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Time-resolved x-ray absorption fine structure (XAFS) spectroscopy with picosecond temporal resolution is a new method to observe electronic and geometric local structures of short-lived reaction intermediates [1]. While it adds to the information available by established ultrafast laser spectroscopies, the combination of both methodologies to the system under investigation can deliver a rather complete picture of the underlying mechanisms. We have implemented ultrafast XAFS at a synchrotron and successfully applied it to different condensed phase chemical systems. The basic experimental setups used at the Advanced Light Source and at the Swiss Light Source (SLS) have been described previously [2-5], and will be only summarized here for the SLS setup. Briefly, x-rays fro