Freshwater: No venom
Saltwater: Venom
As Miles stated, the spine is similiar in structure to our fingernails, only much denser (harder).
Growth of the spine is relative to the overall health of the ray, primarily its nutrition.
It takes proper nutrition to grow a new spine. In captivity, a well fed ray should be expected to shed its spine every three months or so. Not uncommon to see mutliple spines attached to the tail before the topmost sheds.
Also, in freshwater rays the spine is encased within a sheath of living "skin" that nourishes and protects the spine. Once the sheath is damaged, the spine no longer grows and is usually shed.
This sheath contains proteins that act as foreign bodies once they enter into your flesh when stung. These proteins can cause ripe, speedy infections at the site of the puncture as well as radiate into nearby cells. This rampant "infection" is commonly mistaken to be "poison"
This rampant infection causes localized necrosis (cell death) swelling and tissues to extavisate (weep fluid profusly)
Once shed the spine of a freshwater stingray can and will still cause these very unpleasent items to occur.
Take the spine and soak in H2o2 (Hydrogen Peroxide) and HOT water. Let soak for an hour or two.
The carefully hold spine at its base ( the end that was in the ray) and scrub the spine with an OLD TOOTHBRUSH. The soak plus the scrub will/should remove the left-over sheath. Allow to air dry.
Enjoy. sometimes goes good on toast with jam.
This was long, but I hope it was helpful.
Respectfully, FireMedic.