The suitability of existing certified reference materials (CRMs) intended for analysis of macro and trace elements in food as effective control materials for single particle inductively coupled plasma-mass spectrometry (spICP-MS) was examined. The presence of nanoparticles (NPs) in these CRMs was evaluated in parallel at two independent laboratories with a focus on matrices such as wheat flour, mussels, and multielement/multivitamin tablets. In general, this bilateral comparison resulted in a good agreement for the determination of different metal-containing NP diameters and particle size distributions (PSDs) for NIST SRM 1567a (wheat flour), NIST SRM 2976 (mussel tissue), NIST SRM 3294 (multielement tablets), and NRC VITA-1 (low-level multivitamin tablets). We provide evidence regarding the impact of the processing software on the computation of the size limit of detection and, hence, on resulting PSDs. However, despite similar sample preparation, instrumental settings, and data processing approaches, the bilateral comparison revealed interlaboratory differences in particle number concentration (PNC), indicating that achieving reproducible PNC results by spICP-MS in complex samples remains analytically challenging. Lastly, a selection of marine animal- and plant-based CRMs was screened for the presence of metal-containing NPs to identify potential candidates suitable for further in-depth quantitative efforts, revealing the presence of large numbers of Al-, Fe-, and Si-containing NPs.

In response to the growing concern of microplastics (1 μm to 5 mm) accumulation affecting human health, the development of analytical methods continues to be critical for the detection and characterization of microplastic particles. In this context, pursuing exceptional particle detection capability down to practical low levels and rapid analyses with high sample throughput makes single particle inductively coupled plasma mass spectrometry (spICP-MS) very attractive for microplastics analysis. Existing spICP-MS-based studies have routinely shown limitations in the accurate sizing and quantification of particle number concentration through targeting carbon content, with reported size limits of detection in the range of 0.62 to 1.8 μm and a substantial reduction in the transport of particles larger than 3 μm. In this work, the linear dynamic range of spICP-MS for the accurate quantification of polystyrene microparticles (PS MPs) via the monitoring of their carbon content (13C+) is extended to larger particle sizes (5 μm) through using a high efficiency sample introduction system with rigorous optimization of the 13C signal and operating at a lowered nebulizer gas flow to improve sample transport of larger particles to the plasma. Reliable quantification of particle number concentration (PNC), accepted as falling within 20% of expected particle stock concentrations, was achieved through a 20% lowered nebulizer gas flow for a full suite of commercial PS MPs ranging from 2 to 5 μm as well as a 2.2 and 4.8 μm PS MP contained within mixtures of the two materials, regardless of PNC ratio.

Silicon dioxide (SiO2), in its amorphous form, is an approved direct food additive in the United States and has been used as an anticaking agent in powdered food products and as a stabilizer in the production of beer. While SiO2 has been used in food for many years, there is limited information regarding its particle size and size distribution. In recent years, the use of SiO2 food additive has raised attention because of the possible presence of nanoparticles. Characterization of SiO2 food additive and understanding their physicochemical properties utilizing modern analytical tools are important in the safety evaluation of this additive. Herein, we present analytical techniques to characterize some SiO2 food additives, which were obtained directly from manufacturers and distributors. Characterization of these additives was performed using dynamic light scattering (DLS), transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), and single-particle inductively coupled plasma mass spectrometry (spICP-MS) after the food additive materials underwent different experimental conditions. The data obtained from DLS, spICP-MS, and electron microscopy confirmed the presence of nanosized (1-100 nm) primary particles, as well as aggregates and agglomerates of aggregates with sizes greater than 100 nm. SEM images demonstrated that most of the SiO2 food additives procured from different distributors showed similar morphology. The results provide a foundation for evaluating the nanomaterial content of regulated food additives and will help the FDA address current knowledge gaps in analyzing nanosized particles in commercial food additives.

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-Nu & ntilde;ez et al. Journal of Analytical Atomic Spectrometry, 2020, DOI: https://doi.org/10.1039/c9ja00415g state that cooled conditions (2 degrees 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 degrees 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-Nu & ntilde;ez et al. to a wide variety of use conditions routinely encountered in spICP-MS analysis.

