Ok... traditional way was to pipe up spirits twice a day, usually 11.30AM and about 4.30AM. Grog (water + rum or wine) was served, usually a quart per man. Worked out to half a pint of rum a day. Then again, sailing ships took a lot of muscle to steer. It was down to the Capitain to decide exactly when and how much though.
These days... it's actually pretty similar. I recall an incident (I think the Uganda, could have been on-shore hospital) during the Falklands where the tot was issued. The purser presented the bill to the CO who sent it to the Ministry of Defence - who paid up.
Captain/commanding officer decides when "arduous duty" is reached. I would guess the one exception would be aircrew, who would need some serious rank to gain access to a preflight snifter.