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http://dev.w3.org/html5/webvtt/#applying-css-properties-to-webvtt-node-objects In the table in this section, we can see that align:middle is the only value which does not match the CSS setting. To align better with CSS, call it 'center'. We could keep 'middle' as an alias, or remove it if compat allows. (Since it is the default value the compat risk ought to be lower.)
Are implementors OK with just renaming middle to center? Compat-wise, any content that specifies align:middle will still be centered since it's the default. The only case where it makes a difference is if you were to use duplicate settings, I think.
This would also affect positionAlign, and the DOM API (which I think would start throwing for cue.align = 'middle' in JS strict mode).
https://github.com/w3c/webvtt/pull/244