pear package: http://www.pecl.php.net/package/Zorba (error 404 link)
NEW (2011): http://www.zorba-xquery.com/html/entry/2011/12/27/PHP_Meets_XQuery
zorba documentation: http://www.zorba-xquery.com/
zorba docs provide a simple example:
//Include for the Object-Oriented API
require ‘zorba_api.php’;
//Initialization of Zorba store
$store = InMemoryStore::getInstance();
//Initialization of Zorba
$zorba = Zorba::getInstance($store);
$xquery = <<< EOT
let $message := ‘Hello World!’
return
<results>
<message>{$message}</message>
</results>
EOT;
//Compile the query
$lQuery = $zorba->compileQuery($xquery);
//Run the query…
echo $lQuery->execute();
//…and destroy it
$lQuery->destroy();
//Shutdown of Zorba
$zorba->shutdown();
//Shutdown of Zorba store
InMemoryStore::shutdown($store);