RESUMO
Extraction and analytical procedures were developed from 1999 to 2005 for the chemical investigation of molybdenum (Mo) in aerial portions of alfalfa ( Medicago sativa L.) grown on a reclaimed mine tailings site at the Highland Valley Copper Mine in British Columbia, Canada. The purification procedures were guided by colorimetric analyses specific for Mo. The Mo levels in freeze-dried plant samples exceeded 100 ppm, which is more than 20 times the maximum level recommended for livestock feed. In contrast to previous work, which detected the inorganic molybdate anion (MoO4(2-)) in alfalfa from the site, the present study identified the major pool of Mo as a chelate bound to malic acid in five sources of plant material. However, the inorganic form of Mo was characterized in aqueous tailings samples, but once imbibed by vegetation, the anion was chelated to the alpha-hydroxy organic acid. Synthetic chelates were synthesized to differentiate the Mo-malate complex from the Mo-citrate by 95Mo NMR. Crystal structure of the synthetic Mo-malate determined that the Mo was bound to two malato ligands as Na 2[MoO2(malate) 2] x 5H2O, which confirmed the structure of the isolates deduced by 95Mo NMR. The chelation of Mo at the site may well explain the apparent lack of long-term clinical effects in cattle grazing the site.