A real-time, noninvasive approach for detecting trace amounts of vapor-phase mercuric chloride (HgCl(2)) in combustion flue gas is demonstrated using a near-infrared pulsed fiber amplifier that is frequency converted to the ultraviolet. Excitation of the HgCl(2) ([see text]) transition at 213 nm generates 253.7 nm emission from the Hg (6(3)P(1)) photoproduct that is proportional to the concentration of HgCl(2). A measured quadratic dependence of the HgCl(2) photofragment emission (PFE) signal on the laser irradiance indicates that the photodissociation process involves two-photon excitation. Additionally, low concentrations of HgCl(2) are detected with the PFE approach in an environment characteristic of coal-fired power-plant flue gas using this compact solid-state laser source. A detection limit of 0.7 ppb is extrapolated from these results.