Increasing the speed and complexity of semiconductor integrated circuits requires advanced processes that put extreme constraints on the level of metal contamination allowed on the surfaces of silicon wafers. Such contamination degrades the performance of the ultrathin SiO2 gate dielectrics that form the heart of the individual transistors. Ultimately, reliability and yield are reduced to levels that must be improved before new processes can be put into production. It should be noted that much of this metal contamination occurs during the wet chemical etching and rinsing steps required for the manufacture of integrated circuits and industry is actively developing new processes that have already brought the metal contamination to levels beyond the measurement capabilities of conventional analytical techniques. The measurement of these extremely low contamination levels has required the use of synchrotron radiation total reflection x-ray fluorescence (SR-TXRF) where sensitivities 100 times better than conventional techniques have been achieved. This has resulted in minimum detection limits for transition metals of 8x107 atoms/cm2. SR-TXRF studies of the amount of metal contamination deposited on a silicon surface as a function of pH and oxygen content of the etching solutions have provided insights into the mechanisms of metal deposition from solutions containing trace amounts of metals ranging from parts per trillion to parts per billion. Furthermore, by using XANES to understand the chemical state of the metal atoms after deposition, it has been possible to develop chemical models for the deposition processes. Examples will be provided for copper deposition from ultra pure water and acidic solutions.