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They used the tar to seal boats.
It's essentially the same as pitch, which is usually made from tree sap and fat, but pitch has to be made, instead of just gathered up.
In my ancestral home (Israel and really everyone around, especially in Saudi), there are tar deposits, which the proto-Semitic peoples until now used to seal boats, as well. It was a big part of why Alexander and later Romans were so interested in the area. In fact, it's mentioned in the Torah in a number of places (e.g., Genesis 14:10 "Now the Valley of Siddim was full of tar pits,"
(I guess we've been fighting over oil reserves for a long time.)
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