass flow (DMF) methods. The TEF and TES methods provide a direct measure of TE but require a single nanoparticle (NP) reference material accurately value-assigned for particle size and number concentration of which few are available. The DMF method provides an indirect measure of TE and only requires measurement of the mass difference between the amount of sample solution introduced to the instrument and the amount of effluent exiting the spray chamber. Because the DMF method relies solely on mass measurements, it can provide an SI traceable measure of TE. However, the DMF method assumes that the mass difference represents the fraction of sample transported to the plasma. The veracity of the three approaches to account for TE is assessed using three different spray chamber types, i.e., Scott-type double pass, conical impact bead, and baffled cyclonic spray chambers operated at cooled (2 °C to 10 °C) and ambient temperature (19 °C to 21 °C) conditions equipped with different nebulizers on different ICP-MS platforms. When operating the spray chamber at ambient temperature, the DMF method yielded systematically higher measures of TE than the TEF and TES methods regardless of nebulizer type, spray chamber type, or ICP-MS platform. While better agreement between the three measures of TE was achieved when operating the spray chambers at 2 °C, DMF repeatability was poor. The deviation of particle number concentration, expressed as the median percent difference from the known value for various in-house value-assigned AuNP suspensions, ranged from – 18% to +8% (TEF) and from – 1% to – 70% (DMF) whereas the deviation for particle size ranged from – 3% to +1% (TES) and from – 4% to +44% (DMF) across all conditions. The large negative bias for counting and positive bias for sizing by the DMF method indicates an overestimation of TE which was traced to low recovery of the mass of effluent exiting the spray chamber. We found that the indirect measure of TE (DMF method) yielded acceptable results (within ±10% of known values for particle size and ± 20% of known values for number concentration) under select conditions (cyclonic spray chamber at 2 °C and Meinhard nebulizer), but the biases inherent to the DMF method are not fully understood for all studied conditions. Only the direct measures of TE (TEF and TES) yielded acceptable results across all use conditions. [Display omitted] • Dynamic Mass Flow (DMF) method reliable only under select use conditions. • DMF method always overestimates the measure of TE when the spray chamber is at ambient temperature. • Biases inherent to DMF method are not fully understood under all use conditions. • Direct measure of TE with nanoparticle reference materials yields superior results. • Accurate size and concentration for direct measure of TE across all use conditions. [ABSTRACT FROM AUTHOR]

A sample preparation method associated to a single particle inductively coupled plasma mass spectrometry (spICP-MS) analysis was developed to ensure a quantitative characterization of TiO 2 particles in food sauces. The method was optimized with a fat sauce matrix for which the pristine E171 additive was available. The highest extracted amount of TiO 2 particles was obtained using an ultrasound-assisted dispersion in tetramethylammonium hydroxide (TMAH). TEM analysis confirmed these results, showing that these conditions effectively solubilised the fat matrix. The trueness of the method evaluated using a Ti-free mayonnaise spiked with the E171 additive or the NM-100 reference material (NM-100 RM) proved satisfactory with quantitative mass recoveries (>90%). A good agreement in terms of particle sizes was also obtained between those of the spiked mayonnaise and the TiO 2 suspensions used for spiking. However, as also shown in the optimization study, the presence of fatty compounds tended to improve particle dispersion. The application of this procedure to E171 labelled food sauces purchased from the EU market showed concentrations of TiO 2 particles in the (0.6 – 6) g/kg range with median diameters between 170 and 320 nm. The TiO 2 nanoparticle fraction (size < 100 nm) was evaluated between 2% and 12%, depending on the sample. No titanium was detected in the food sauces not labelled E171. Conclusively, the developed method can provide an efficient and reliable analytical approach for TiO 2 particles determination in fat food samples which complies with the EU current regulations. • TMAH for an efficient TiO 2 particle extraction from fatty food sauces. • Characterization of TiO 2 particle by single particle ICP-MS. • The TiO 2 PSD in a processed food and the pristine E171 additive were compared. • The method was applied to commercialized food sauces from the EU market. [ABSTRACT FROM AUTHOR]

