I guess it really doesn't tie directly to the pi-hole/dnsmasq service. It just monitors the pihole.log file when new lines are entered. I'm not really linux savvy at all, just learning; so after a bunch of googling ;), the easiest way I've found to get this working is to setup a cron job that calls the script when the pi starts up.
Save the above script in /home/pi/ directory and call the file what ever you'd like, in the following, I called it "ledPiHoleBlinker.sh"
I'm not sure if root was required to talk to the gpio or not, so I ran the crontab utility (manages a set of automated tasks) as root and entered a new line that tells it to start at boot:
As root (or add sudo before the command), enter the following into your terminal:
crontab -e
It may ask what editor you want to use first, I chose 'nano' because it was installed, and I'm no where near comfortable using vim editor. Crontab isn't too complicated, but takes a lot of room to explain in detail, this guide is what I referenced. 
The shorthand to get this script to work at startup is to enter the following on one line at the bottom of the file, then save and exit:
@reboot bash /home/pi/ledPiHoleBlinker.sh
This tells the rapsberry pi to run the script located at /home/pi/ledPiHoleBlinker.sh as a bash script when the pi is booted. Since the crontab editor (-e) was launched as root, editing root's list of jobs, the script will run with root access.
Reboot your pi, and if you followed the script, and didn't make any changes, you should see your LED blink 5 times, then resume blinking when a block is detected.
There are probably better ways to do this, but I haven't really messed with it beyond this tutorial.