The choice is yours, Here are some guidelines of the ratios of (whole?) blood to serum. Most important elements are Zn [6:1], Cu [1:1] (base these elements on their electrode potentials, that is, oxidising and reducing), then Se [1:1], Co [3:5] and Rb [10:1]. I have not yet analysed for S and P in whole blood and serum, so ratios available; google scholar Mars and, my student, Kunsevi-Kilola; her thesis is on our internet (CPUT). Note the enzymes present in whole blood and those present in serum. I assume that you intend to investigate cancer with respect to enzyme activity. About 34% of enzymes (metalloproteins) have inorganic (trace) elements in their moieties.
Imho, analyse both, more information at hand. If possible use ICP analysis such as AES (also known as OES)-you get parts per billion concentrations. Take care with the Se and S analyses. On the other hand carefully freeze dry the specimens, press into a pellet, coat with thin layer of carbon, (10 nm) and perform SEM-EDX (for C (H) O, N, P, S-H by difference; these are the major elements in the whole blood and serum matrices) and PIXE (trace elements, depends on the concentrations) analyses. My unpublished data indicate significant differences, for the major elements in N and O and at times S concentrations, and definitely in Cu and Zn for the low concentration elements. Cu will be higher and Zn lower than normal.
Hope I can reference your work very soon in my follow-up publications. Hope this helps. Regards