Even if the URL of the namespace is a 404, using it in a domain configuration does work, and is documented on the libvirt homepage:
Additionally, the following XML additions allow fine-tuning of the command line given to qemu when starting a domain (Since 0.8.3). In order to use the XML additions, it is necessary to issue an XML namespace request (the special xmlns:name attribute) that pulls in http://libvirt.org/schemas/domain/qemu/1.0; typically, the namespace is given the name of qemu. With the namespace in place, it is then possible to add an element <qemu:commandline> under domain, with the following sub-elements repeated as often as needed:
qemu:arg
Add an additional command-line argument to the qemu process when starting the domain, given by the value of the attribute value.
qemu:env
Add an additional environment variable to the qemu process when starting the domain, given with the name-value pair recorded in the attributes name and optional value.
This is also tested in various places in libvirt:
I tested this solution on a kvm domain by changing the beginning of the definition to
<domain type='kvm' xmlns:qemu='http://libvirt.org/schemas/domain/qemu/1.0'>
<qemu:commandline>
<qemu:arg value='-unknown'/>
<qemu:arg value='parameter'/>
</qemu:commandline>
in virsh -c qemu:///system edit <domain>. On subsequent edits, those changes still exist (the new elements are moved to the end of the document, though).
Starting the domain also fails with qemu complaining about an unknown parameter:
↪ virsh -c qemu:///system start <domain>
error: Failed to start domain <domain>
error: Interner Fehler: qemu unexpectedly closed the monitor: qemu-system-x86_64: -unknown: invalid option
Note that an XML namespace does not need to be a URL that resolves to something ... usable.