There was only one solution here and it was the following:
edit /etc/httpd/conf/httpd.conf
Comment the lines for the Mime Magic Module:
# MIMEMagicFile /usr/share/magic.mime
# MIMEMagicFile conf/magic
*Don't forget to restart Apache and clear your browser cache twice
I was using DefaultType and ForceType and the weird thing is for MOST files it was fine, but a few randomly did not like this becuase it appears Mime Magic was determing and rewriting the Mime Type and basically overruling the .htaccess I had (yes I had AllowOverride in the VHOST conf too).
I hope this helps out someone else as it took me ages to sort out.
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