Speciation analysis of arsenic in edible mushrooms by high-performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry

Some varieties of edible mushrooms can accumulate high contents of arsenic, which is a public health concern. In this study, we developed a high-performance liquid chromatography method linked to inductively coupled plasma triple quadrupole mass spectrometry (HPLC-ICP-MS/MS) for sensitive and accurate determination of arsenite, arsenate, monomethylarsonic acid, dimethylarsinic acid, arsenocholine and arsenobetaine in edible mushrooms. The six arsenic species were extracted ultrasonically from mushrooms using ultrapure water at 60 °C as the solvent, separated on a PRP-X100 anion exchange column (4.1 × 250 mm, 10 µm), with 20 mmol/L NH4HCO3 and 50 mmol/L (NH4)2CO3 as the mobile phase, and quantified using ICP-MS/MS in the oxygen reaction mode. The linear range of the method was 0.5 µg/L-100 µg/L with detection and quantification limits of 2.5 µg/kg-10 µg/kg (S/N = 3), and 8 µg/kg-33 µg/kg (S/N = 10), respectively. This method was applied successfully to the detection and speciation of arsenic in eight varieties (266 samples) of mushrooms. Our results indicated that most wild edible mushrooms contained organic arsenic, mainly arsenobetaine and arsenocholine. However, the inorganic arsenic content of Armillariella tabescens (3.63 mg/kg) and parts of the cultivated Agaricus blazei murrill (up to 4.50 mg/kg) were relatively high, which is potential risk to the health of consumers.