Attribute values from xquery

To get attribute values use data function on node.

 SELECT CAST(r.query('data(VALUE)')AS NVARCHAR)[ApproverID], r.query('data(VALUE/@DATATYPE)').value('.','nvarchar(10)') [DataType]
FROM @doc.nodes('/ITEMS[@ID="VAL"]/ITEM[@ID="DEFAULTS"][NAME="ApproverID"]') a (r)

http://msdn.microsoft.com/en-us/library/ms187038.aspx