In this work, twelve heavy metals and arsenic, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, and Zn, in a rice sample collected from some areas of Vietnam have been quantified and implemented by using multiple analytical platforms such as ICP-MS, AAS, and mercury analyser. Seventy rice samples collected from the Red River Delta and mining zone activity were analysed. Concentration of heavy metals and arsenic in rice was analysed after appropriated sample digestion using internal or external calibration curves. The mean concentration (mg kg−1 dried weight) of the analysed elements in rice samples decreased on the order of Mn (19.268) > Fe (13.624) > Zn (8.163) > Cu (3.138) > Ni (0.384) > Cr (0.296) > Co (0.279) > As (0.115) > Cd (0.111) > Pb (0.075) > Hg (0.007) > Se (<LOD). Mercury, a highly toxic element, has been only found in rice samples collected in the mining activity zone (frequency detection 14.5% of total samples). The experimental results indicated that the heavy metals and arsenic found in rice collected from mining activity zone were higher than those in rice harvested from normal cultivated areas like the Red River Delta. The heavy metals and arsenic content in Vietnamese rice samples were also compared with the concentration of heavy metals in other foreign rice samples in some recent publications. The estimated daily intake through rice consumption was calculated and compared with the level proposed by the Food and Agriculture Organization of the United Nations. The results indicated that the provisional daily intake of Cd was higher than the level proposed by FAO, while the intake of other heavy metals was in an acceptable range of CODEX standard.
An ultrahigh-performance liquid chromatography in combination with high-resolution mass spectrometry Thermo Q-Extractive Focus Orbitrap MS has been introduced for analysis of multiclass pesticides in vegetable samples collected in Hanoi, Vietnam. Multiclass pesticides were separated on the Thermo Hypersil Gold PFP column utilizing a gradient of the mobile phase consisting of 5 mM ammonium formate, 0.1% formic acid in deionized water, and methanol. The target analytes were detected in the full-scan mode on Thermo Scientific Q-Exactive Focus Orbitrap MS for quantitation at the optimum operating conditions. These conditions included, but not limit to, the resolution of 70000 at the full width at half maximum in both positive and negative mode, mass range from 80 to 1000 m/z, and optimized parameters for the heated electrospray ionization source. The identification of the analytes in real samples was based on retention times, mass to charge ratios, mass accuracies, and MS/MS spectra at the confirmation mode with the inclusion list of target analytes. The mass accuracies of target analytes were from −4.14 ppm (dinotefuran) to 1.42 ppm (cinosulfuron) in the neat solvent and from −3.91 ppm (spinosad D) to 1.29 ppm (cinosulfuron) in the matrix-matched solution. Target analytes in the vegetable-based matrix were extracted by the QuEChERS method. Some critical parameters of the analytical method such as linearity, repeatability, limit of detection, and limit of quantitation have been evaluated and implemented. Excellent LOD and LOQ of the developed method were achieved at the range of 0.04–0.85 and 0.13–2.9 μg·kg−1, respectively. Intraday and interday repeatability of the analytical signal (peak area, n=6) of the developed method were below 3% and 10%, correspondingly. The matrix effect, extraction recovery, and overall recovery were fully investigated by spiking experiments. Experimental results demonstrated that the ionization suppression or enhancement was the main contribution on the overall recoveries of target analytes. Finally, the in-house validated method was applied to pesticides screening in vegetables samples in local villages in Hanoi, Vietnam. The concentrations of all target analytes were below limit of quantitation and lower than US-FDA or EU maximum residue levels.
In this work, high-performance liquid chromatography in combination with inductively coupled plasma dynamic reaction cell quadrupole mass spectrometry was introduced and optimized for speciation analysis of five major arsenic species including arsenobetain (AsB), arsenite (As(III)), monomethylarsonic (MMA), dimethylarsenonic acid (DMA), and arsenate (As(V)) in rice samples. Five arsenic compounds were separated on a Hamilton PRP X100 strong anion-exchange column employed with the mobile phase that is compatible with mass spectrometry, containing ammonium carbonate, methanol, and disodium ethylenediaminetetraacetic acid. Arsenic compounds were detected online by inductively coupled plasma dynamic reaction cell quadrupole mass spectrometry utilizing oxygen as the reaction gas at a flow rate of 0.7 mL·min−1. Five selected arsenic species were baseline separated at the optimum experimental conditions. The excellent LOD and LOQ values of the developed method were achieved in the range of 0.5 to 2.9 μg·kg−1 and 1.7 to 9.6 μg·kg−1 for all species of arsenic, respectively. The ionization effect in plasma during chromatographic gradient elution was systematically investigated by using postcolumn injector. Arsenic compounds in rice samples were extracted by diluted nitric acid at elevated temperature. The extraction efficiency and the interconversion of target compounds during sample preparation were also assessed. The full validation of the developed method was performed by using certified reference material, BRC 211, from European Institute of Reference and Standard for speciation analysis. The recovery of all selected arsenic species was in the range of 70 to 135.5%. The validated method was also applied to analyze rice samples collected from some contaminated rice fields. The results showed that As(III), DMA, and As(V) were found in all rice samples. Average concentration (range) of inorganic arsenic and DMA in all rice samples were 130.3 (65.5–228.1) and 32 (8.2–133.01) μg·kg−1, respectively. However, total concentration of inorganic arsenic in most of investigated rice samples was below the maximum residual level according to US-FDA and European Union standards.
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