PGP and S/MIME are protocols for securing email communications. PGP uses public/private key encryption and digital signatures to provide confidentiality, authentication, and integrity. It operates using a "web of trust" model where users can sign each other's keys. S/MIME uses X.509 certificates and relies on certificate authorities similarly to PGP to secure email. IPsec provides authentication and encryption of IP packets through protocols like AH and ESP to secure network traffic at the IP layer.