There is a very simple way using the Exchange Management Shell that you can find these users and evaluate if they have a legitimate reason to not be subject to the Database limits.
Open an Exchange Management session and type in the following command:
get-mailbox | where {$_.UseDatabaseQuotaDefaults -ne $true}
Open You will be presented with an output similar to that below:
Name Alias ServerName ProhibitSendQuota
—- —– ———- —————–
DiscoverySearchMailbox… DiscoverySearchMa… prod-ex2010-01 50 GB (53,687,091,200 bytes)
Alannah.Shaw Alannah.Shaw prod-ex2010-01 unlimited
Almaz.Duggan Almaz.Duggan prod-ex2010-01 600 MB (629,145,600 bytes)