Clean the seam connecting the brick fireplace profile with a hot, soapy water solution made with a mild dish soap. Scrub the areas with a sponge and scrub brush as necessary. Dry the seam with a clean cloth. If you need a stronger cleaner, use a solution of 1 tablespoon boric acid in 1 gallon of hot water.
Spray the seam with plain water to dampen.
Cut 1/4 inch off the tip of the caulk canister by sliding it in the cutting hole on the side of the caulk gun and squeezing the trigger. Alternatively, cut the tip with a utility knife.
Insert the caulk canister into the caulk gun so that the rod rests against the back of the canister.
Place the tip at the base of the seam on one side of the fireplace. Squeeze the caulk gun trigger to start the flow of caulk. Move the tip of the gun slowly upward at a 45-degree angle. When you reach the end of the seam, release the trigger, then pull the tip away.
Smooth the seam with a caulk smoother or wet putty knife.
Apply and smooth caulk to the seam on the other side of the fireplace.
Light a small fire in the fireplace. After an hour, add more wood to the fire and allow the hotter fire to burn for at least an hour to cure the caulk.