Depletion of Ozone and Reservoir Species of Chlorine and Nitrogen Oxide in the Lower Antarctic Polar Vortex Measured from Aircraft

Novel airborne in situ measurements of inorganic chlorine, nitrogen oxide species, and ozone were performed inside the lower Antarctic polar vortex and at its edge in September 2012. We focus on one flight during the Transport and Composition of the LMS/Earth System Model Validation (TACTS/ESMVal) campaign with the German research aircraft HALO (High-Altitude LOng range research aircraft), reaching latitudes of 65°S and potential temperatures up to 405 K. Using the early winter correlations of reactive trace gases with N2O from the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS), we find high depletion of chlorine reservoir gases up to ∼40% (0.8 ppbv) at 12 km to 14 km altitude in the vortex and 0.4 ppbv at the edge in subsided stratospheric air with mean ages up to 4.5 years. We observe denitrification of up to 4 ppbv, while ozone was depleted by 1.2 ppmv at potential temperatures as low as 380 K. The advanced instrumentation aboard HALO enables high-resolution measurements with implications for the oxidation capacity of the lowermost stratosphere. ©2017. American Geophysical Union

A quantitative analysis of stratospheric HCl, HNO3, and O3 in the tropopause region near the subtropical jet

The effects of chemical two-way mixing on the Extratropical Transition Layer (ExTL) near the subtropical jet are investigated by stratospheric tracer-tracer correlations. To this end, in situ measurements were performed west of Africa (25–32◦N) during the Transport and Composition of the Upper Troposphere Lower Stratosphere (UTLS)/Earth System Model Validation (TACTS/ESMVal) mission in August/September 2012. The Atmospheric chemical Ionization Mass Spectrometer sampling HCl and HNO3 was for the first time deployed on the new German High Altitude and Long range research aircraft (HALO). Measurements of O3, CO, European Centre for Medium-Range Weather Forecasts (ECMWF) analysis, and the tight correlation of the unambiguous tracer HCl to O3 and HNO3 in the lower stratosphere were used to quantify the stratospheric content of these species in the ExTL. With increasing distance from the tropopause, the stratospheric content increased from 10% to 100% with differing profiles for HNO3 and O3. Tropospheric fractions of 20% HNO3 and 40% O3 were detected up to a distance of 30 K above the tropopause

Chemistry, transport and dry deposition of trace gases in the boundary layer over the tropical Atlantic Ocean and the Guyanas during the GABRIEL field campaign

We present a comparison of different Lagrangian and chemical box model calculations with measurement data obtained during the GABRIEL campaign over the tropical Atlantic Ocean and the Amazon rainforest in the Guyanas, October 2005. Lagrangian modelling of boundary layer (BL) air constrained by measurements is used to derive a horizontal gradient (≈5.6 pmol/mol km<sup>−1</sup>) of CO from the ocean to the rainforest (east to west). This is significantly smaller than that derived from the measurements (16–48 pmol/mol km<sup>−1</sup>), indicating that photochemical production from organic precursors alone cannot explain the observed strong gradient. It appears that HCHO is overestimated by the Lagrangian and chemical box models, which include dry deposition but not exchange with the free troposphere (FT). The relatively short lifetime of HCHO implies substantial BL-FT exchange. The mixing-in of FT air affected by African and South American biomass burning at an estimated rate of 0.12 h<sup>−1</sup> increases the CO and decreases the HCHO mixing ratios, improving agreement with measurements. A mean deposition velocity of 1.35 cm/s for H<sub>2</sub>O<sub>2</sub> over the ocean as well as over the rainforest is deduced assuming BL-FT exchange adequate to the results for CO. The measured increase of the organic peroxides from the ocean to the rainforest (≈0.66 nmol/mol d<sup>−1</sup>) is significantly overestimated by the Lagrangian model, even when using high values for the deposition velocity and the entrainment rate. Our results point at either heterogeneous loss of organic peroxides and/or their radical precursors, underestimated photodissociation or missing reaction paths of peroxy radicals not forming peroxides in isoprene chemistry. We calculate a mean integrated daytime net ozone production (NOP) in the BL of (0.2±5.9) nmol/mol (ocean) and (2.4±2.1) nmol/mol (rainforest). The NOP strongly correlates with NO and has a positive tendency in the boundary layer over the rainforest

