The way this is accomplished is that the unused data pairs of the RJ-45 connector broken out to the 4-pin header in the corner of the shield. The 'V-' pin on that header breaks out the 7 8 pair of RJ-45 pins, and the 'V+' pin breaks out the 4 5 pair. You can use a couple of jumpers to connect those pins to 'GND' and 'VIN' respectively. This will send the PoE through the Arduino, to be regulated to 5 and 3.3V. This works really well with our passive PoE cable set! The shield also includes an SD card slot that can be accessed using the SD library.
Note: This is not 802.3af-compatible PoE, it's more of a home-brew Power-over-Ethernet scheme that we like to call "DIY PoE." You shouldn't apply anything outside the 7-12V range to those pins (The input voltage range of the Arduino board) unless you regulate the power off-board.
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