Take a look @ the API:
String expression = "/Employees/Employee";
NodeList nodeList = (NodeList) xPath.compile(expression).evaluate(xmlDocument, XPathConstants.NODESET);
for (int i = 0; i < nodeList.getLength(); i++) {
Node employeeNode = nodeList.item(i);
String emplId = employeeNode.getAttributes().getNamedItem("emplid").getNodeValue();
}
(http://docs.oracle.com/javase/6/docs/api/org/w3c/dom/Node.html#getAttributes())