Get original URL for Link to a Document content type

Given you are capturing ItemAdded in document library most likely youare AfterProperties will always be null. Read the following blog post. Though its written for MOSS 2007 I am assuming this will stay the same for SP2010.

http://www.synergyonline.com/Blog/Lists/Posts/Post.aspx?ID=122

Instead use this code and see if it works

SPListItem item = Properties.ListItem;

SPFieldUrlValue itmURL = new SPFieldUrlValue();        

if(!String.IsNullOrEmpty(item["URL"]))
{
     itmURL = item["URL"];        
     String URLDesc = itmURL.Description;        
     String URL = itmURL.Url ;
}

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Amit