Finally got around to trying your suggestion of formatting in FAT 32 and using clean my drive on the HDD. I still got the alignment fault. I also was looking around and saw that there was a newer version of volumio out for the Pine64. I was running 2.118-2017-03-07 and the one on the site is now 2.129-2017-03-26. The automatic updater would not work. So I refreshed my card with the new OS. Still got the same problem when attaching the external HDD (alignment fault). I also tried my to mount my NAS again too but no luck.
Is there any one out there who has got the Pine64 to work with a larger library?