Monitoring data have shown that the total monomethylmercury (CH(3) Hg(+) and its complexes; collectively referred as MeHg hereafter) concentrations in Arctic marine mammals have remained very high in recent decades. Toward a better understanding of the metabolic and toxicological implications of these high levels of MeHg, we report here on the molecular forms of MeHg in the muscle, brain, liver, and kidneys of 10 beluga whales from the western Canadian Arctic. In all tissues analyzed, monomethylmercury was found to be dominated by methylmercuric cysteinate, a specific form of MeHg believed to be able to transport across the blood-brain barrier. Another MeHg-thiol complex, methylmercuric glutathionate, was also detected in the muscle and, to a much lesser extent, in the liver and brain tissues. Furthermore, a profound inorganic Hg peak was detected in the liver and brain tissues, which showed the same retention time as a selenium (Se) peak, suggesting the presence of an Hg-Se complex, most likely an inorganic Hg complex with a selenoamino acid. These results provide the first analytical support that the binding of MeHg with glutathione and Se may have protected beluga whales from the toxic effect of high concentrations of MeHg in their body.