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As soon as I logged into Facebook using Omniauth
Andrei's answer didn't work for me on Mac OSX 10.8.3. I had reinstalled openssl to install ruby 2.0 some time ago and since then always got this error. I fixed it thanks to Andrei's answer and instructions from the Rails project.
I ran:
$ rvm -v
$ rvm get head
# Installation of latest version of rvm...
$ rvm -v
# rvm 1.19.5 (master)
$ rvm osx-ssl-certs status all
# Certificates for /usr/local/etc/openssl/cert.pem: Old.
# Certificates for /Users/mpapis/.sm/pkg/versions/openssl/0.9.8x/ssl/cert.pem: Old.
$ sudo rvm osx-ssl-certs update all
# Updating certificates...
Then I checked if the certificates were correctly updated by running rvm osx-ssl-certs status all again but /usr/local/etc/openssl/cert.pem was still not updated. I don't know if that was necessary but I did the following:
$ cd /usr/local/etc/openssl/
$ curl -O http://curl.haxx.se/ca/cacert.pem
$ mv cacert.pem cert.pem
After that the problem was fixed. Hope that helps someone else who runs into the same issue.