XML is to authentication bypasses what C is to buffer overflow attacks
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In the context of saml that's hardly the least of it. Lots of the problems are things like allowing comments to sort of change the meaning of the document, allowing signatures to sign only part of the document. Allowing multiple signatures to sign different parts of the document, etc.
Now, xml has also been used for a lot of things where a hierarchical format like json would have worked better than a markup format, of which SAML would be a good example. But there are also cases where a markup format makes more sense, like svg or docbook, or odf.