Potential occupational arsenic exposure is a significant problem in smelting plants. The metabolites containing arsenic with an oxidation of +3 have been considered more cytotoxic and genotoxic than their parent inorganic species. The current study examined the capacity of arsenic methylation and its risk on skin lesions. The primary aim of this study is to determine if methylation capacity, as measured by urinary arsenic metabolites, differed in workers with skin lesions compared to workers without skin lesions. Hydride generation-atomic absorption spectrometry was used to determine three arsenic species in urine of workers who had been working in arsenic plants, and primary and secondary methylation indexes were calculated. Skin lesions were examined at the same time. Many workers had obvious skin lesions (36/91). The mean concentrations of inorganic arsenic (iAs), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) in urine of workers are obviously higher than those of the control group. There are more iAs, MMA, and DMA in urine, higher MMA%, lower iAs% for workers with skin lesions compared with those without skin lesions. Workers with skin lesions have the lowest SMI (3.50 +/- 1.21), and they may be in danger. Our results support the viewpoint that individuals who metabolize inorganic arsenic to MMA easily, but metabolize MMA to DMA difficulty have more risk of skin lesions. (C) 2012 Elsevier B.V. All rights reserved.