it will gradually raise your pH as mentioned.
as for being harmful, if you give them a boil for 10 minutes then scrub each shell, then boil for another 10 minutes then smash them up and put into your tank they will be fine.
ive donethis with shells from clams that i bought to eat. just saved and washed all the shells and added them in the above manor to my filter...but it was my intention to raise pH(and give my tanks a bit more buffering capacity as i have soft water).
cheers