Elevated concentrations of hazardous metals in aquatic systems are known to threaten human health. Mobility, bioavailability, and toxicity of metals are controlled by chemical speciation, a dynamic process. Understanding metal behavior is limited by the lack of analytical methods that can provide rapid, sensitive, in situ measurements. While electrochemistry shows promise, it is limited by its temporal resolution and the necessity for Hg modified electrodes. In this letter, we apply fast-scan deposition-stripping voltammetry at carbon-fiber microelectrodes for in situ measurements of Cu(II). We present a novel, Hg-free technique that can measure Cu(II) with ppb sensitivity at 100 ms temporal resolution.