It's just condensation. There is normally a "weep" hole in the muffler to allow the condensation trapped there to get out and minimize the rust.
A byproduct of combustion is water. With a hot exhaust you barely notice it. On a cold start you will see a lot of water vapor until the exhaust heats up. When you stop your engine, the remaining water vapor condenses inside your exhaust.
Patriot is right on the mark. If it is a concern of yours get a stainless steel exhaust. That water is what causes the system to rust out.
Black Lingenfelter Lux
Like Patriot said, all internal combustion engines generate water vapor in a humid environment. At startup, the exhaust system is cold and this vapor is instantly returned to the water state until the exhaust system heats to the point to where it will keep it in the gaseous state. But you have to have the water in your atmosphere to begin with and since you are just now noticing it, it's either raining out there or it's about to.
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