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Abstract. The atmosphere's most important oxidizer, the hydroxyl radical (OH), is generated in abundance by lightning, but the contribution of this electrically generated OH (LOH) to global OH oxidation needs to be better quantified. Part of the uncertainty in this contribution is due to the abundant nitric oxide (NO) also generated in lightning, which rapidly removes the LOH before it can oxidize other pollutants in the atmosphere. However, atmospheric observations and a previous laboratory study show extreme LOH coexists with extreme NO. The only way this electrically generated HOx (LHOx) can possibly survive is if LOH production is spatially separated from the NO production in lightning flashes and laboratory sparks. This hypothesis of spatially separate OH and NO production is further tested here in a series of laboratory experiments, where the OH decays were measured from spark discharges in air which had increasing amounts of NO added to it. The LOH decayed faster as more NO was added to the air, indicating that the LOH was reacting with the added NO and not the spark NO. Thus, LOH from lightning flashes is not immediately consumed by the electrically generated NO but is available to oxidize other pollutants in the atmosphere and contribute to global OH oxidation. Subsequent modeling of the laboratory data also supports the spatially separate production of LOH and NO and further suggests that substantial HONO may also be produced by sparks and lightning in the atmosphere. 

Atmospheric electrical discharges are now known to generate unexpectedly large amounts of the atmosphere’s primary oxidant, hydroxyl (OH), in thunderstorm anvils, where electrical discharges are caused by atmospheric charge separation. The question is “Do other electrical discharges also generate large amounts of oxidants?” In this paper, we demonstrate that corona formed on grounded metal objects under thunderstorms produce extreme amounts of OH, hydroperoxyl (HO 2 ), and ozone (O 3 ). Hundreds of parts per trillion to parts per billion of OH and HO 2 were measured during seven thunderstorms that passed over the rooftop site during an air quality study in Houston, TX in summer 2006. A combination of analysis of these field results and laboratory experiments shows that these extreme oxidant amounts were generated by corona on the inlet of the OH-measuring instrument and that corona are easier to generate on lightning rods than on the inlet. In the laboratory, increasing the electric field increased OH, HO 2 , and O 3 , with 14 times more O 3 generated than OH and HO 2 , which were equal. Calculations show that corona on lightning rods can annually generate OH that is 10–100 times ambient amounts within centimeters of the lightning rod and on high-voltage electrical power lines can generate OH that is 500 times ambient a meter away from the corona. Contrary to current thinking, previously unrecognized corona-generated OH, not corona-generated UV radiation, mostly likely initiates premature degradation of high-voltage polymer insulators.