Bicarbonate-activated hydrogen peroxide and efficient decontamination of toxic sulfur mustard and nerve gas simulants

13 C NMR spectra showed that peroxymonocarbonate (HCO 4 − ) was generated in the NaHCO 3 -activated H 2 O 2 solution and pH was a key factor in its production. A cycle for the bicarbonate anion was proposed as HCO 3 −   →   HCO 3 → (CO 2 ) 2 *   →   CO 2 (aq)   →   HCO 4 − (H 2 CO 4 )   →   HCO 3 − ( HCO 3 ) basing on the results of NMR, electron paramagnetic resonance, chemiluminescence analysis. In this cycle, (CO 2 ) 2 * was the key intermediate and (CO 2 ) 2 *   →   2CO 2   +   hv was the rate controlling step. Thioanisole and paraoxon, the simulants of sulfur mustard gas and nerve gas, respectively, were efficiently decontaminated by the NaHCO 3 -activated H 2 O 2 solution. While HCO 4 − was the primary oxidant for the oxidation of thioanisole, O 2 − generated during the decomposition of HCO 4 − or H 2 O 2 led to the secondary oxidation of the sulfide. Paraoxon was degraded in the NaHCO 3 -activated H 2 O 2 solution via nucleophilic substitution by OOH − and OH − , and the degradation rate increased exponentially with increasing pH. Alkali metal ions had a catalytic effect on the degradation of paraoxon. Mustard gas and soman degraded efficiently into nontoxic products in NaHCO 3 -activated H 2 O 2 . A pH range of 9–10 was found to be optimum for the broad-spectrum decontamination of chemical warfare agents and other eco-toxicants using NaHCO 3 -activated H 2 O 2 .