Application of copper(II)-based chemicals induces CH₃Br and CH₃Cl emissions from soil and seawater

Methyl bromide (CH₃Br) and methyl chloride (CH₃Cl) are major carriers of atmospheric bromine and chlorine, respectively, which can catalyze stratospheric ozone depletion. However, in our current understanding, there are missing sources associated with these two species. Here we investigate the effect of copper(II) on CH₃Br and CH₃Cl production from soil, seawater and model organic compounds: catechol (benzene-1,2-diol) and guaiacol (2-methoxyphenol). We show that copper sulfate (CuSO₄) enhances CH₃Br and CH₃Cl production from soil and seawater, and it may be further amplified in conjunction with hydrogen peroxide (H₂O₂) or solar radiation. This represents an abiotic production pathway of CH₃Br and CH₃Cl perturbed by anthropogenic application of copper(II)-based chemicals. Hence, we suggest that the widespread application of copper(II) pesticides in agriculture and the discharge of anthropogenic copper(II) to the oceans may account for part of the missing sources of CH₃Br and CH₃Cl, and thereby contribute to stratospheric halogen load.