Cant Change Colour?

I have an image of a waterfall (layer attached below) that was scanned from a 4X5 transparancy, and is now a large 800mb TIFF file. I am trying to adjust the highlights on the water, the sky, and the midground all seperately. I need to make 3 layers to do this. I was able to make a layer for the water and a layer for the sky, but am having a problem making a layer for the rest of the image.
I remember a bit about watching a video on turning everything one colour and then.....? Anyhow, I was able to turn everything that I don't need to adjust black, by first multiplying a layer that I had already made and then only multiplying the selected colours that the first 4 multiplys missed. So now I am trying to turn the black a bright RGB Magenta. I tried doing this by using the Colour Replacement Tool, but that only seems to turn it grey. Then I tried using Replace Colour, but that only turned it a greyish colour also. Any idea why I cannot seem to be able to turn black into Magenta? The Paint Bucket Tool will do it, but there are thousands of little parts that are not attached so it cannot be used effectively.
When I finally get this done, how do I attach this layer over the copy of the background layer, so I can select the Magenta and delete it?
I am using Photoshop CS6 on Windows 7 Home 64bit.
If your curious to what the finished image will look like, I should have it posted on my facebook page latter this week, which can be found at http://www.facebook.com/pages/Northscape-Photography/336657619774914
Thanks in advance.

The problem is that black and white are not colors, so the tools will not work as expected.
THere are several tricks to do this as usual.
Here is one.
1.  Make selection of black
2. In channel tab clic "save selectin as Channel
3.Click on rgb channel
4. Switch to layer tab
5. Creae new layer above balck object layer
6. Set forground to light brown
7. Shift F5 choose normal preserve transparency unchecked
8.  Rt click on fill layer and select Blending  Option select screen or linear dodge
9.  Image/adjustement/change color
A few steps but hope this helps.

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