Hydroxyl radicals in the tropical troposphere over the Suriname rainforest: airborne measurements

Direct measurements of OH and HO<sub>2</sub> over a tropical rainforest were made for the first time during the GABRIEL campaign in October 2005, deploying the custom-built HORUS instrument (HydrOxyl Radical measurement Unit based on fluorescence Spectroscopy), adapted to fly in a Learjet wingpod. Biogenic hydrocarbon emissions were expected to strongly reduce the OH and HO<sub>2</sub> mixing ratios as the air is transported from the ocean over the forest. However, surprisingly high mixing ratios of both OH and HO<sub>2</sub> were encountered in the boundary layer over the rainforest. <br><br> The HORUS instrumentation and calibration methods are described in detail and the measurement results obtained are discussed. The extensive dataset collected during GABRIEL, including measurements of many other trace gases and photolysis frequencies, has been used to quantify the main sources and sinks of OH. Comparison of these measurement-derived formation and loss rates of OH indicates strong previously overlooked recycling of OH in the boundary layer over the tropical rainforest, occurring in chorus with isoprene emission

Hydroxyl radicals in the tropical troposphere over the Suriname rainforest: airborne measurements

Direct measurements of OH and HO<sub>2</sub> over a tropical rainforest were made for the first time during the GABRIEL campaign in October 2005, deploying the custom-built HORUS instrument (HydrOxyl Radical measurement Unit based on fluorescence Spectroscopy), adapted to fly in a Learjet wingpod. Biogenic hydrocarbon emissions were expected to strongly reduce the OH and HO<sub>2</sub> mixing ratios as the air is transported from the ocean over the forest. However, surprisingly high mixing ratios of both OH and HO<sub>2</sub> were encountered in the boundary layer over the rainforest. <br><br> The HORUS instrumentation and calibration methods are described in detail and the measurement results obtained are discussed. The extensive dataset collected during GABRIEL, including measurements of many other trace gases and photolysis frequencies, has been used to quantify the main sources and sinks of OH. Comparison of these measurement-derived formation and loss rates of OH indicates strong previously overlooked recycling of OH in the boundary layer over the tropical rainforest, occurring in chorus with isoprene emission

Hydroxyl radicals in the tropical troposphere over the Suriname rainforest: comparison of measurements with the box model MECCA

As a major source region of the hydroxyl radical OH, the Tropics largely control the oxidation capacity of the atmosphere on a global scale. However, emissions of hydrocarbons from the tropical rainforest that react rapidly with OH can potentially deplete the amount of OH and thereby reduce the oxidation capacity. The airborne GABRIEL field campaign in equatorial South America (Suriname) in October 2005 investigated the influence of the tropical rainforest on the HOx budget (HOx = OH + HO2). The first observations of OH and HO2 over a tropical rainforest are compared to steady state concentrations calculated with the atmospheric chemistry box model MECCA. The important precursors and sinks for HOx chemistry, measured during the campaign, are used as constraining parameters for the simulation of OH and HO2. Significant underestimations of HOx are found by the model over land during the afternoon, with mean ratios of observation to model of 12.2 ± 3.5 and 4.1 ± 1.4 for OH and HO2, respectively. The discrepancy between measurements and simulation results is correlated to the abundance of isoprene. While for low isoprene mixing ratios (above ocean or at altitudes \u3e3 km), observation and simulation agree fairly well, for mixing ratios \u3e200 pptV (rainforest) the model tends to underestimate the HOx observations as a function of isoprene. Box model simulations have been performed with the condensed chemical mechanism of MECCA and with the detailed isoprene reaction scheme of MCM, resulting in similar results for HOx concentrations. Simulations with constrained HO2 concentrations show that the conversion from HO2 to OH in the model is too low. However, by neglecting the isoprene chemistry in the model, observations and simulations agree much better. An OH source similar to the strength of the OH sink via isoprene chemistry is needed in the model to resolve the discrepancy. A possible explanation is that the oxidation of isoprene by OH not only dominates the removal of OH but also produces it in a similar amount. Several additional reactions which directly produce OH have been implemented into the box model, suggesting that upper limits in producing OH are still not able to reproduce the observations (improvement by factors of ≈2.4 and ≈2 for OH and HO2, respectively). We determine that OH has to be recycled to 94% instead of the simulated 38% to match the observations, which is most likely to happen in the isoprene degradation process, otherwise additional sources are required

