Having been given a few pointers in the general direction I have now discovered the cause of the whitespace issue before the XML and DOCTYPE declaration when Opencart is viewed in Page Source and therefore unable to be validated.
The problem is caused by unwanted line spaces AFTER the closing
in language files. A number of the language files in the download for OC 1.3.2 contain these already so I would suggest checking these before upload, however the files that seem to be the likely offenders are the common files.
Open the 5 files in: catalog/language/common/ and remove any line spaces after the closing
in these files.
If your editor does not show line numbers you will literally have to click after the closing code and hit delete until any line spaces are removed.
This of course assumes that you have not added any before the opening
which would also generate this problem. But they are easy to spot.
If the common language files do not fix this, then you will need to go through all of the language files one by one and check that there are no unwanted line spaces in those files.
Whitespace - removed, XHTML validation - sorted!