I was able to resolve this. I upgraded from PHP 7.3 to 7.4 and now it's working. I suspect though that the service just needs to be restarted to pick up the most recent environment changes which hadn't happened since the service has been running non-stop for months.
Azure Web App unable to connect to services using Lets Encrypt SSL Certificates (Expired Certificate Error)
On 30 September the Lets Encrypt root certificate expired. There are fixes that have been deployed to get around the expired root certificate and allow successful connections, however, this has not been deployed to Azure Web Apps. So how do we fix this, as we have a number of App services that don't work anymore?
To confirm: We cannot make outbound connections from our Azure Web Apps to a service using a Lets Encrypt certificate because we get an expired certificate error. This requires updating the CA Stores on the Azure Web App, but we don't have access to it.
ie. this fails from our web app:
curl https://letsencrypt.org
curl: (60) SSL certificate problem: certificate has expired