Option 1. sounds a bit risky. Anything could happen. If you could find a permanent position for more than say £20k though, living at home on the cheap, you could probably sail through to a fATPL. You would also have a job to stick with if you couldn't find work as a pilot.
Option 2. Judging by your post this is what you want to do, though I would have a good look at some of the ATPL books first (if you haven't already) if you're planning to take on the ATPL's alongside a PhD.
If I were you I wouldn't worry too much about being 30-ish when you qualify but do you really want to fly as a career? No one really knows when the industry will pick up or if it will at all so again I wouldn't really worry about that either. You will have your non-flying qualifications to fall back on regardless.
Now there's nothing wrong with having a backup plan but it sounds from your post like you would be quite happy working in business support or whatever, so do you really want the extra hassle and expense of learning to fly for a job instead of just for fun?
If you're dead set on flying then go for it! I don't think there are many people that could tackle the ATPL's alongside a PhD but if you think you can pull it off, and the money from the PhD isn't an issue, best of luck to you.
I'm planning on starting the ATPL distance learning with London Met next month. I'm in the reasonably fortunate position of having a full-time permanent job that pays more than enough that I can fund my training. I decided a while back that I will go all the way to fATPL regardless of whether I can get a job flying on not because it is really what I want to do. If I can't get a job flying I already have a cosy alternative.
Good luck whatever you decide. I can see either of your options working out quite nicely.