Do you think an ACH can be rejected (incurring reject fees) if we verify the balance ahead of time?

Of course, it can. Let’s say a couple has US$ 2,000 in the account. The husband decides to send US$ 1,000 to his parents in India. You do a balance check and it shows you US$ 2,000. Unbeknownst to the husband, the wife earlier wrote a check for US$ 1,200 that was cashed later on that day. Now the available balance would be US$ 800. When the ACH file is sent for processing later in the evening. It will be an NSF (Non-Sufficient Funds). This is just one example.

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