Negative chlorine ion chemistry in the upper stratosphere and its application to an artificially created dense electron cloud

This paper discusses new potential reactions of chlorine-bearing anions (negative ions) in the upper stratosphere. These reactions are then applied to the negative-ion chemistry following the injection of an electron cloud of very high density, of the order of 10^6-10⁷ e^- cm⁻³, in the 40-45-km region. The idea is to evaluate the recently proposed scheme to mitigate ozone depletion by converting the reactive chlorine atoms at these altitudes into Cl^- ions which are unreactive towards ozone, i.e., electron scavenging of Cl. We find that the previously neglected photodetachment from Cl^- is fast. For an overhead sun, this process may have a rate coefficient of 0.08 s⁻¹ when multiple scattering is included. The rate could be even higher, depending on the ground albedo. Switching reaction between Cl^-·H₂O and HCl might lead to the formation of Cl^-·HCl anion. Possible reactions of Cl^-·H₂O and Cl^-·HCl with O atoms could produce ClO^- and Cl^-₂. The production of ClO^- in this manner is significant because Cl^- having a high photodetachment rate constant would be regenerated in the very likely reactions of ClO^- with O. When these possibilities are considered, then it is found that the chlorine anions may not be the major ions inside the electron cloud due to the rapid photodetachment from Cl^-. Furthermore, in such a cloud, there may be the hazard that the Cl^--Cl^-·H₂O-ClO^--Cl^- cycle amounts to catalytic destruction of two O atoms. Thus, the scheme could be risky if practised in the altitude region where atomic oxygen is an important constituent. Similar conclusions apply even if the ClO^- species forms ClO^-₃ by three-body association with O₂, instead of reacting with O. It must be emphasized that the present study is speculative at this time, because none of the relevant reactions have been investigated in the laboratory as yet. Nevertheless, it is very safe to say that the scheme of ozone preservation by electron scavenging of the upper stratospheric Cl is much less certain than implied in the studies reported by its original proponents, because those studies neglected the photodetachment from Cl^- and made the highly unlikely assumption that the Cl^-·H₂O anion neither photodissociates nor reacts any further. The situation at the lower altitudes could be even more complex due to the formation of large cluster ions and the ion-induced aerosol formation. The lower atmospheric situation, therefore, requires much more study. The uncertainties in the scavenging scheme due to the electrostatic repulsion in the cloud should also be addressed. Despite the uncertainties about its environmental engineering usefulness, the emerging technology for artificial creation of plasmas, with any desired density and charge in the stratosphere, could have significant pure scientific values in the studies of stratospheric ion chemistry and ion-induced aerosol formation. Such studies have perennially suffered from the extremely low densities of the naturally occurring plasma.