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The illnesses seem typical for inhaling light hydrocarbons. Considering that the dispersant being sprayed is made of light hydrocarbons (petroleum distillate), it's only making it worse in the air column above the area where it is applied. Dioxins are not present in the crude oil as is, they are being formed when the oil is burned; it is a product of incomplete combustion of the oil. Getting the oil to burn completely as it is floating on water is practically impossible. It is going to give off lots of harmful combustion by products such as carbon monoxide, dioxins, and soot, but burning it is a net plus since it gets rid of more mass of toxic volatile fractions than it leaves behind.
What's left after the crude burns is a bigger environmental problem -- the heavier fractions and the tars. They will have to be broken down by organisms in the environment. Once it is broken down, it can enter the food chain in a normal way, like other rotted organic matter.
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