Development and validation of a liquid chromatographic tandem mass spectrometric method for the analysis of patulin in apple and apple juice.

This study reports a robust and sensitive method for rapid testing of patulin in apple and apple juice. The method involved extraction of homogenised samples (10 g) with ethyl acetate (10 mL) and clean up by dispersive-solid phase extraction using primary secondary amine (25 mg/mL). Prior to the LC-MS/MS analysis, the cleaned extract was reconstituted in methanol/water (2:8). The optimised LC-MS condition provided a symmetric peak of patulin within a short LC-runtime of 5 min. The recoveries at the limit of quantification (0.005 mg/kg) and higher levels were satisfactory (> 80%), with the precision-RSDr (< 11%). In an inter-laboratory comparison study involving 13 accredited laboratories, the reproducibility-RSDR and HorRat values ranged between 4.80 and 6.08% and between 0.18 and 0.23 respectively, indicating a satisfactory method-precision. The z-scores of the participating laboratories were within ± 2. When the method was applied to incurred samples, the contamination range was 0.008-0.225 mg/kg and 0.018-0.034 mg/kg for apple and juice respectively, demonstrating a satisfactory performance in terms of precision. Based on the solvent standard, matrix-matched standard and standard-addition approaches, the calibration graphs provided similar quantitative performances. Because of its reliability, robustness and time-effectiveness, the method can be recommended for regulatory testing purposes.

NIR spectroscopic method for the detection of calcium carbide in artificial ripening of mangoes (Magnifera indica).

The present study presents a novel method employing Near Infrared Spectroscopy (NIR) for detection of the use of calcium carbide in artificial ripening of mangoes. Use of calcium carbide has been banned in artificial ripening of fruits as it contains traces of arsenic. Mango samples were ripened artificially using calcium carbide and compared with naturally ripened mangoes using NIR spectroscopic wavelength ranging from 600 to 1100 nm. The captured NIR spectra from mango samples were analysed using multivariate methods including principal component analysis, particle least square and successive projection algorithm. The obtained results showed distinguishing zones for naturally and artificially ripened mangoes. Furthermore, the arsenic content was obtained through ICP-MS analysis, and it was found that mangoes ripened artificially using calcium carbide have a higher content of arsenic. Hence, arsenic was used as a principal component in the analysis. The developed method is not unique to samples that were grown in any particular region or year as it and can be used universally as NIR will give the distinguishing comparison between naturally- and artificially ripened mangoes. This method is simple, non-invasive, non-destructive and rapid for detection of use of calcium carbide in the artificial ripening of mangoes.

Multi-residue analysis of captan, captafol, folpet, and iprodione in cereals using liquid chromatography with tandem mass spectrometry.

In this study, we propose an improved analytical method for the multiresidue analysis of captan (plus its metabolite, tetrahydrophthalimide), folpet (plus its metabolite, phthalimide), captafol, and iprodione in cereals using liquid chromatography tandem mass spectrometry (LC-MS/MS). As captan, captafol, and folpet are easily degraded during homogenisation and extraction, samples were comminuted with liquid nitrogen, and both QuEChERS and ethyl acetate-based extraction workflows provided a satisfactory method performance. The optimised LC-MS/MS procedure with electrospray ionisation did not degrade these compounds, and offered sufficient method selectivity by resolving and minimising co-eluting matrix-derived interferences. The method also resolved the problem of non-specific mass spectra that these compounds usually produce on GC-MS analysis involving electron ionisation. The method performance was satisfactory for all 6 compounds at 0.01 mg kg-1 and higher levels of fortification, and validated as per the SANTE/11813/2017 guidelines of analytical quality control in a wide range of cereals including rice, wheat, sorghum, and corn. The method provides special advantage of simultaneous analysis of captan, and folpet along with their metabolites (tetrahydrophthalimide, and phthalimide, respectively) in combination with captafol, and iprodione in a single chromatographic run. Although iprodione is known to degrade to 3,5-dichloroaniline, since this metabolite is not a part of the residue definition, it was not included in the scope of this method. As the method demonstrates satisfactory selectivity, sensitivity, accuracy, precision, and robustness in a wide range of cereal matrices, it is recommended for regulatory testing of these compounds in cereals.

Gold nanoparticle-based method for detection of calcium carbide in artificially ripened mangoes (Magnifera indica).

A new approach was developed for a simple and easy colorimetric detection assay to detect the use of calcium carbide in artificial ripening of fruits. Residues of arsenic on the fruit surface were used as an indicator for this. Use of calcium carbide in artificial ripening has been banned in many countries including India. In the present study, we have used a gold nanoparticle (AuNP)-based colorimetric detection method for determination of artificial ripening of fruits. ICP-MS analysis showed the presence of higher amounts of arsenic on fruits ripened using calcium carbide. Lauryl sulphate (LS)-capped AuNP aggregates in the presence of arsenic, replacing the LS, resulting in a colour change from red to purple. Hence, the developed method can be used for easy and rapid detection of use of calcium carbide in artificial ripening of fruits.