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 degrees C to 10 degrees C) and ambient temperature (19 degrees C to 21 degrees 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 degrees C, DMF repeatability was poor. The deviation of particle number concentration, expressed as the median percent difference from the known value for various inhouse 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 degrees 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.

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.

To fully understand the potential ecological and human health risks from nanoplastics and microplastics (NMPs) in the environment, it is critical to make accurate measurements. Similar to past research on the toxicology of engineered nanomaterials, a broad range of measurement artifacts and biases are possible when testing their potential toxicity. For example, antimicrobials and surfactants may be present in commercially available NMP dispersions, and these compounds may account for toxicity observed instead of being caused by exposure to the NMP particles. Therefore, control measurements are needed to assess potential artifacts, and revisions to the protocol may be needed to eliminate or reduce the artifacts. In this paper, we comprehensively review and suggest a next generation of control experiments to identify measurement artifacts and biases that can occur while performing NMP toxicity experiments. This review covers the broad range of potential NMP toxicological experiments, such as in vitro studies with a single cell type or complex 3-D tissue constructs, in vivo mammalian studies, and ecotoxicity experiments testing pelagic, sediment, and soil organisms. Incorporation of these control experiments can reduce the likelihood of false positive and false negative results and more accurately elucidate the potential ecological and human health risks of NMPs.

We describe the outcome of a large international interlaboratory study of the measurement of particle number concentration of colloidal nanoparticles, project 10 of the technical working area 34, "Nanoparticle Populations" of the Versailles Project on Advanced Materials and Standards (VAMAS). A total of 50 laboratories delivered results for the number concentration of 30 nm gold colloidal nanoparticles measured using particle tracking analysis (PTA), single particle inductively coupled plasma mass spectrometry (spICP-MS), ultraviolet-visible (UV-Vis) light spectroscopy, centrifugal liquid sedimentation (CLS) and small angle X-ray scattering (SAXS). The study provides quantitative data to evaluate the repeatability of these methods and their reproducibility in the measurement of number concentration of model nanoparticle systems following a common measurement protocol. We find that the population-averaging methods of SAXS, CLS and UV-Vis have high measurement repeatability and reproducibility, with between-labs variability of 2.6%, 11% and 1.4% respectively. However, results may be significantly biased for reasons including inaccurate material properties whose values are used to compute the number concentration. Particle-counting method results are less reproducibile than population-averaging methods, with measured between-labs variability of 68% and 46% for PTA and spICP-MS respectively. This study provides the stakeholder community with important comparative data to underpin measurement reproducibility and method validation for number concentration of nanoparticles.

Analytical techniques capable of determining the spatial distribution and quantity (mass and/or particle number) of engineered nanomaterials in organisms are essential for characterizing nano-bio interactions and for nanomaterial risk assessments. Here, we combine the use of dynamic secondary ion mass spectrometry (dynamic SIMS) and single particle inductively coupled mass spectrometry (spICP-MS) techniques to determine the biodistribution and quantity of gold nanoparticles (AuNPs) ingested by Caenorhabditis elegans. We report the application of SIMS in image depth profiling mode for visualizing, identifying, and characterizing the biodistribution of AuNPs ingested by nematodes in both the lateral and z (depth) dimensions. In parallel, conventional- and sp-ICP-MS quantified the mean number of AuNPs within the nematode, ranging from 2 to 36 NPs depending on the size of AuNP. The complementary data from both SIMS image depth profiling and spICP-MS provides a complete view of the uptake, translocation, and size distribution of ingested NPs within Caenorhabditis elegans.

