Water is made up of molecules consiting of 2 hydrogen atoms and one oxygen atom, H2O. When you heat, and indeed boil, water you provide energy. When boiling the energy is sufficient to break the association between different H2O molecule, causing them to vapourise and form a gas.
Hence the bubbles are filled with gas. I am not sure if this gas is H2O in the gas phase, or if the energy provided by boiling the water is sufficient to break the bonds holging the hydrogen and oxygen atoms together. But I`d imagine it is H2O, as if not boiling water would produce two explosive gases as a product.
As for the second part, pure water has a defined boiling point, 99.7oC or their abouts, but if you modify the composition of water by disolving things in it you can reduce this. Therefore if you get close to boiling temperature, say 95oC, and add say salt, this might reduce the boiling point of the new solution, causing it to suddenly boil.