Quantitative detection of iodine in the stratosphere.

Oceanic emissions of iodine destroy ozone, modify oxidative capacity, and can form new particles in the troposphere. However, the impact of iodine in the stratosphere is highly uncertain due to the lack of previous quantitative measurements. Here, we report quantitative measurements of iodine monoxide radicals and particulate iodine (Iy,part) from aircraft in the stratosphere. These measurements support that 0.77 ± 0.10 parts per trillion by volume (pptv) total inorganic iodine (Iy) is injected to the stratosphere. These high Iy amounts are indicative of active iodine recycling on ice in the upper troposphere (UT), support the upper end of recent Iy estimates (0 to 0.8 pptv) by the World Meteorological Organization, and are incompatible with zero stratospheric iodine injection. Gas-phase iodine (Iy,gas) in the UT (0.67 ± 0.09 pptv) converts to Iy,part sharply near the tropopause. In the stratosphere, IO radicals remain detectable (0.06 ± 0.03 pptv), indicating persistent Iy,part recycling back to Iy,gas as a result of active multiphase chemistry. At the observed levels, iodine is responsible for 32% of the halogen-induced ozone loss (bromine 40%, chlorine 28%), due primarily to previously unconsidered heterogeneous chemistry. Anthropogenic (pollution) ozone has increased iodine emissions since preindustrial times (ca. factor of 3 since 1950) and could be partly responsible for the continued decrease of ozone in the lower stratosphere. Increasing iodine emissions have implications for ozone radiative forcing and possibly new particle formation near the tropopause.

Quantifying Methane and Ozone Precursor Emissions from Oil and Gas Production Regions across the Contiguous US.

We present an updated fuel-based oil and gas (FOG) inventory with estimates of nitrogen oxide (NOx) emissions from oil and natural gas production in the contiguous US (CONUS). We compare the FOG inventory with aircraft-derived ("top-down") emissions for NOx over footprints that account for ∼25% of US oil and natural gas production. Across CONUS, we find that the bottom-up FOG inventory combined with other anthropogenic emissions is on average within ∼10% of top-down aircraft-derived NOx emissions. We also find good agreement in the trends of NOx from drilling- and production-phase activities, as inferred by satellites and in the bottom-up inventory. Leveraging tracer-tracer relationships derived from aircraft observations, methane (CH4) and non-methane volatile organic compound (NMVOC) emissions have been added to the inventory. Our total CONUS emission estimates for 2015 of oil and natural gas are 0.45 ± 0.14 Tg NOx/yr, 15.2 ± 3.0 Tg CH4/yr, and 5.7 ± 1.7 Tg NMVOC/yr. Compared to the US National Emissions Inventory and Greenhouse Gas Inventory, FOG NOx emissions are ∼40% lower, while inferred CH4 and NMVOC emissions are up to a factor of ∼2 higher. This suggests that NMVOC/NOx emissions from oil and gas basins are ∼3 times higher than current estimates and will likely affect how air quality models represent ozone formation downwind of oil and gas fields.

Measurements of Volatile Organic Compounds During the COVID-19 Lockdown in Changzhou, China.

The COVID-19 outbreak in 2020 prompted strict lockdowns, reduced human activity, and reduced emissions of air pollutants. We measured volatile organic compounds (VOCs) using a proton-transfer-reaction mass spectrometry instrument in Changzhou, China from 8 January through 27 March, including periods of pre-lockdown, strict measures (level 1), and more relaxed measures (level 2). We analyze the data using positive matrix factorization and resolve four factors: textile industrial emissions (62 ± 10% average reduction during level 1 relative to pre-lockdown), pharmaceutical industrial emissions (40 ± 20%), traffic emissions (71 ± 10%), and secondary chemistry (20 ± 20%). The two industrial sources showed different responses to the lockdown, so emissions from the industrial sector should not be scaled uniformly. The quantified changes in VOCs due to the lockdowns constrain emission inventories and inform chemistry-transport models, particularly for sectors where activity data are sparse, as the effects of lockdowns on air quality are explored.

Active and widespread halogen chemistry in the tropical and subtropical free troposphere.

Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O3), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O3 and methane (CH4) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10 °N to 40 °S), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric O3. The observed BrO concentrations increase strongly with altitude (∼ 3.4 pptv at 13.5 km), and are 2-4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5-6.4 pptv total inorganic bromine (Bry), or model overestimated Bry wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Bry source from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. The halogen-catalyzed loss of tropospheric O3 needs to be considered when estimating past and future ozone radiative effects.

Detection of iodine monoxide in the tropical free troposphere.