Liver plays a major role in metabolism and acts as a source of energy for the body by storing glycogen. With the growing interest and investigation in the biological effects in recent years, it is important and necessary to develop accurate and comparable analytical methods for elements in bio-samples. It has, however, been 10 years since the tissue sample (bovine liver) of CCQM-K49 key comparison. The purpose of CCQM-K145 is to ensure the comparable and traceable measurement results for essential and toxic elements such as P, S, Zn, Mn, Ni, Mo, Sr, Cr, Co, Pb, As and Hg in bovine liver among NMIs and other designated measurement bodies worldwide. The comparison was agreed by IAWG as 6th IAWG Benchmarking Exercise with Zn and Ni as exemplary elements at the meeting in Korea in the early October 2016. The results of CCQM-K145 are expected to cover the measurement capability and support CMCs claiming for inorganic elements in the similar biological tissue materials and food samples. 30 NMIs and DIs registered in CCQM-K145. With respect to the methodology, a variety of techniques such as IDMS, ICP-OES, ICP-MS(non-ID), AAS and NAA were adopted by the participants. For Zn, Ni, Sr, Pb and Hg measurements, most participants chose ID-ICP-MS method, which showed the better performance in terms of consistency and reliability of the measurement results. In aspect of the traceability for the measurement results in CCQM-K145, most participants used their own (in house) CRMs or other NMI's CRMs to guarantee trace to SI unit. Most participants used similar matrix CRMs for quality control or method validation. Base on different statistic way to calculate the reference mass fraction values and associated uncertainties for each measurand, removal of the suspected extreme values, and discussion at the IAWG meetings, the median values are proposed as the KCRV for Zn, Ni, Mn, Mo, Cr, Pb and Hg; the arithmetic mean values are proposed as the KCRV for P, S, Sr, Co and As. In general, the performances of the majority of CCQM-K145 participants are very good, illustrating their measurement capabilities for Zn, Ni, P, S, Mn, Mo, Sr, Cr, As, Co, Pb and Hg in a complex biological tissue matrix. Bovine liver contains many kinds of nutrients and microelements, it can be regarded as a typical representative material of biological tissue and food. In CCQM-K145, the analytes involved alkali metals and transition elements, metalloids / semi-metals and non metals with a range of mass fraction from mg/g to μg/kg. CCQM-K145 also tested the ability of NMIs/DIs to determine elements that were easy to be lost and polluted, and interfered significantly. The chemical pretreatment methods of samples used in the comparison is suitable for general food and biological matrix samples. A variety of measurement methods used in the comparison represent the main instrumental technology for elemental analysis. Therefore, for supporting CMC claim, CCQM-K145 is readily applicable to measurement of more elements in a wide range of biological materials (including liquids and solids) and meat products. Main text To reach the main text of this paper, click on Final Report . Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/ . The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

The nematode Caenorhabditis elegans is used extensively in molecular, toxicological and genetics research. However, standardized methods for counting nematodes in liquid culture do not exist despite the wide use of nematodes and need for accurate measurements. Herein, we provide a simple and affordable counting protocol developed to maximize count accuracy and minimize variability in liquid nematode culture. Sources of variability in the counting process were identified and tested in 14 separate experiments. Three variables resulted in significant effects on nematode count: shaking of the culture, priming of pipette tips, and sampling location within a microcentrifuge tube. Between-operator variability did not have a statistically significant effect on counts, even among differently-skilled operators. The protocol was used to assess population growth rates of nematodes in two different but common liquid growth media: axenic modified Caenorhabditis elegans Habitation and Reproduction medium (mCeHR) and S-basal complete. In mCeHR, nematode populations doubled daily for 10 d. S-basal complete populations initially doubled every 12 h, but slowed within 7 d. We also detected a statistically significant difference between embryo-to-hatchling incubation period of 5 d in mCeHR compared to 4 d in S-basal complete. The developed counting method for Caenorhabditis elegans reduces variability and allows for rigorous and reliable experimentation.

Silver nanoparticles (AgNPs) show different physical and chemical properties compared to their macroscale analogs. This is primarily due to their small size and, consequently, the exceptional surface area of these materials. Presently, advances in the synthesis, stabilization, and production of AgNPs have fostered a new generation of commercial products and intensified scientific investigation within the nanotechnology field. The use of AgNPs in commercial products is increasing and impacts on the environment and human health are largely unknown. This article discusses advances in AgNP production and presents an overview of the commercial, societal, and environmental impacts of this emerging nanoparticle (NP), and nanomaterials in general. Finally, we examine the challenges associated with AgNP characterization, discuss the importance of the development of NP reference materials (RMs) and explore their role as a metrological mechanism to improve the quality and comparability of NP measurements.

