I will presume that you mean static headspace sampling.
What are your analytes? What equipment do you have at your disposal? The more information you can provide, the more help you will get from us. Have you looked for application notes on analysis of blood? I found this one on the Restek website:
http://www.restek.com/pdfs/59895B.pdfIt might be helpful to you.
To minimize O2 effects you'll only have to prepare your samples in a glove box or glove bag. There should be no other O2 in your system unless you're using a flame detector and even then, it's outside the processing of your sample so it doesn't matter.
As far as water goes, it really isn't a problem. The majority of applications of static headspace GC involve aqueous samples incubated at temperatures well below the boiling point of water.