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I should know this, but how long does this period last?
I think it's day 6, and the book I want is available from so many others, and my order isn't even marked "accepted" yet. If the member is as pokey in actually mailing it, it will be a long time before I get the book. It's not WLed or anything.
Take a look at the request date--it may have already rolled over to a new person. It's 5 days that they have to respond, but it depends in part on what time of day you requested it--the requests roll over to the next person sometime in the night. There are 'abandoned' accounts here...people lose interest and walk away, leaving their bookshelves up. When a book is requested, if they don't respond, that book is removed from their shelf. If I understand things correctly, if it happens again, their account is deactivated and their whole shelf is removed from the system...so by being patient and waiting, you are helping everyone at PBS by weeding those inactive accounts out.
This tends to happen most for books that are heavily posted--if someone joins and posts mostly books that aren't requested right away, they get discouraged because no one is requesting their books. Eventually your request will get to someone who wants to send their copy to you!