Nanomedicine utilizes the remarkable properties of nanomaterials for the diagnosis, treatment, and prevention of disease. Many of these nanomaterials have been shown to have robust antioxidative properties, potentially functioning as strong scavengers of reactive oxygen species. Conversely, several nanomaterials have also been shown to promote the generation of reactive oxygen species, which may precipitate the onset of oxidative stress, a state that is thought to contribute to the development of a variety of adverse conditions. As such, the impacts of nanomaterials on biological entities are often associated with and influenced by their specific redox properties. In this review, we overview several classes of nanomaterials that have been or projected to be used across a wide range of biomedical applications, with discussion focusing on their unique redox properties. Nanomaterials examined include iron, cerium, and titanium metal oxide nanoparticles, gold, silver, and selenium nanoparticles, and various nanoscale carbon allotropes such as graphene, carbon nanotubes, fullerenes, and their derivatives/variations. Principal topics of discussion include the chemical mechanisms by which the nanomaterials directly interact with biological entities and the biological cascades that are thus indirectly impacted. Selected case studies highlighting the redox properties of nanomaterials and how they affect biological responses are used to exemplify the biologically-relevant redox mechanisms for each of the described nanomaterials.

Single particle inductively coupled plasma mass spectrometry (spICP-MS) is shown to be a practical technique to study the efficacy of rate-zonal sucrose density gradient centrifugation (SDGC) separations of mixtures of gold nanoparticles (AuNPs) in liquid suspension. spICP-MS enabled measurements of AuNP size distributions and particle number concentrations along the gradient, allowing unambiguous evaluations of the effectiveness of the separation. Importantly, these studies were conducted using AuNP concentrations that are directly relevant to environmental studies (sub ng mL−1). At such low concentrations, other techniques [e.g., dynamic light scattering (DLS), transmission and scanning electron microscopies (TEM and SEM), UV–vis spectroscopy, atomic force microscopy (AFM)] do not have adequate sensitivity, highlighting the inherent value of spICP-MS for this and similar applications. In terms of the SDGC separations, a mixture containing three populations of AuNPs, having mean diameters of 30, 80, and 150 nm, was fully separated, while separations of two other mixtures (30, 60, 100 nm; and 20, 50, 100 nm) were less successful. Finally, it is shown that the separation capacity of SDGC can be overwhelmed when particle number concentrations are excessive, an especially relevant finding in view of common methodologies taken in nanotechnology research.

Previously, catalytic cerium oxide nanoparticles (CNPs, nanoceria, CeO2-x NPs) have been widely utilized for chemical mechanical planarization in the semiconductor industry and for reducing harmful emissions and improving fuel combustion efficiency in the automobile industry. Researchers are now harnessing the catalytic repertoire of CNPs to develop potential new treatment modalities for both oxidative- and nitrosative-stress induced disorders and diseases. In order to reach the point where our experimental understanding of the antioxidant activity of CNPs can be translated into useful therapeutics in the clinic, it is necessary to evaluate the most current evidence that supports CNP antioxidant activity in biological systems. Accordingly, the aims of this review are three-fold: (1) To describe the putative reaction mechanisms and physicochemical surface properties that enable CNPs to both scavenge reactive oxygen species (ROS) and to act as antioxidant enzyme-like mimetics in solution; (2) To provide an overview, with commentary, regarding the most robust design and synthesis pathways for preparing CNPs with catalytic antioxidant activity; (3) To provide the reader with the most up-to-date in vitro and in vivo experimental evidence supporting the ROS-scavenging potential of CNPs in biology and medicine.

The possibility of immobilization of scandium and other chemical elements by biogenic materials derived from an aquatic macrophyte was explored. The concentrations of scandium and some other chemical elements were measured in the dried biomass (mortmass) of aquatic plants Myriophyllum aquaticum. In the experiments, the mortmass was incubated in aquatic systems where some chemical elements were added to the aquatic medium. After the incubation, the concentrations of these chemical elements in the mortmass were measured using inductively coupled plasma atomic emission spectroscopy (ICP-AES), also referred to as inductively coupled plasma optical emission spectrometry (ICP-OES). Increases in the concentrations of scandium and some other chemical elements (Ce, In, Se, Ru, Pd, U, and Zr) were observed in the biogenic material.