Constraints on instantaneous ozone production rates and regimes during DOMINO derived using in-situ OH reactivity measurements

In this study air masses are characterized in terms of their total OH reactivity which is a robust measure of the reactive air pollutant loading . The measurements were performed during the DOMINO campaign (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) held from 21/11/2008 to 08/12/2008 at the Atmospheric Sounding Station - El Arenosillo (37.1° N-6.7° W, 40 m a.s.l.). The site was frequently impacted by marine air masses (arriving at the site from the southerly sector) and air masses from the cities of Huelva (located NW of the site), Seville and Madrid (located NNE of the site). OH reactivity values showed strong wind sector dependence. North eastern continental air masses were characterized by the highest OH reactivities (average: 31.4 ± 4.5 s−1; range of average diel values: 21.3-40.5 s−1), followed by north western industrial air masses (average: 13.8 ± 4.4 s−1; range of average diel values: 7-23.4 s−1) and marine air masses (average: 6.3 ± 6.6 s−1; range of average diel values: below detection limit −21.7 s−1), respectively. The average OH reactivity for the entire campaign period was ~18 s−1 and no pronounced variation was discernible in the diel profiles with the exception of relatively high values from 09:00 to 11:00 UTC on occasions when air masses arrived from the north western and southern wind sectors. The measured OH reactivity was used to constrain both diel instantaneous ozone production potential rates and regimes. Gross ozone production rates at the site were generally limited by the availability of NOx with peak values of around 20 ppbV O3 h−1. Using the OH reactivity based approach, derived ozone production rates indicate that if NOx would no longer be the limiting factor in air masses arriving from the continental north eastern sector, peak ozone production rates could double. We suggest that the new combined approach of in-situ fast measurements of OH reactivity, nitrogen oxides and peroxy radicals for constraining instantaneous ozone production rates, could significantly improve analyses of upwind point sources and their impact on regional ozone levels

Long-range transport pathways of tropospheric source gases originating in Asia into the northern lower stratosphere during the Asian monsoon season 2012

Global simulations with the Chemical Lagrangian Model of the Stratosphere (CLaMS) using artificial tracers of air mass origin are used to analyze transport mechanisms from the Asian monsoon region into the lower stratosphere. In a case study, the transport of air masses from the Asian monsoon anticyclone originating in India/China by an eastward-migrating anticyclone which broke off from the main anticyclone on 20 September 2012 and filaments separated at the northeastern flank of the anticyclone are analyzed. Enhanced contributions of young air masses (younger than 5 months) are found within the separated anticyclone confined at the top by the thermal tropopause. Further, these air masses are confined by the anticyclonic circulation and, on the polar side, by the subtropical jet such that the vertical structure resembles a bubble within the upper troposphere. Subsequently, these air masses are transported eastwards along the subtropical jet and enter the lower stratosphere by quasi-horizontal transport in a region of double tropopauses most likely associated with Rossby wave breaking events. As a result, thin filaments with enhanced signatures of tropospheric trace gases were measured in the lower stratosphere over Europe during the TACTS/ESMVal campaign in September 2012 in very good agreement with CLaMS simulations. Our simulations demonstrate that source regions in Asia and in the Pacific Ocean have a significant impact on the chemical composition of the lower stratosphere of the Northern Hemisphere. Young, moist air masses, in particular at the end of the monsoon season in September/October 2012, flooded the extratropical lower stratosphere in the Northern Hemisphere with contributions of up to ≈30% at 380K (with the remaining fraction being aged air). In contrast, the contribution of young air masses to the Southern Hemisphere is much lower. At the end of October 2012, approximately 1.5 ppmv H$_{2}$O is found in the lower Northern Hemisphere stratosphere (at 380 K) from source regions both in Asia and in the tropical Pacific compared to a mean water vapor content of ≈5 ppmv. In addition to this main transport pathway from the Asian monsoon anticyclone to the east along the subtropical jet and subsequent transport into the northern lower stratosphere, a second horizontal transport pathway out of the anticyclone to the west into the tropics (TTL) is found in agreement with MIPAS HCFC-22 measurements

Aircraft-based measurements of High Arctic springtime aerosol show evidence for vertically varying sources, transport and composition

