This work describes the development of a novel method for quantitative mapping of Hg and Se in mushroom fruit body tissues with laser ablation coupled to inductively coupled plasma-mass spectrometry (LA-ICP-MS). Different parameters of the protocol for preparation of the standards used for quantification via external calibration were assessed, e.g., the dissolution temperature of gelatin standards and the addition of chitosan and L-cysteine as additives to the gelatin-based calibration droplets to better match the sample matrix. While chitosan was not suited for this purpose, the presence of L-cysteine considerably improved the figures of merit of the calibration, leading to limits of detection of 0.006 and 0.3 µg g-1 for Hg and Se, respectively, at a pixel size of 20 × 20 µm. Further, an in-house reference material, ideally suited for the validation of the method for application to mushroom samples, was successfully prepared from a paste of Boletus edulis. The newly developed method was used to investigate the distribution of Hg and Se in tissue sections of five porcini mushroom individuals of three different species (Boletus edulis, Boletus aereus, and Boletus pinophilus) and one sample of a parasol mushroom (Macrolepiota procera). For one sample, additional areas were ablated at higher spatial resolution, with a laser spot size down to 5 µm, which allows a detailed investigation of the spatial distribution of Hg and Se in mushrooms.

Atomic and Mass Spectrometry A and MS research unit Department of Chemistry Ghent University Campus Sterre Krijgslaan 281 S12 9000 Ghent Belgium

Institute of Chemistry University of Graz Universitaetsplatz 1 8010 Graz Austria

Institute of Geology of the Czech Academy of Sciences Rozvojová 269 16500 Prague 6 Czech Republic

Laboratory of Functional Plant Biology Department of Biology Ghent University K L Ledeganckstraat 35 9000 Ghent Belgium

Nuclear Physics Institute of the Czech Academy of Sciences Hlavní 130 25068 Husinec Řež Czech Republic

Research Group Mycology Department of Biology Ghent University K L Ledeganckstraat 35 9000 Ghent Belgium

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Quantitative mapping of mercury and selenium in mushroom fruit bodies with laser ablation-inductively coupled plasma-mass spectrometry