When one object dumps charge to another with enough energy to make a spark, then you don't need any sophisticated instruments to tell the polarity. A couple of anti-parallel-connected LEDs will suffice. Electrostatics was pretty well figured out by brilliant minds long ago, with comparatively crude instruments, way before tubes and transistors and ICs. Except for scientific curiosity, there's no need to recreate it (aka reinvent the wheel) to answer the question.
Any DMM in its voltage mode can sense the currents flowing in an electrostatic situation, so just bring a handheld DMM in its lowest VDC range, clamped with those anti-paralleled LEDs or regular diodes, and have at it. Use a simple, cheap DMM, like a Harbor Freight one, in case you accidentally discharge into a bad spot. Or, just leave out the DMM and use the LEDs. Don't forget the clipboard, paper, and pen to record the results, and try to look cool while doing it. Don't use a phone - keep it well away from all this activity.
One thing that may help is to look at the various HBM (human body model) electrostatic specifications, to get an idea of magnitudes involved. You can only store so much energy in practical conditions.
Ed