Atmospheric iodine monoxide (IO) is a radical that catalytically destroys heat trapping ozone and reacts further to form aerosols. Here, we report the detection of IO in the tropical free troposphere (FT). We present vertical profiles from airborne measurements over the Pacific Ocean that show significant IO up to 9.5 km altitude and locate, on average, two-thirds of the total column above the marine boundary layer. IO was observed in both recent deep convective outflow and aged free tropospheric air, suggesting a widespread abundance in the FT over tropical oceans. Our vertical profile measurements imply that most of the IO signal detected by satellites over tropical oceans could originate in the FT, which has implications for our understanding of iodine sources. Surprisingly, the IO concentration remains elevated in a transition layer that is decoupled from the ocean surface. This elevated concentration aloft is difficult to reconcile with our current understanding of iodine lifetimes and may indicate heterogeneous recycling of iodine from aerosols back to the gas phase. Chemical model simulations reveal that the iodine-induced ozone loss occurs mostly above the marine boundary layer (34%), in the transition layer (40%) and FT (26%) and accounts for up to 20% of the overall tropospheric ozone loss rate in the upper FT. Our results suggest that the halogen-driven ozone loss in the FT is currently underestimated. More research is needed to quantify the widespread impact that iodine species of marine origin have on free tropospheric composition, chemistry, and climate.

Ozone depletion due to dust release of iodine in the free troposphere.

Iodine is an atmospheric trace element emitted from oceans that efficiently destroys ozone (O3). Low O3 in airborne dust layers is frequently observed but poorly understood. We show that dust is a source of gas-phase iodine, indicated by aircraft observations of iodine monoxide (IO) radicals inside lofted dust layers from the Atacama and Sechura Deserts that are up to a factor of 10 enhanced over background. Gas-phase iodine photochemistry, commensurate with observed IO, is needed to explain the low O3 inside these dust layers (below 15 ppbv; up to 75% depleted). The added dust iodine can explain decreases in O3 of 8% regionally and affects surface air quality. Our data suggest that iodate reduction to form volatile iodine species is a missing process in the geochemical iodine cycle and presents an unrecognized aeolian source of iodine. Atmospheric iodine has tripled since 1950 and affects ozone layer recovery and particle formation.

Daily Satellite Observations of Methane from Oil and Gas Production Regions in the United States.

Production of oil and natural gas in North America is at an all-time high due to the development and use of horizontal drilling and hydraulic fracturing. Methane emissions associated with this industrial activity are a concern because of the contribution to climate radiative forcing. We present new measurements from the space-based TROPOspheric Monitoring Instrument (TROPOMI) launched in 2017 that show methane enhancements over production regions in the United States. In the Uintah Basin in Utah, TROPOMI methane columns correlated with in-situ measurements, and the highest columns were observed over the deepest parts of the basin, consistent with the accumulation of emissions underneath inversions. In the Permian Basin in Texas and New Mexico, methane columns showed maxima over regions with the highest natural gas production and were correlated with nitrogen-dioxide columns at a ratio that is consistent with results from in-situ airborne measurements. The improved detail provided by TROPOMI will likely enable the timely monitoring from space of methane emissions associated with oil and natural gas production.

Formaldehyde in the Tropical Western Pacific: Chemical sources and sinks, convective transport, and representation in CAM-Chem and the CCMI models.

Formaldehyde (HCHO) directly affects the atmospheric oxidative capacity through its effects on HOx. In remote marine environments, such as the Tropical Western Pacific (TWP), it is particularly important to understand the processes controlling the abundance of HCHO because model output from these regions is used to correct satellite retrievals of HCHO. Here, we have used observations from the CONTRAST field campaign, conducted during January and February 2014, to evaluate our understanding of the processes controlling the distribution of HCHO in the TWP as well as its representation in chemical transport/climate models. Observed HCHO mixing ratios varied from ~500 pptv near the surface to ~75 pptv in the upper troposphere. Recent convective transport of near surface HCHO and its precursors, acetaldehyde and possibly methyl hydroperoxide, increased upper tropospheric HCHO mixing ratios by ~33% (22 pptv); this air contained roughly 60% less NO than more aged air. Output from the CAM-Chem chemistry transport model (2014 meteorology) as well as nine chemistry climate models from the Chemistry-Climate Model Initiative (free-running meteorology) are found to uniformly underestimate HCHO columns derived from in situ observations by between 4 and 50%. This underestimate of HCHO likely results from a near factor of two underestimate of NO in most models, which strongly suggests errors in NOx emissions inventories and/or in the model chemical mechanisms. Likewise, the lack of oceanic acetaldehyde emissions and potential errors in the model acetaldehyde chemistry lead to additional underestimates in modeled HCHO of up to 75 pptv (~15%) in the lower troposphere.