Thanks for everyone's help here. I've had our plumber round once again and he's checked everything and it's all doing what it should be. There was a question as to whether there was a slight issue with one of the 2 port valves, so we changed that just in case.
However we still have problems.
For example last night we stayed away, but the hot water was still on between 6am and 7pm. So no one used it or showered. When I went to wash up at 2pm I had a small amount of hot water but then it was cold. I'm not being stupid here am I? We should still have hot water if it heated it for an hour and none was used?
Everything is serviced every year, and only 13 years old, it is all operating as expected. No leaks, nothing different from last year, yet we have a huge amount of variation in the gas usage.
Looking at my usage from last year the hour of heating the hot water in the morning used an average of 11kwh, this year it's an average of 20kwh, so nearly double, for the exact same usage.
Other than getting a second opinion from another plumber / heating engineer does anyone have any idea what it could be?