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I have been sending secondary claims electronically for years, and this is the first time I got this error message.

Value of element CAS05 has been already used. Claim Adjustment
Reason Codes are expected to have unique values within segment CAS. Segment CAS is defined
in the guideline at position 5450. Invalid data: 96

This was a zero payment by the primary insurance, but I have had this before.
Any help would be appreciated!

The primary carrier gave an adjustment reason code if 96 which is non-covered charge. Therefore, the remaining balance is the patient's responsibility rather than secondary insurance responsibility.

I have sent these to the secondary before as they always pick up the deductibles and coinsurance and have never had this happen before.
Thanks anyway

Well, the insurance is not covering this anymore. You'll need to contact the PRIMARY insurance to find out why it is not covered. Possibly they require an authorization, etc. We will need more details on why the service was not covered.