Arsenic and its species were investigated for the first time in nine collections of Elaphomyces spp. ("deer truffles") from the Czech Republic with inductively coupled plasma mass spectrometry (ICPMS) and high-performance liquid chromatography coupled to ICPMS. The total arsenic concentrations ranged from 12 to 42 mg kg-1 dry mass in samples of E. asperulus and from 120 to 660 mg kg-1 dry mass in E. granulatus and E. muricatus. These concentrations are remarkably high for terrestrial organisms and demonstrate the arsenic-accumulating ability of these fungi. The dominating arsenic species in all samples was methylarsonic acid which accounted for more than 30% of the extractable arsenic. Arsenobetaine, dimethylarsinic acid, and inorganic arsenic were present as well, but only at trace concentrations. Surprisingly, we found high amounts of trimethylarsine oxide in all samples (0.32-28% of the extractable arsenic). Even more remarkable was that all but two samples contained significant amounts of the highly toxic trivalent arsenic compound methylarsonous acid (0.08-0.73% of the extractable arsenic). This is the first report of the occurrence of trimethylarsine oxide and methylarsonous acid at significant concentrations in a terrestrial organism. Our findings point out that there is still a lot to be understood about the biotransformation pathways of arsenic in the terrestrial environment. Graphical abstract Trimethylarsine oxide and methylarsonous acid in "deer truffles".

Institute of Chemistry Analytical Chemistry for Health and Environment University of Graz Universitaetsplatz 1 8010 Graz Austria

The Czech Academy of Sciences Nuclear Physics Institute Hlavní 130 25068 Husinec Řež Czech Republic The Czech Academy of Sciences Institute of Geology Rozvojová 269 16500 Prague 6 Czech Republic

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