Methodology for SI traceable determination of particle number concentration by reference NM-free spICP-MS.

The industrial exploitation of high value nanoparticles is in need of robust measurement methods to increase the control over product manufacturing and to implement quality assurance. InNanoPart, a European metrology project responded to these needs by developing methods for the measurement of particle size, concentration, agglomeration, surface chemistry and shell thickness. This paper illustrates the advancements this project produced for the traceable measurement of nanoparticle number concentration in liquids through small angle X-ray scattering (SAXS) and single particle inductively coupled plasma mass spectrometry (spICPMS). It also details the validation of a range of laboratory methods, including particle tracking analysis (PTA), dynamic light scattering (DLS), differential centrifugal sedimentation (DCS), ultraviolet visible spectroscopy (UV-vis) and electrospray-differential mobility analysis with a condensation particle counter (ES-DMA-CPC). We used a set of spherical gold nanoparticles with nominal diameters between 10 nm and 100 nm and discuss the results from the various techniques along with the associated uncertainty budgets.

Toxicological studies concerning nanomaterials in complex biological matrices usually require a carefully designed workflow that involves handling, transportation and preparation of a large number of samples without affecting the nanoparticle...

A novel strategy for the absolute quantification of selenium (Se) included in selenoprotein P (SEPP1), an important biomarker for human nutrition and disease, including diabetes and cancer, is presented here for the first time. It is based on the use of species-specific double isotope dilution mass spectrometry (SSIDA) in combination with HPLC-ICP-MS/MS for the determination of protein bound Se down to the peptide level in a complex plasma matrix with a total content of Se of 105.5 μg kg(-1). The method enabled the selective Se speciation analysis of human plasma samples without the need of extensive cleanup or preconcentration steps as required for traditional protein mass spectrometric approaches. To assess the method accuracy, two plasma reference materials, namely, BCR-637 and SRM1950, for which literature data and a reference value for SEPP1 have been reported, were analyzed using complementary hyphenated methods and the species-specific approach developed in this work. The Se mass fractions obtained via the isotopic ratios (78)Se/(76)Se and (82)Se/(76)Se for each of the Se-peptides, namely, ENLPSLCSUQGLR (ENL) and AEENITESCQUR (AEE) (where U is SeCys), were found to agree within 2.4%. A relative expanded combined uncertainty (k = 2) of 5.4% was achieved for a Se (as SEPP1) mass fraction of approximately 60 μg kg(-1). This work represents a systematic approach to the accurate quantitation of plasma SEPP1 at clinical levels using SSIDA quantification. Such methodology will be invaluable for the certification of reference materials and the provision of reference values to clinical measurements and clinical trials.

Systematic approach for the accurate quantification of selenoproteins (SEPP1) in human plasma/serum by IDA-LC-ICP-MS.

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This study compared results of nanoparticle number concentration measurements collected from 74 instruments hosted across 50 laboratories, providing users with useful discussion and reference data to assess and benchmark their measurement capability.

Fractionation data for cadmium in tobacco products, as obtained by sequential leaching of cadmium species with ICP-MS/MS analysis, and separately by X-ray absorption near edge structure (XANES) are presented here for the first time. The total amount of cadmium found in 3R4F cigarette cut tobacco was 1526 ± 42 μg kg, of which 5% was found in the smoke under ISO smoking conditions. XANES analysis showed that Cd in tobacco, cigarette smoke and ash was present in the + 2 oxidation state. Examination of the gas-particle partitioning of smoke cadmium suggests that Cd in mainstream smoke is best viewed as semi-volatile, existing in both particulate and gas phases. Sequential extraction of trapped tobacco smoke was carried out to get a deeper insight into the chemistry of cigarette smoke cadmium compounds. Consecutive extractions with ultrapure water, dilute (1%) nitric acid and 10% nitric acid led to extraction of a total amount of Cd which agreed with that obtained after microwave digestion of the whole sample, suggesting that cadmium was quantitatively leachable into aqueous/acidic solutions. Most Cd (~ 90% of the total Cd in the smoke condensate) was extracted into dilute nitric acid (likely as CdO, Cd(OH) and CdCO) with a minor percentage (3%) extracted into water (likely as CdCl) and in 10% nitric acid (likely as CdS). Extraction of trapped mainstream smoke with pentane, followed by ICP-MS/MS analysis, to examine the possible presence of organocadmium in 3R4F tobacco smoke, did not show the presence of organocadmium compounds above the method LOQ (2 μg kg), possibly due to their reactivity under the experimental conditions. The high selectivity with sufficient sensitivity achieved by ICP-MS/MS was invaluable to quantify Cd (at low μg kglevels) simultaneously with sulphur and chlorine in the tobacco smoke fractions of complex matrix. The cadmium chemistry in the smoke, identified in this study, is consistent with both relatively high lung absorption and DNA binding; both potentially important factors for disease progression in smokers. Graphical Abstract This paper provides quantitative fractionation data for cadmium in tobacco and smoke by using sequential leaching with ICPMS and XANES.