Nanosilver-based materials as feed additives: Evaluation of their transformations along in vitro gastrointestinal digestion in pigs and chickens by using an ICP-MS based analytical platform.

The use of a new nanomaterial in the feed chain requires a risk assessment that involves in vitro gastrointestinal digestions to predict its degradation and oral exposure to nanoparticles. In this study, a nanosilver-based material was incorporated into pig and chicken feed as a growth-promoting additive and subjected to the corresponding in vitro gastrointestinal digestions. An inductively coupled plasma mass spectroscopy (ICP-MS) analytical platform was used to obtain information about the silver released in the different digestion phases. It included conventional ICP-MS for total silver determination, but also single particle ICP-MS and coupling to hydrodynamic chromatography for detection of dissolved and particulate silver. The bioaccessible fraction in the intestinal phase accounted for 8-13% of the total silver, mainly in the form of dissolved Ag(I) species, with less than 0.1% as silver-containing particles. Despite the additive behaving differently in pig and chicken digestions, the feed matrix played a relevant role in the fate of the silver.

Comparative study of extraction methods of silver species from faeces of animals fed with silver-based nanomaterials.

Extractions methods based on ultrapure water, tetramethylammonium hydroxide (TMAH), and tetrasodium pyrophosphate (TSPP) were applied to faeces collected from two in vivo experiments of pigs and chickens fed with a silver-based nanomaterial to study the fate and speciation of silver. For TMAH extraction, cysteine and CaCl2 were used to evaluate their stabilization effect on the silver forms. The analytical techniques single-particle inductively coupled plasma mass spectrometry (SP-ICP-MS), hydrodynamic chromatography hyphenated to ICP-MS (HDC-ICP-MS) and asymmetric flow field flow fractionation coupled to ICP-MS (AF4-ICP-MS) were applied to the simultaneous detection of particulate and dissolved silver. Results have shown that water extraction was a suitable option to assess the environmental release of silver, with percentages of 3 and 9% for faeces of pigs and chickens, respectively. The use of TMAH extraction combined with SP-ICP-MS analysis was useful to characterize Ag-containing particles (less than 1%). Both stabilizers, cysteine and CaCl2, have a similar effect on silver nanoparticle preservation for chicken faeces, whereas cysteine-Triton was better for pig samples. In any case, silver extraction efficiency with TMAH was low (39-42%) for both types of faeces due to a matrix effect. TSPP followed by ICP-MS enabled the fractionation of the silver in the faeces, with silver sulphide (41%) and ionic silver (62%) being the most abundant fractions.

How to trust size distributions obtained by single particle inductively coupled plasma mass spectrometry analysis.

Single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) is a technique widely used to obtain direct information about the number concentration and the size distribution of nanoparticles in liquid suspensions. However, its methods still lack clear quality control strategies to confirm the validity of the information derived from them. Only the detection of the complete size distribution of the nanoparticles in a sample over the size critical value ensures obtaining unbiased quantitative information, otherwise information should be restricted to report the presence of nanoparticles over a certain size and number concentration since their actual total number concentration is underestimated and the size overestimated. Under the latter conditions, data processing produces histograms showing the tails of the incomplete size distributions, although apparently, complete distributions can also be obtained when particle events are recorded as peaks, as reported here for the first time. The occurrence of these misleading situations must be critically evaluated for each SP-ICP-MS analysis. An approach, based on estimation of size critical values and successive dilutions, is proposed for the assessment of the validity of the quantitative information obtained, together with specific criteria for reconsidering the information that can be derived from those measurements. The approach was verified with different case studies and applied to the analysis of complex nanomaterials, confirming the validity of the reported information by comparison with other techniques. A calculation tool is also included to facilitate the estimation of size critical values under experimental conditions.

Analytical applications of single particle inductively coupled plasma mass spectrometry: a comprehensive and critical review.

Single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) refers to the use of ICP-MS as a particle counting technique. When ICP-MS measurements are performed at very high data acquisition frequencies, information about (nano)particles containing specific elements and their dissolved forms can be obtained (element mass per particle, size and number and mass concentrations). As a result of its outstanding performance, SP-ICP-MS has become a relevant technique for the analysis of complex samples containing inorganic nanoparticles. This review discusses the maturity level achieved by the technique through the methods developed for the detection, characterisation and quantification of engineered and natural (nano)particles. The application of these methods in different analytical scenarios is comprehensively reviewed and critically discussed, with special attention to their current technical and metrological limitations. The emergent applications of SP-ICP-MS in the field of nanoparticle-tagged immunoassay and hybridization methods are also reviewed.