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Whether it's water soluble or not does not affect toxicity. Plenty of water-soluble chemicals are very harmful. The trouble with PCBs being non-water soluble means that you don't piss it back out, it accumulates in fatty tissues like reproductive organs and nerve tissue.
Water-soluble chemicals can still damage the hell out of your cells and tissues, but you then rid yourself of them.
PCBs, because they are fat soluble, bioaccumulate. That means there only has to be a little bit in the water to really screw us. Each little plankton absorbs a little bit. If a silverside eats 200,000 plankton, the PCBs from them accumulate in his fatty tissues. If a striper eats 5,000 silversides, it absorbs the PCBs from each of them, and stores it in her fatty tissues. Therefore,the concentration of PCBs in that bass you eat is MUCH higher than the concentration in the water. Many thousands of times higher.
You can minimize your PCB intake by: skinning the fish, since much of the fat is in the skin; grilling it. Much of the left-over fat will melt and drip out of the fish.
Water-soluble chemicals may still cause cancer if they damage the genes responsible for regulation of cell division. They may also cause mutation leading to birth defects in developing embryos.
To finally answer your question, though, Benzene is a non-polar molecule, and therefore not water soluble. That explains the long slick in the water. If it was soluble, it would have diffused into the water, and not have been detectable after a short time.
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