The detection and characterization of soluble metal nanoparticles in plant tissues are an analytical challenge, though a scientific necessity for regulating nano-enabled agrichemicals. The efficacy of two extraction methods to prepare plant samples for analysis by single particle ICP-MS, an analytical method enabling both size determination and quantification of nanoparticles (NP), was assessed. A standard enzyme-based extraction was compared to a newly developed methanol-based approach. Au, CuO, and ZnO NPs were extracted from three different plant leaf materials (lettuce, corn, and kale) selected for their agricultural relevance and differing characteristics. The enzyme-based approach was found to be unsuitable because of changes in the recovered NP size distribution of CuO NP. The MeOH-based extraction allowed reproducible extraction of the particle size distribution (PSD) without major alteration caused by the extraction. The type of leaf tissue did not significantly affect the recovered PSD. Total metal losses during the extraction process were largely due to the filtration step prior to analysis by spICP-MS, though this did not significantly affect PSD recovery. The methanol extraction worked with the three different NPs and plants tested and is suitable for studying the fate of labile metal-based nano-enabled agrichemicals. [ABSTRACT FROM AUTHOR]

Titanium dioxide nanoparticles (TiO2NPs) are widely produced and used NPs in different applications. To evaluate the risk from anthropogenic TiO2NPs, more information is needed on their occurrence in the environment. For the first time, this study reports the levels of TiO2NPs in waters and sediments at selected sampling sites along the Sava River using inductively coupled plasma mass spectrometry in single particle mode (spICP-MS). The highest concentrations of TiO2NPs were determined in river water at Vrhovo (VRH), Jasenovac (JAS), and Slavonski Brod (SLB) sampling locations impacted by urban, agricultural, and/or industrial activities, suggesting that these NPs are likely of anthropogenic origin. The results further showed that hydrological conditions and sediment composition significantly influence the levels of TiO2NPs in river water at most locations. Moreover, the Ti/Al elemental concentration ratios of NPs in water and sediments at JAS were higher than the natural background ratios, further confirming their anthropogenic origin. The outcome of this study provides first information on the presence of (anthropogenic) TiO2NPs in different environmental compartments of the Sava River, contributing to more reliable risk assessments and better regulation of TiO2NPs emissions in the future.

In single particle inductively coupled plasma mass spectrometry (spICP-MS), the transport efficiency is fundamental for the correct determination of both particle number concentration and size. In the present study, transport efficiency was systematically determined on three different days with six carefully characterised gold nanoparticle (AuNP) suspensions and in seven European and US expert laboratories using different ICP-MS instruments and spICP-MS software. Both particle size—(TES)—and particle frequency—(TEF)—methods were applied. The resulting transport efficiencies did not deviate much under ideal conditions. The TEF method however systematically resulted in lower transport efficiencies. The extent of this difference (0–300% rel. difference) depended largely on the choice and storage conditions of the nanoparticle suspensions used for the determination. The TES method is recommended when the principal measurement objective is particle size. If the main aim of the measurement is the determination of the particle number concentration, the TEF approach could be preferred as it might better account for particle losses in the sample introduction system.

Titanium dioxide nanoparticles (TiO2 NPs) are increasingly used in a wide range of consumer products and industrial applications, causing their presence in the environment, where they can interact with plants including edible ones. In addition, the released TiO2 NPs can undergo chemical and physical transformations, which may influence their potential toxicity. However, the study of TiO2 NPs in environmental samples by the technique offering the highest sensitivity, ICP-MS, is hampered by the presence of some elements (such as, e.g., Ca abundant in plant tissues) that cause polyatomic and/or isobaric interferences. This study proposed, for the first time, the use of a triple-quadrupole ICP operating in tandem mass spectrometry and single-particle mode (SP-ICP-QQQ-MS) to study the uptake, translocation, and possible transformations of TiO2 NPs with two different nominal sizes in a model plant (Raphanus sativus L.). A careful optimization of the reaction cell conditions (O2 and H2 gas flows) allowed the reduction in background level and resulted in a significant increase in the sensitivity of the analysis, bringing size detection limits for TiO2 NPs down to 15 nm in ultrapure water and to 21 nm in a matrix containing 50 mg L–1 of Ca. In addition, an enzymatic digestion procedure was applied in order to extract intact nanoparticles from the tissues of plants treated with TiO2 NPs, followed by size characterization by SP-ICP-MS. The size distributions obtained in roots treated with TiO2 NPs suggested a preferential uptake of smaller nanoparticles. Results also revealed that the majority of TiO2 NPs were retained in roots. Additionally, no significant dissolution was observed, as well as no differences for nanoparticles found in roots and leaves, proving that radish is able to translocate intact TiO2 NPs up to aboveground organs.

