Can I have multiple values for rel attributes? Like so:
<a href="#" rel="value1 nofollow">Link</a>
.. is it valid and cross-browser compatible?
It's valid. I'm not sure if it's supported by all browsers, though, but I would guess that it is.
rel = link-types [CI] This attribute describes the relationship from the current document to the anchor specified by the href attribute. The value of this attribute is a space-separated list of link types.
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