See page 23 and onwards in manual.
My best guess is that the 3 pin header on the right side is the rs232 .. the text seems to say V+ , TX and RX
The 4 pin header is probably the input for the MAX232 chip .. see page 24, the TXD0, RTS, RXD0, and CTS pins ... these are expected to be -12v ...0 level voltages... I think. The 3 pin header is ttl level signals, 3.3v or 5v? see manual.
the 5 contact edge connector ... well, first contact looks to me like 5v or some input voltage, as it goes through a diode (probably reverse voltage protection) and then a capacitor and seems to power the max232 chip.
I'd look on the back side for the ground contact pad, if the edge connector is double sided.
2nd contact .. no idea, but trace seems too thin to be ground ... so I would guess it's an enable/sleep pin for the max232 chip or maybe some option to not do voltage level conversion
3rd contact seems unused and 4th and 5th are shorted together, i suspect it's a sort of key/detection mechanism for the device the card is supposed to be plugged in (for that device to determine there's something installed in the slot)
Don't have a picture of the back side so no idea if there's contacts there or not.
edit : the green stuff by the ethernet connector ... if those are dip switches , see page 26, seems like low speed/high speed mode setting by adjusting two switches.