So, that's interesting. The rise in sugar/drop in protein does seem to be linked to the CO2 levels, as demonstrated in the goldenrod example... but I have a harder time with staple crops like corn or barley. Yes, surely the environment has had an effect, but those crops have also been specifically bred to produce more carbohydrates. When starch/sugar is your main commodity that's what you target.
I wouldn't deny the changes from climate, but I feel our own pressures have been more drastic. It is worrying with the non-food crops like the goldenrod, so it's certainly a "thing", but I feel like we've made more changes to barley on purpose than slow creep of natural evolution.
I could totally be wrong, but from my food science background those changes seem more targeted and bred rather than a slow change over time.
My understanding of the mash thing is that the grains have been bred to have higher levels of the enzymes so they do convert quicker and more completely. I don't know if that has anything to do with the amount of sugar in the grain rather than simply it being a more efficient process. Modern breeding and modern malting have done a lot of the work for us.