An official website of the United States government
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.
more »
« less
Extreme hydroxyl amounts generated by thunderstorm-induced corona on grounded metal objects
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.
more »
« less
- PAR ID:
- 10359359
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 119
- Issue:
- 37
- ISSN:
- 0027-8424
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Jenkins, Jena M (Ed.)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 remains highly uncertain. Part of this uncertainty is due to the abundant nitric oxide (NO) also generated in lightning, which could rapidly remove the LOH before it can oxidize other pollutants in the atmosphere. However, evidence from a previous laboratory study indicated LOH is not immediately consumed by NO, possibly because LOH’s production is spatially separated from the NO production in lightning flashes. 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 modelling of the laboratory data also supports the spatially separate production of LOH and NO, and further suggests that substantial HONO is also produced by sparks and lightning in the atmosphere.more » « less
-
Environmental chambers have been playing a vital role in atmospheric chemistry research for seven decades. In last decade, oxidation flow reactors (OFR) have emerged as a promising alternative to chambers to study complex multigenerational chemistry. OFR can generate higher-than-ambient concentrations of oxidants via H 2 O, O 2 and O 3 photolysis by low-pressure-Hg-lamp emissions and reach hours to days of equivalent photochemical aging in just minutes of real time. The use of OFR for volatile-organic-compound (VOC) oxidation and secondary-organic-aerosol formation has grown very rapidly recently. However, the lack of detailed understanding of OFR photochemistry left room for speculation that OFR chemistry may be generally irrelevant to the troposphere, since its initial oxidant generation is similar to stratosphere. Recently, a series of studies have been conducted to address important open questions on OFR chemistry and to guide experimental design and interpretation. In this Review, we present a comprehensive picture connecting the chemistries of hydroxyl (OH) and hydroperoxy radicals, oxidized nitrogen species and organic peroxy radicals (RO 2 ) in OFR. Potential lack of tropospheric relevance associated with these chemistries, as well as the physical conditions resulting in it will also be reviewed. When atmospheric oxidation is dominated by OH, OFR conditions can often be similar to ambient conditions, as OH dominates against undesired non-OH effects. One key reason for tropospherically-irrelevant/undesired VOC fate is that under some conditions, OH is drastically reduced while non-tropospheric/undesired VOC reactants are not. The most frequent problems are running experiments with too high precursor concentrations, too high UV and/or too low humidity. On other hand, another cause of deviation from ambient chemistry in OFR is that some tropospherically-relevant non-OH chemistry ( e.g. VOC photolysis in UVA and UVB) is not sufficiently represented under some conditions. In addition, the fate of RO 2 produced from VOC oxidation can be kept relevant to the troposphere. However, in some cases RO 2 lifetime can be too short for atmospherically-relevant RO 2 chemistry, including its isomerization. OFR applications using only photolysis of injected O 3 to generate OH are less preferable than those using both 185 and 254 nm photons (without O 3 injection) for several reasons. When a relatively low equivalent photochemical age (<∼1 d) and high NO are needed, OH and NO generation by organic-nitrite photolysis in the UVA range is preferable. We also discuss how to achieve the atmospheric relevance for different purposes in OFR experimental planning.more » « less
-
Explosive volcanic eruptions generate electrical discharges, a phenomenon termed volcanic lightning (VL). VL is increasingly well-investigated and monitored for modern eruptions, however volcanism has been active since Earth’s origin. Thus, investigating VL under different atmospheric conditions is relevant for studies of early atmospheric chemistry and potential prebiotic reactions. We developed an experimental setup to investigate VL in varying atmospheres. We present the first experiments of laboratory discharges in particle-laden jets in varying atmospheric conditions. The new experimental setup is a mobile fragmentation bomb erupting into a gas-tight particle collector tank. This setup enables the testing of different atmospheric conditions, changes in the carrier gas of the jet, changes in the pressure within the tank, monitoring of the jet behaviour, and sampling of the atmosphere together with the decompressed solid materials. We find that the number and magnitude of near-vent electrical discharge events are similar in CO2-CO and air atmospheres.more » « less
-
Abstract During November 2018–April 2019, an 11-station very high frequency (VHF) Lightning Mapping Array (LMA) was deployed to Córdoba Province, Argentina. The purpose of the LMA was validation of the Geostationary Lightning Mapper (GLM), but the deployment was coordinated with two field campaigns. The LMA observed 2.9 million flashes (≥ five sources) during 163 days, and level-1 (VHF locations), level-2 (flashes classified), and level-3 (gridded products) datasets have been made public. The network’s performance allows scientifically useful analysis within 100 km when at least seven stations were active. Careful analysis beyond 100 km is also possible. The LMA dataset includes many examples of intense storms with extremely high flash rates (>1 s−1), electrical discharges in overshooting tops (OTs), as well as anomalously charged thunderstorms with low-altitude lightning. The modal flash altitude was 10 km, but many flashes occurred at very high altitude (15–20 km). There were also anomalous and stratiform flashes near 5–7 km in altitude. Most flashes were small (<50 km2 area). Comparisons with GLM on 14 and 20 December 2018 indicated that GLM most successfully detected larger flashes (i.e., more than 100 VHF sources), with detection efficiency (DE) up to 90%. However, GLM DE was reduced for flashes that were smaller or that occurred lower in the cloud (e.g., near 6-km altitude). GLM DE also was reduced during a period of OT electrical discharges. Overall, GLM DE was a strong function of thunderstorm evolution and the dominant characteristics of the lightning it produced.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript
- Journal Article:
- https://doi.org/10.1073/pnas.2201213119
