Since ACH works with a bank account, unlike a credit card transaction there is not a way to authorize a charge, or know that funds are available.
By default you just get a response that an ACH transaction was received and that the routing number was for a valid US or Canadian bank.
Some Payment Gateways do offer add-on validation services for ACH / eCheck, however. These services can validate that the bank account number is correct, and even confirm available balance in some cases.
If you are looking to reduce returns and get more information about ACH transactions at the time of the submission, you should contact your payment gateway / payment processor to see if they offer these services.
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