The sources, chemical transformations and removal mechanisms of aerosol transported to the Arctic are key factors that control Arctic aerosol–climate interactions. Our understanding of sources and processes is limited by a lack of vertically resolved observations in remote Arctic regions. We present vertically resolved observations of trace gases and aerosol composition in High Arctic springtime, made largely north of 80°&thinsp;N, during the NETCARE campaign. Trace gas gradients observed on these flights defined the polar dome as north of 66–68°&thinsp;30′&thinsp;N and below potential temperatures of 283.5–287.5&thinsp;K. In the polar dome, we observe evidence for vertically varying source regions and chemical processing. These vertical changes in sources and chemistry lead to systematic variation in aerosol composition as a function of potential temperature. We show evidence for sources of aerosol with higher organic aerosol (OA), ammonium and refractory black carbon (rBC) content in the upper polar dome. Based on FLEXPART-ECMWF calculations, air masses sampled at all levels inside the polar dome (i.e., potential temperature  &lt; 280.5&thinsp;K, altitude  &lt;  ∼ 3.5&thinsp;km) subsided during transport over transport times of at least 10 days. Air masses at the lowest potential temperatures, in the lower polar dome, had spent long periods ( &gt; 10 days) in the Arctic, while air masses in the upper polar dome had entered the Arctic more recently. Variations in aerosol composition were closely related to transport history. In the lower polar dome, the measured sub-micron aerosol mass was dominated by sulfate (mean 74&thinsp;%), with lower contributions from rBC (1&thinsp;%), ammonium (4&thinsp;%) and OA (20&thinsp;%). At higher altitudes and higher potential temperatures, OA, ammonium and rBC contributed 42&thinsp;%, 8&thinsp;% and 2&thinsp;% of aerosol mass, respectively. A qualitative indication for the presence of sea salt showed that sodium chloride contributed to sub-micron aerosol in the lower polar dome, but was not detectable in the upper polar dome. Our observations highlight the differences in Arctic aerosol chemistry observed at surface-based sites and the aerosol transported throughout the depth of the Arctic troposphere in spring.</p

Temporally delineated sources of major chemical species in high Arctic snow

Long-range transport of aerosol from lower latitudes to the high Arctic may be a significant contributor to climate forcing in the Arctic. To identify the sources of key contaminants entering the Canadian High Arctic an intensive campaign of snow sampling was completed at Alert, Nunavut, from September 2014 to June 2015. Fresh snow samples collected every few days were analyzed for black carbon, major ions, and metals, and this rich data set provided an opportunity for a temporally refined source apportionment of snow composition via positive matrix factorization (PMF) in conjunction with FLEXPART (FLEXible PARTicle dispersion model) potential emission sensitivity analysis. Seven source factors were identified: sea salt, crustal metals, black carbon, carboxylic acids, nitrate, non-crustal metals, and sulfate. The sea salt and crustal factors showed good agreement with expected composition and primarily northern sources. High loadings of V and Se onto Factor 2, crustal metals, was consistent with expected elemental ratios, implying these metals were not primarily anthropogenic in origin. Factor 3, black carbon, was an acidic factor dominated by black carbon but with some sulfate contribution over the winter-haze season. The lack of K+ associated with this factor, a Eurasian source, and limited known forest fire events coincident with this factor's peak suggested a predominantly anthropogenic combustion source. Factor 4, carboxylic acids, was dominated by formate and acetate with a moderate correlation to available sunlight and an oceanic and North American source. A robust identification of this factor was not possible; however, atmospheric photochemical reactions, ocean microlayer reaction, and biomass burning were explored as potential contributors. Factor 5, nitrate, was an acidic factor dominated by NO3−, with a likely Eurasian source and mid-winter peak. The isolation of NO3− on a separate factor may reflect its complex atmospheric processing, though the associated source region suggests possibly anthropogenic precursors. Factor 6, non-crustal metals, showed heightened loadings of Sb, Pb, and As, and correlation with other metals traditionally associated with industrial activities. Similar to Factor 3 and 5, this factor appeared to be largely Eurasian in origin. Factor 7, sulfate, was dominated by SO42− and MS with a fall peak and high acidity. Coincident volcanic activity and northern source regions may suggest a processed SO2 source of this factor