The recent expansion in the use of nanomaterials in consumer and industrial applications has led to a growing concern over their behavior, fate, and impacts in environmental systems. However, engineered nanoparticles comprise only a small fraction of the total nanoparticle mass in aquatic systems. Human activities, particularly in urban watersheds, are increasing the population of incidental nanoparticles and are likely altering the cycling of more abundant natural nanoparticles. Accurate detection, quantification, characterization, and tracking of these different populations is important for assessing both the ecological risks of anthropogenic particles, and their impact on environmental health. The urban portion of the South Platte watershed in Denver, Colorado (United States) was sampled for zinc to identify and quantify different nanomaterial sources. Single particle ICP-QMS was employed, to provide single elemental (Zn) signals arising from particle detection events. Coupling spICP-QMS to sample pre-fractionation (sedimentation, filtration) provided some insights into Zn association with nanoparticulate, colloidal, and suspended sediment phases. Single particle ICP-TOFMS (spICP-TOFMS) provided quantification across a large atomic mass range, yielding an even more detailed characterization (elemental ratios) on a particle-by-particle basis, providing some delineation of multiple sources of particles. Across the watershed, on average, 21% of zinc mass was present as zinc-only particles with a rather uniform mean size of 40.2 nm. Zinc that was detected with one or more other elements, primarily Al, Fe, and Si, is likely to be present as heteroagglomerates or within mineral colloids. Although spICP-TOFMS provides a substantial amount of information, it is still in its early stages as an analytical technique and currently lacks the requisite sensitivity to study the smallest of nanoparticles. As this technique continues to develop, it is anticipated that this methodology can be broadly applied to study sources, behavior and effects of a disparate variety of nanoparticles from both geogenic and anthropogenic origins.

Assessing the impact of nanoparticles in living systems implies a proper evaluation of their behaviour at single-cell level. Due to the small size of nanoparticles, their accumulation, transformation and location within single cells is challenging. In this work, the combination of single cell/single particle triple quadrupole inductively coupled plasma mass spectrometry (SC/SP-ICP-TQ-MS) analysis along with X-ray diffraction (XRD) and transmission electron microscopy (TEM) measurements has been applied to go deeper into the uptake and biotransformation of tellurium nanoparticles (TeNPs) in two bacterial model organisms, S. aureus and E. coli. The use of SC-ICP-TQ-MS enabled the individual introduction of bacterial cells where tellurium and phosphorous (as constitutive element) were monitored and detected at concentration levels down to femtogram (fg) per cell. S.aureus uptake of TeNPs was 0.5–1.9 fg Te cell−1 and 7–30 fg Te cell−1 in presence of 0.5 and 15 mg Te L−1 of TeNPs, respectively, whereas for E. coli , the amount of Te ranged from 0.08 to 0.88 fg Te cell−1 and from 2 to 36 fg Te cell−1 in presence of 0.5 and 15 mg Te L−1 of TeNPs, respectively. TEM and XRD analysis confirmed the occurrence of TeNPs biotransformation (from nanospheres to nanorods) as the nanoparticles were incorporated into both bacterial strains. Finally, SP-ICP-MS analysis after cell lysis was applied to determine the number of particles/rods per bacteria cell and to perform the dimensional characterization of the rod-shaped TeNPs. The results obtained clearly confirmed high cell-to-cell variability in terms of Te nanorods dimensions and TeNPs uptake. To the best of our knowledge, this is the first time that SC/SP-ICP-TQ-MS along with TEM and XRD analysis have been applied to investigate, quantitatively, nanoparticle uptake in bacterial cells and to estimate the dimensions of biogenic Te nanorods. Image 1 • SC-ICP-MS was used to quantify the uptake of TeNPs in single bacterial cells. • S.aureus uptake of TeNPs ranged from 0.5 to 1.9 fg Te cell−1. • E. coli uptake of TeNPs ranged from 0.08 to 0.88 fg Te cell−1. • Mass distribution histograms confirm high cell to cell variability in TeNPs uptake. • Dimensions of Te nanorods were estimated by SP-ICP-MS and TEM measurements. [ABSTRACT FROM AUTHOR]

