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We investigated in total 80 wine samples of different types and seven grape juice and 23 beer samples purchased from markets in Central Europe in order to understand the arsenic (As) speciation and help assess the potential As toxicity via intake of alcoholic beverages. Generally, total As concentrations in most samples investigated were below the drinking water limit 10 µg l−1 published by the World Health Organization (WHO); ranging from 0.46 to 21.0 µg l−1 As in red and white wines and from 0.75 to 13.4 µg l−1 As in beers. In addition, concentrations of total As in rice wine and in rice beer were 0.63–6.07 and 3.69–8.23 µg l−1 As, respectively. The total As concentrations in ice wine ranged from 7.94 to 18.8 µg l−1 As, significantly higher than in white and red wine. Arsenite predominated as the As species in most of the wine samples, whereas arsenate was the dominant species in rice wine, beer and rice beer. Methyl As components were usually minor components in all wine and beer samples. Monomethylarsonic acid, dimethylarsinic acid and two additional unknown As species were frequently found in grape juice, late harvest and ice wine with higher sweetness. After air exposure, arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid were stable at 4°C for months, probably due to the acidic conditions of wine and beer samples. The presence of sulfite had little influence on As speciation in wine. Despite the predominance of more toxic arsenite and arsenate in wine and beer, the estimated weekly exposure to As (via consumption of beer, wine and rice wine) is low. The As intake per capita is 6.81 µg from beer, <1.93 µg from wine and 0.88 µg from rice wine, estimated using the median of total As concentration multiplied by the average consumption per capita of the corresponding beverage. [ABSTRACT FROM AUTHOR]