Mobility of Arsenic (As) from metallurgical wastes in Matehuala, Mexico has been accounted for ultra-high concentration of As in water (4.8–158 mg/L) that is used for recreational purposes as well as cultivation of maize. In this study, we (i) measured As concentrations in soils irrigated with this water, (ii) investigated the geochemical controls of available As, and (iii) measured bioaccumulation of As in maize. Water, soil, and maize plant samples were collected from 3 different plots to determine As in environmental matrices as well as water soluble As in soils. Soil mineralogy was determined by X-ray diffraction analysis. Bioaccumulation of As in maize plants was estimated from the bioconcentration and translocation factors. We recorded As built-up in agricultural soils to the extent of 172 mg/kg, and noted that this As is highly soluble in water (30% on average). Maize crops presented high bioaccumulation, up to 2.5 times of bioconcentration and 45% of translocation. Furthermore, we found that water extractable As was higher in soils rich in calcite, while it was lower in soils containing high levels of gypsum, but As bioconcentration showed opposite trend. Results from this study show that irrigation with As rich water represents a significant risk to the population consuming contaminated crops.