Silicon dioxide (silica, SiO2, SAS) and titanium dioxide (TiO2) are produced in high volumes and applied in many consumer and food products. As a consequence, there is a potential human exposure and subsequent systemic uptake of these particles. In this study we show the characterization and quantification of both total silicon (Si) and titanium (Ti), and particulate SiO2 and TiO2 in postmortem tissue samples from 15 deceased persons. Included tissues are liver, spleen, kidney and the intestinal tissues jejunum and ileum. Low-level analysis was enabled by the use of fully validated sample digestion methods combined with (single particle) inductively coupled plasma high resolution mass spectrometry techniques (spICP-HRMS). The results show a total-Si concentration ranging from <2 to 191 mg Si/kg (median values of 5.8 (liver), 9.5 (spleen), 7.7 (kidney), 6.8 (jejunum), 7.6 (ileum) mg Si/kg) while the particulate SiO2 ranged from <0.2 to 25 mg Si/kg (median values of 0.4 (liver), 1.0 (spleen), 0.4 (kidney), 0.7 (jejunum, 0.6 (ileum) mg Si/kg), explaining about 10% of the total-Si concentration. Particle sizes ranged from 150 to 850 nm with a mode of 270 nm. For total-Ti the results show concentrations ranging from <0.01 to 2.0 mg Ti/kg (median values of 0.02 (liver), 0.04 (spleen), 0.05 (kidney), 0.13 (jejunum), 0.26 (ileum) mg Ti/kg) while particulate TiO2 concentrations ranged from 0.01 to 1.8 mg Ti/kg (median values of 0.02 (liver), 0.02 (spleen), 0.03 (kidney), 0.08 (jejunum), 0.25 (ileum) mg Ti/kg). In general, the particulate TiO2 explained 80% of the total-Ti concentration. This indicates that most Ti in these organ tissues is particulate material. The detected particles comprise primary particles, aggregates and agglomerates, and were in the range of 50–500 nm with a mode in the range of 100–160 nm. About 17% of the detected TiO2 particles had a size <100 nm. The presence of SiO2 and TiO2 particles in liver tissue was confirmed by scanning electron microscopy with energy dispersive X-ray spectrometry. [ABSTRACT FROM AUTHOR]

This study reports on the development of a single-particle (sp) inductively coupled plasma mass spectrometry (ICP-MS) technique suitable for the multi-mode determination of nanoparticle (NP) metal mass fraction and number concentration. The described technique, which is based on a dual inlet system consisting of a pneumatic nebulizer (PN) and a microdroplet generator (MDG), allows for the sequential introduction of ionic metal calibrant solutions and nanoparticle suspensions via all combinations of the two inlets; thus allowing for a combination of three independent modes of analysis. A novel interface, assembled using standard analytical components (a demountable quartz ICP-MS torch, flexible non-conducting silicon tubing and various connectors), was used to interface the dual inlet system to an ICP-MS. The interface provided improved functionality, compared to a previous design. It is now possible to conveniently exchange and introduce standard solutions and samples via all inlet combinations, analyze them, and also wash the sample inlet systems while the whole setup is still connected to an operating ICP-MS. This setup provided seamless and robust operation in a total of three analysis modes, i.e. three ways to independently determine the metal mass fraction and NP number concentration. All three analyses modes could be carried out within a single analytical run lasting approximately 20 min. The unique feature of the described approach is that each analysis mode is based on a different calibration principle, thus constituting an independent way to determine metal mass fractions and nanoparticle number concentrations. Conducting the three independent state-of-the-art analysis, within a single analytical run, improves substantially the validation capabilities of sp-ICP-MS for NP analysis. To assess the technique's analytical performance, Au, Ag and CeO 2 nanoparticles were analyzed. The determined average diameters for Au (56.7 ± 1.5 nm), Ag (72.8 ± 3.4 nm) and CeO 2 (69.0 ± 6.4 nm) NPs were in close agreement for all three modes of analysis, as well as with the values provided by suppliers' for Au and Ag NPs (56.0 ± 0.5 for Au, 74.6 ± 3.8 nm for Ag). However, the determined average value for CeO 2 was much higher than the expected 28.4 ± 10.4 nm, possibly due to NP agglomeration and the inability to detect NPs existing within the lower size range. The determined NP number concentrations, using analysis modes –I and –II, gave recoveries between 91 and 100% for the Au and Ag NP number concentrations. Whereas analysis mode –III showed a recovery of 70–88% for the same materials. Because of the polydispersity, the small size and polyhedral shape of the CeO 2 NPs it was not possible to make NP number concentration comparisons for this material. Image 1 • Development of a dual interface for inductively coupled plasma mass spectrometer. • Application of a microdroplet generator and a nebulizer for sample introduction. • Robust and reliable interface for nanoparticle size characterization. • Enabling three different analysis modes to determine nanoparticle size characteristics. • Reference material independent size characterization. [ABSTRACT FROM AUTHOR]

