Levels of magnesium, potassium, sodium and calcium in post-mortem vitreous humour from human controls, fire fatalities and drowning victims have been determined. The effects of time-related internal changes, external environmental parameters and different causes of death are evaluated. Despite the positive correlation and marked increase of potassium and, to a lesser extent, of magnesium and calcium with the length of the post-mortem interval, individual biological variability severely limits the usefulness of predictions of post-mortem interval based on electrolyte metal data. At best, there is only a 2/3 chance of a prediction being within 12 h of the true value. Vitreous humour metal concentrations are affected by external influences, such as the elevated temperatures of fires which increase the rate of release of intracellular magnesium and potassium. In cases where drowning is suspected, establishment or exclusion of this cause of death is not possible on the basis of vitreous humour electrolyte metal data because of possible post-immersion diffusion across the permeable membrane of the eyeball. It appears, however, that magnesium in salt-water cases and sodium in fresh-water cases are related, albeit erratically, to the length of the immersion period.