There are a few too many variables in your question to easily answer. For instance, what type of tires, what speed?
But if you had a power meter on the bicycle you could measure watts and get an estimation of calories burned. Typically an average person is only 20-25% efficient so going backwards you can get calories burned. Energy (kcal) = Power (watts) * Time (hours) * 3.6
Same issue with walking. How fast, how heavy is person, how efficient is their walking? In this case you could put the person on a treadmill and hook a mask up to measure oxygen uptake and then calculate calories burned.
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