The Sigma EF-500 DG Super has E-TTL wireless master capability, but...
1) It's only designed to work with other Sigma Supers or Canon EX flash units with E-TTL slave capability.
2) It doesn't work very well, in my experience.
However, if the Sunpak you mention is a regular old automatic/manual flash unit such as their 383 model, then it can be used as a slave by attaching an inexpensive optical slave sensor.
Any flash unit can be a "master" to optical slaves, as long as the master is not in E-TTL mode. Your Sigma Super, in manual mode, can be a master.
What's more, the Sigma Super has an optical slave sensor built-in. So it can be the slave while the Sunpak plays the role of master. Because of this capability, the Sigma Super and Sunpak 383 plus slave attachment are a wonderfully versatile combination. Both units are in my bag at all times.