Dinotefuran (DNT) belongs to the third-generation neonicotinoid pesticides, which are among the most common residuals in a variety of food commodities. To guarantee accurate quantification and traceability of results in food samples, certified reference materials (CRMs) are the indispensable benchmark. In this work, a DNT CRM was characterized and its purity was assessed by two independent methods, including mass balance (MB) and quantitative nuclear magnetic resonance spectroscopy (qNMR). The mass fraction of moisture was 0.33 mg/g, the inorganic impurity was 0.01 mg/g, and no detectable organic solvent was detected. Benzoic acid was chosen as the internal standard for qNMR. Its mass fraction was 997.9 mg/g and 992.9 mg/g by MB and qNMR, respectively. Eventually, the DNT CRM was assigned a mass fraction of 995 mg/g, with expanded uncertainty of 5 mg/g (k = 2). This CRM can be used to prepare calibrant solutions and is applicable to national routine monitoring of DNT residuals in agro-products and food.

Selenium-enriched yeast possesses the unique ability of transforming chemical selenium, such as sodium selenite, into a biologically active form, which mitigates its toxic effects on the human body. The transformation product of this process, selenomethionine, can be safely and effectively absorbed and utilized by the human body; hence, it has been spiked into a selenium-enriched supplement. This study employs two distinct measurement strategies to determine the selenomethionine content in two candidate reference materials, a selenium-enriched yeast powder and supplement, using both organic and inorganic mass spectrometry. The concentrations of selenomethionine in the selenium-enriched yeast were determined using HPLC-ICP-MS and HPLC- ESI-MS/MS, with mass fractions measured at 718 mg SeMet kg⁻¹ and 715 mg SeMet kg⁻¹, respectively. Notably, both methods yielded consistent results for the selenium supplement, with a selenomethionine mass fraction of 59 mg SeMet kg⁻¹. Ultimately, the certified values of these candidate reference materials were determined as 716 mg kg⁻¹ and 59 mg SeMet kg⁻¹ with expanded uncertainties of 36 mg SeMet kg⁻¹ (k = 2) and 5 mg SeMet kg⁻¹ (k = 2), respectively. The development of these candidate reference materials serves as a valuable reference for diverse methods aiming to determine the value of organic selenium speciation in complex food substrates.

It is well established that arsenic (As) has many toxic compounds, and in particular, inorganic As (iAs) has been classified as a type-1 carcinogen. The measuring of As species in rice flour is of great importance since rice is a staple of the diet in many countries and a major contributor to As intake in the Asian diet. In this study, several solvents and techniques for the extraction of As species from rice flour samples prior to their analysis by HPLC-ICP-MS were investigated. The extraction methods were examined for their efficiency in extracting various arsenicals from a rice flour certified reference material, NMIJ-7532a, produced by the National Metrology Institute of Japan. Results show that ultrasound-assisted extraction at 60 °C for 1 h and then heating at 100 °C for 2.5 h in the oven using a thermostable α-amylase aqueous solution was highly effective in liberating the arsenic species. The recoveries of iAs and dimethylarsinic acid (DMA) in NMIJ-7532a were 99.7% ± 1.6% (n = 3) and 98.1% ± 2.3% (n = 3), respectively, in comparison with the certificated values. Thus, the proposed extraction method is a green procedure that does not use any acidic, basic, or organic solvents. Moreover, this extraction method could effectively maintain the integrity of the native arsenic species of As(III), As(V), monomethylarsonate (MMA), DMA, arsenobetaine (AsB) and arsenocholine (AsC). Under the optimum extraction, chromatography and ICP-MS conditions, the limits of detection (LOD) obtained were 0.47 ng g⁻¹, 1.67 ng g⁻¹ and 0.80 ng g⁻¹ for As(III), As(V) and DMA, respectively, while the limits of quantification (LOQ) achieved were 1.51 ng g⁻¹, 5.34 ng g⁻¹ and 2.57 ng g⁻¹ for As(III), As(V) and DMA, respectively. Subsequently, the proposed method was successfully applied to As speciation analysis for several rice flour samples collected from contaminated areas in China.