Due to their unique physical and chemical properties, the production and use of cerium oxide nanoparticles (CeO 2 NPs) in different areas, especially in automotive industry, is rapidly increasing, causing their presence in the environment. Released CeO 2 NPs can undergo different transformations and interact with the soil and hence with plants, providing a potential pathway for human exposure and leading to serious concerns about their impact on the ecosystem and human organism. This study investigates the uptake, bioaccumulation, possible translocation and localization of CeO 2 NPs in a model plant (Raphanus sativus L.), whose edible part is in direct contact with the soil where contamination is more likely to happen. The stability of CeO 2 NPs in plant growth medium as well as after applying a standard enzymatic digestion procedure was tested by single particle ICP-MS (SP-ICP-MS) showing that CeO 2 NPs can remain intact after enzymatic digestion; however, an agglomeration process was observed in the growth medium already after one day of cultivation. An enzymatic digestion method was next used in order to extract intact nanoparticles from the tissues of plants cultivated from the stage of seeds, followed by size characterization by SP-ICP-MS. The results obtained by SP-ICP-MS showed a narrower size distribution in the case of roots suggesting preferential uptake of smaller nanoparticles which led to the conclusion that plants do not take up the CeO 2 NPs agglomerates present in the medium. However, nanoparticles at higher diameters were observed after analysis of leaves plus stems. Additionally, a small degree of dissolution was observed in the case of roots. Finally, after CeO 2 NPs treatment of adult plants, the spatial distribution of intact CeO 2 NPs in the radish roots was studied by laser ablation ICP-MS (LA-ICP-MS) and the ability of NPs to enter and be accumulated in root tissues was confirmed. Unlabelled Image • A particle ionization efficiency of 10% was determined for CeO 2 NPs. • CeO 2 NPs undergo aggregation after 24 h in contact with growth media. • A preferential uptake of CeO 2 NPs by radish was observed. • CeO 2 NPs agglomerate at the endpoint of their translocation from roots to leaves. • CeO 2 NPs can enter and be accumulated in root tissues. [ABSTRACT FROM AUTHOR]

• Studies on the degradation of Au nanoparticles in rat liver after intraperitoneal injection. • Liver extracts analysed by TEM, spICP-MS and HPLC-ICP-MS. • Smaller Au nanoparticles and low-molecular Au species could be detected. Due to the increased use of engineered nanoparticles (NPs), their tracing in environmental and biological systems is of utmost importance. Besides their accumulation within a biological specimen, little is known about their degradation and transformation into corresponding low-molecular species that might influence any toxicological impact. Wistar rats underwent intraperitoneal injections of 40 nm citrate-stabilized gold nanoparticles. Different liver samples were analysed for the occurrence of nanoparticles and potential degradation products by means of spICP-MS, TEM and HPLC-ICP-MS. Studies using spICP-MS revealed the presence of the originally administrated Au NPs (40 nm diameter) and some evidences of other Au-containing species due to the increased background signal. Images obtained by transmission electron microscopy (TEM) showed the predominant presence of particles of significantly smaller diameter (6 ± 2 nm). As complementary method, HPLC-ICP-MS confirmed the presence of both particle types indicating a degradation of the Au NPs accompanied by detection of low-molecular Au species. This study underlines that degradation of gold nanoparticles to low-molecular gold species might have to be taken into account in future for studies on their toxicological behaviour and their potential use in clinical applications. [ABSTRACT FROM AUTHOR]

