Production of Perchlorate by Laboratory Simulated Lightning Process

Perchlorate (ClO 4 − ), a thyroid hormone disruptor, is both naturally occurring and a man-made contaminant increasingly found in a variety of terrestrial environments. The environmental presence of ClO 4 − is considered to be the result of atmospheric formation and deposition processes. The ultimate processes, particularly heterogeneous-based reactions, leading to natural ClO 4 − formation are not well understood. Oxidation of chlorine species by an energetic source such as lightning is considered to be one of the potential heterogeneous sources of natural ClO 4 − . Currently, there is very little information available on lightning-induced ClO 4 − . We designed a laboratory electrical discharge reactor capable of evaluating ClO 4 − formation by the oxidation of “dry” sodium chloride (NaCl) aerosols (relative humidity (RH) <70%) in electrical discharge plasma at voltages and energies up to 24 kV and 21 kJ, respectively. Similar to other non-electrochemical ClO 4 − production processes, the amount of ClO 4 − produced (0.5–4.8 μg) was 3 orders of magnitude lower than the input Cl− (7.1–60.1 mg). The amount of ClO 4 − generated increased with peak voltage (V) and theoretical maximum discharge energy with ΔClO 4 − /ΔV = 0.28 × 10−3 μg V−1 (R 2 = 0.94) and ΔClO 4 − /ΔE = 0.44 × 10−3 μg J−1 (R 2 = 0.83). The total ClO 4 − generated decreased with an increase in relative humidity from 2.8 ± 0.1 μg (RH ∼46%) to 0.9 ± 0.1 μg (RH ∼62%) indicating that the presence of moisture inhibits the formation of ClO 4 − . Additional modifications to the reactor support the hypothesis of ClO 4 − formation due to the action of plasma on Cl− aerosols as opposed to direct oxidation on the surface of the electrodes. Finally, the contribution of lightning-induced ClO 4 − in North America is calculated to have a wide range from 0.006 × 105 to 5 × 105 kg/year and is within the range of the measured ClO 4 − depositional flux in precipitation samples obtained across the USA (0.09 × 105–1.2 × 105 kg/y).