FireMonkey images use a 32-bit per pixel schema with 8 bits each for red, green and blue plus an extra 8 bits for transparency, also called an alpha channel. If the value of the alpha channel is #FF the pixel will be opaque, #00 will be completely transparent and values in between will vary the transparency accordingly.
Therefore a colour in FireMonkey (actually a TAlphaColor) can be set with an 8 digit hex number where the bits map to #AARRGGBB where AA is the transparency/alpha channel.
Thus, #FF00FF00 is opaque green and #88FF0000 is semi-transparent red. Any color value in which the first two digits are #00 with be completely transparent.
FireMonkey includes are pre-defined constant claNull for a completely transparent colour.
You can also use the TAlphaColorRec record to access individual colours of a TAlphaColor variable using it's fields, A, R, G and B. E.g.
Red := TAlphaColorRec(MyColour).R;
TAlphaColorRec(MyColour).A := #00;