A good time for colourful outdoor portraiture is around sunset / twilight. Around this time the background can get very colourful, but output from our flashes are usually daylight balanced, and this gives us two vastly different coloured light sources, which can work "OK", but if we change the colour of the light coming from the flash by putting a coloured piece of plastic in front of the light (called a gel), then we can really start to mix things up a bit.
Gels come in all colours, but the two most common are called CTO (Colour Temperature Orange) and CTB (Colour Temperature Blue); for flashes they're typically about 6 inches long, and a couple of inches high, and you just bend them around the flash head and hold them in place with duck tape / velcro / ruber band etc. Some flashes have proper gel holders, and for others you can download fancy templates so you can cut gels to the exact size/shape, but in reality, they all work the same; it doesn't have to be pretty - it just has to work! They also come in different strengths, typically 1/4, 1/2, and "full" - so if someone says they used a 1/2 cut CTO gel you'll know it was a 1/2 strength orange gel (like I've used below).
So lets take a quick look at how gels work:
Lets assume we have a typical sunset with rich and colourful reds and oranges. If we take a shot with this lovely scene behind our subject - and reflect some of this light back onto the face of our subject - then the reflected light will be the same colour, and the subject will take on some of this character. If we use flash instead of a reflector though, the light hitting the subject will be much whiter, and the skintones of the subject - although technically accurate (assuming we white balance to the flash light) - will none-the-less result in a subject that looks "out of place". So a CTO gel helps to balance the subject with the background - but - wait, there's more ...
... If one then shifts the colour temperature of the shot in post processing towards cooler (by adding blue) then skintones will shift from quite orange towards more natural. Unfortunately this also adds blue to the sunset and starts to neutralise the reds and oranges - but - it also adds blue to an already blue sky, thus resulting is highly saturated "lush" blues (especially if you under-expose the background slightly). Take a look at this shot as an example ... I've used a 1/2 cut CTO (so only "1/2 strength") - adjusted for a relatively normal skintone - and I STILL had to knock back the saturation by 50%! So it's powerful stuff; allowing you to get dramatic shots right out of the camera.
CTB (Colour Temperature Blue) works the opposite way ... adding blue to the subject - which means you must add orange in post processing to offset it; that orange also gets added to the background diminishing the saturation of anything blue, but adding to the satuaration of anything red / orange, and again, you get far more dramatic colours than you would of without using a gel.
In this first shot, my gelled flashes didn't recycle fast enough, and thus I was able to get an accurate white balance from the showing shoot-through umbrella; The colour temperature is 7500 Kelvin. Pretty "dull and boring" colours.
In this 2nd shot, the gelled flashes do fire, and the scene correctly white balances at 4100 Kelvin. Look at the diference! (and that's just a 1/2 cut of CTO gel!) (Although I should probably add that this isn't necessarily a perfect out of the camera shot, but it's certainly a better place to start from than the one above).
On a final note, I thought I'd include a couple of shots just to show you how much work the flash is really doing; in the first of the two, the flash didn't fire, and I haven't attempted to adjust the scene in any way (keeping in mind here we're shooting into the light too) ...
and here in the second - with the umbrella visible - you get a good feeling for the light it's throwing on our subject ...
Hope this helps
Happy to answer any questions!