Room temperature sonolysis-based advanced oxidation process for degradation of organomercurials: application to determination of inorganic and total mercury in waters by flow injection-cold vapor atomic absorption spectrometry

A new oxidation method based on room-temperature ultrasonic irradiation (sonolysis) is proposed for conversion of organomercurials into inorganic mercury and subsequent determination by flow injection-cold vapor atomic absorption spectrometry. This advanced oxidation process eliminates the need for chemical oxidants, high temperature, and pressure for degradation of organomercurials so that total mercury can be determined with sodium tetrahydroborate(III) or tin(II) chloride as reducing agents. Complete oxidations can be accomplished within 3 min, using a 40% sonication amplitude (100 W nominal power) provided by a probe ultrasonic device (20 kHz frequency) and a 1 mol L(-1) HCl liquid medium. The presence of HCl was seen to be necessary for fast oxidation of organomercurials, in contrast to other chemical oxidants such as H2O2 or HNO3 which yielded incomplete oxidation. Further advantages of the proposed method over existing methods which are currently employed for oxidation prior to total Hg determination are the removal of hazardous wastes and the decreased risk of Hg losses by volatilization. Oxidation kinetics indicated a pseudofirst-order reaction with apparent rate constants (k) of 3.2 x 10(-2) and 1.6 x 10(-2) s(-1) for methylmercury and phenylmercury, respectively. Oxidation experiments in the presence of foreign substances acting as OH radical scavengers showed a tolerance at least up to a concentration of 1000 mg L(-1). Likewise, model wastewaters with chemical oxygen demand of up to 1000 mg L(-1) could be processed without diminishing the oxidation efficiency. The method was applied to determination of inorganic and total mercury in simulated wastewaters and spiked environmental waters in combination with selective reduction.