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my @vol = $doc->findnodes('//Volume[@VolumeCategory="6444"]');
for my $element (@vol) {
...
    print $parent, "\n";
    print $element->textContent(), "\n";
}

<Test size="50">
    <Job tags="boo baa">
...
    <Volume VolumeCategory="6444" MeasurementCategory="Real">2.2</Volu
+me>
</Test>
2.2