Abstract Municipal water resource recovery facilities are the primary recipients of a significant fraction of discharged silver nanoparticle (AgNP)-containing wastes, yet the fate and potential risks of AgNPs in attached-growth biological wastewater treatment processes are poorly understood. The fate and inhibitory effects of polyvinylpyrrolidone (PVP)-coated AgNPs at environmentally-relevant nominal concentrations (10, 100, 600 μg/L) were investigated, for the first time, in high rate moving bed biofilm reactors (MBBRs) for soluble organic matter removal. The behavior and removal of continuously added AgNPs were characterized using single-particle inductively coupled plasma mass spectrometry (spICP-MS). While no inhibitory effect at average influent concentration of 10.8 μg/L Ag was observed, soluble COD removal efficiency was significantly decreased at 131 μg/L Ag in 18 days and 631 μg/L Ag in 5 days with suppressed biofilm viability. The inhibitory effect of AgNPs on treatment efficiency was highly correlated to the retained mass of total Ag in attached biofilm on the carriers. Biofilm demonstrated limited retention capacity for AgNPs over 18 days. Considerable mass of Ag (38% to 75%) was released via effluent, predominantly as NPs. We detected some chemically transformed and potentially less toxic forms of silver nanoparticles (Ag 2 S, AgCl), over the exposure period. This study demonstrated the distinct interaction dynamics, bioavailability and inhibitory effects of AgNPs in a biofilm system. Release of bioavailable AgNPs via effluent and AgNP-rich biofilm, sloughing off the carriers, can affect the treatment chain efficiency of downstream processes. Thus, the inhibitory effects of AgNPs can be a concern even at concentrations as low as 100 to 600 μg/L Ag in biological attached growth wastewater treatments. Graphical abstract Unlabelled Image Highlights • Silver nanoparticles (AgNPs) at 100–600 μg/L suppressed the soluble COD removal efficiency and biofilm viability. • Significant amounts of established biofilm detached from the carriers, exposed to 100–600 μg/L AgNPs. • Aerobic heterotrophic biofilm had a limited retention capacity for AgNPs. • A dominant proportion of the effluent Ag was in the NP form. [ABSTRACT FROM AUTHOR]

We tested six kinds of commercially available baby products containing nano-silver and divided them into two categories: baby food containers and baby oral care products, according to usage. We measured the total mass of silver, particle size, particle number concentration and the mobility under different simulated conditions. The total mass of silver in baby products and migration solutions was quantified by ICP-MS analysis, and the size of the migrated particles was investigated by single particle ICP-MS and transmission electron microscopy-energy dispersive spectrometer. Nano-silver has different migration behaviour in different materials, and the total mass of silver released in 3% acetic acid was generally highest for plastic material, while highest in 10% ethanol for silicone material. For baby food containers and baby oral care products, the total amount of silver in the migration solutions varied from 2.98 to 126.46 ng/dm2 and from 2.01 to 2.83 ng/g, respectively. The research shows that the use of baby products containing silver may expose babies to silver nanoparticles. [ABSTRACT FROM AUTHOR]

As the production and use of cerium oxide nanoparticles (CeO2 NPs) increases, so does the concern of the scientific community over their release into the environment. Single particle inductively coupled plasma mass spectrometry is emerging as one of the best techniques for NP detection and quantification; however, it is often limited by high size detection limits (SDL). To that end, a high sensitivity sector field ICP-MS (SF-ICP-MS) with microsecond dwell times (50 µs) was used to lower the SDL of CeO2 NPs to below 4.0 nm. Ag and Au NPs were also analyzed for reference. SF-ICP-MS was then used to detect CeO2 NPs in a Montreal rainwater at a concentration of (2.2 ± 0.1) × 108 L−1 with a mean diameter of 10.8 ± 0.2 nm; and in a St. Lawrence River water at a concentration of ((1.6 ± 0.3) × 109 L−1) with a higher mean diameter (21.9 ± 0.8 nm). SF-ICP-MS and single particle time of flight ICP-MS on Ce and La indicated that 36% of the Ce-containing NPs detected in Montreal rainwater were engineered Ce NPs.