CatalyticEfficiencies for Methane Removal: Impactof HO<i>x</i>, NO<i>x</i>, and Chemistry in theHigh-Chlorine Regime

Catalytic production of chlorine atoms from iron salt aerosols has been suggested as a means of achieving atmospheric methane removal. The feasibility of this approach, its efficiency, and the optimum conditions for deployment must be determined, but this is not straightforward as the mechanism involves interlocking nonlinear atmospheric free radical chain reactions; under some conditions added chlorine is known to increase methane lifetime. Here we evaluate the catalytic efficiency of atmospheric methane oxidation under different conditions, initiated by the photocatalytic conversion of chloride to chlorine by iron chlorides Fe(III)Cl_<i>n</i>^{(3–<i>n</i>)} using a box model. While HO<i>x</i> and high NO<i>x</i> behaviors are well-known, a new regime for tropospheric chemistry is found and described, one characterized by high ClO<i>x</i> conditions. We find that at chlorine production rates below 1 × 10⁶ Cl₂ /(cm³ s) and ambient NO<i>x</i> and O₃ levels of 4–80 ppt NO<i>x</i> at 14 ppb O₃, 8–180 ppt NO<i>x</i> at 30 ppb O₃, and 14–200 ppt NO<i>x</i> at 40 ppb O₃ the net effect on CH₄ is negative, increasing CH₄ concentrations. This variation is driven by the formation and hydrolysis of ClONO₂ leading to the loss of O₃ and NO₂. At high rates of Cl₂ addition the reaction of CH₃OOH with Cl becomes the major source of OH and CH₄ is removed. At elevated ClO<i>x</i>, ClO^• usurps the role of NO in converting HO₂ to OH and CH₃O₂ to CH₃O. The efficiencies seen in the model range from −0.62 to 2.81 CH₄/Cl. The modeling shows that due to the dispersion of a ship’s plume into low NO<i>x</i> conditions, iron emitted by ships is likely to increase the lifetime of atmospheric methane.