I want a color overlay on this header element. How can I do this with CSS?
Use mutple backgorund on the element, and use a linear-gradient as your color overlay by declaring both start and end color-stops as the same value.
Note that layers in a multi-background declaration are read much like they are rendered, top-to-bottom, so put your overlay first, then your bg image:
#header {
background:
linear-gradient(to bottom, rgba(100, 100, 0, 0.5), rgba(100, 100, 0, 0.5)) cover,
url(../img/bg.jpg) 0 0 no-repeat fixed;
height: 100%;
overflow: hidden;
color: #FFFFFF
}