1. Merino sheep fed on a diet of chopped wheaten hay, chopped lucerne (Medicago saliva) hay and oat grain were the source of rumen contents for the study. The diet contained (mg/kg dry weight) 3.3 copper, 024 molybdenum and 2-8 sulphur. The effects of adding between 5 and 25 mg Mo/kg as ammonium molybdate (AM) or tetrathiomolybdate (TTM) on the distribution and forms of Cu and Mo in rumen contents were investigated in vivo and in vitro.
2.Approximately 88 YO of the Cu and 94% of the Mo in rumen contents were associated with the solid phase.When AM or TTM was added to rumen contents in vivo or in vitro the proportion of these elements in the solid phase was increased at the expense of the fluid phase.3. The addition of AM and TTM to rumen contents also decreased the proportion of Cu that was soluble in trichloroacetic acid (50 g/l ; TCA) and increased the proportion of Cu that was not extractable by sequential treatment with TCA and neutral detergent.4. Column chromatography of neutral-detergent extracts of rumen contents revealed that TTM treatment caused Cu to be strongly bound to proteins of high molecular weight.5. Addition of sulphide to rumen contents did not result in significant changes in the distribution of Cu between the fluid and solid phases, or in the solubility of Cu in TCA.6. It is postulated that constant removal of TTM from the fluid phase via reaction with proteins and other macromolecules in the solid phase results in greater formation of TTM in vivo than would be expected from solution chemistry. The molybdo-proteins so formed are strong chelators of Cu and may be the agents responsible for the decrease in Cu absorption in animals that consume diets containing high concentrations of Mo.When relatively high concentrations of molybdenum and sulphur are simultaneously present in the diet of ruminants the availability of copper to the animal is seriously compromised (Dick, 1956). The production of thiomolybdates in the rumen, and the subsequent decrease in the availability of Cu due to the formation of insoluble Cu thiomolybdates has been suggested as a hypothesis for the interaction (Dick et al. 1975). Confirmation of the hypothesis via spectrophotometric evidence of the presence of these compounds in rumen contents has been hampered by interference from other compounds, and by the low concentrations of Mo normally present. However, at moderately high molybdate concentrations, absorption spectra typical of thiomolybdates have been found in washed suspensions of rumen micro-organisms (Dick et al. 1975;El Gallad et al. 1983), in an artificial rumen apparatus (Bray et al. 1982), and in whole rumen contents (El Gallad et al. 1983), thereby indicating that the potential for thiomolybdate formation does exist .Interest has also centred on the particular species of thiomolybdates that may occur in vivo. Based on observations of solution chemistry, Clarke 8z Laurie (1980) concluded that tetrathiomolybdate (TTM) would not form unless the sulphide : Mo ratio was very high, and that at the lower ratios mor...