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5194/acp-2020-315
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Global-scale distribution of ozone in the remote troposphere from

ATom and HIPPO airborne field missions.
Ilann Bourgeois1,2, Jeffrey Peischl1,2, Chelsea R. Thompson1,2, Kenneth C. Aikin1,2, Teresa
Campos3, Hannah Clark4, Róisín Commane5, Bruce Daube6, Glenn W. Diskin7, James W.
Elkins8, Ru-Shan Gao2, Audrey Gaudel1,2, Eric J. Hintsa1,8, Bryan J. Johnson8, Rigel Kivi9,
Kathryn McKain1,8, Fred L. Moore1,8, David D. Parrish1,2, Richard Querel10, Eric Ray1,2,
Ricardo Sánchez11, Colm Sweeney7, David W. Tarasick12, Anne M. Thompson13, Valérie
Thouret14, Jacquelyn C. Witte3, Steve C. Wofsy6, and Thomas B. Ryerson2.

1
Cooperative Institute for Research in Environmental Sciences, University of Colorado
Boulder, Boulder, CO, USA
2
NOAA CSL, Boulder, CO, USA
3
National Center for Atmospheric Research, Boulder, CO, USA
4
IAGOS-AISBL, Brussels, Belgium
5
Department of Earth and Environmental Sciences, Lamont-Doherty Earth Observatory of
Columbia University, New York, NY, USA
6
School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA
7
NASA Langley Research Center, Hampton, VA, USA
8
NOAA GML, Boulder, CO, USA
9
Finnish Meteorological Institute, Space and Earth Observation Centre, Sodankylä, Finland
10
National Institute of Water & Atmospheric Research (NIWA), Lauder, NZ
11
Servicio Meteorológico Nacional, Buenos Aires, Argentina
12
Experimental Studies Research Division, MSC/Environment and Climate Change Canada,
Downsview, Ontario, CA
13
Earth Sciences Division, NASA/Goddard Space Flight Center, Greenbelt, MD, USA
14
Laboratoire d’Aérologie, CNRS and Université Paul Sabatier, Université de Toulouse,
Toulouse, FR
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1 Abstract
2 Ozone is a key constituent of the troposphere where it drives photochemical
3 processes, impacts air quality, and acts as a climate forcer. Large-scale in situ observations of
4 ozone commensurate with the grid resolution of current Earth system models are necessary to
5 validate model outputs and satellite retrievals. In this paper, we examine measurements from
6 the Atmospheric Tomography (ATom, 4 deployments in 2016–2018) and the HIAPER Pole-
7 to-Pole Observations (HIPPO; 5 deployments in 2009–2011) experiments, two global-scale
8 airborne campaigns covering the Pacific (HIPPO and ATom) and Atlantic (ATom) basins.
9 ATom and HIPPO represent the first global-scale, vertically resolved measurements
10 of O3 distributions throughout the troposphere, with HIPPO sampling the Pacific basin and
11 ATom sampling both the Pacific and Atlantic basins. Given the relatively limited temporal
12 resolution of these two campaigns, we first compare ATom and HIPPO ozone data to longer-
13 term observational records to establish the representativeness of our dataset. We show that
14 these two airborne campaigns captured on average 53, 54, and 38 % of the ozone variability
15 in the marine boundary layer, free troposphere, and upper troposphere/lower stratosphere
16 (UTLS), respectively, at nine well-established ozonesonde sites. Additionally, ATom
17 captured the most frequent ozone concentrations measured by regular commercial aircraft
18 flights in the northern Atlantic UTLS. We then use the repeated vertical profiles carried out
19 during these two campaigns to provide a global-scale picture of tropospheric ozone spatial
20 and vertical distributions throughout the remote troposphere. We highlight a clear
21 hemispheric gradient, with greater ozone in the northern hemisphere consistent with greater
22 precursor emissions. We also show that the ozone distribution below 8 km was similar in the
23 extra-tropics of the Atlantic and Pacific basins due to zonal circulation patterns. However,
24 twice as much ozone was found in the tropical Atlantic than in the tropical Pacific, due to
25 well-documented dynamical patterns transporting continental air masses over the Atlantic.
26 We finally show that the seasonal variability of tropospheric ozone over the Pacific and the
27 Atlantic basins is driven by transported continental plumes and photochemistry, and the
28 vertical distribution is driven by photochemistry and mixing with stratospheric air. This new
29 dataset is essential for improving our understanding of both ozone production and loss
30 processes in remote regions, as well as the influence of anthropogenic emissions on baseline
31 ozone.
32
33

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34 1. Introduction
35 Tropospheric ozone (O3) plays a major role in local, regional, and global air quality and
36 significantly influences Earth’s radiative budget (IPCC, 2013; Shindell et al., 2012). In addition,
37 O3 drives tropospheric photochemical processes by controlling hydroxyl radical (OH)
38 abundance, which subsequently controls the lifetime of other pollutants including volatile
39 organic compounds (VOCs), greenhouse gases, and some stratospheric ozone-depleting
40 substances (Crutzen, 1974; Levy, 1971). Sources of O3 to the troposphere include downward
41 transport from the stratosphere (Junge, 1962) and photochemical production from precursors
42 such as carbon monoxide (CO), methane (CH4), and VOCs in the presence of nitrogen oxides
43 (NOx) emitted by natural or anthropogenic sources (Monks et al., 2009). Tropospheric O3 sinks
44 include photo-dissociation, chemical reactions, and dry deposition. Owing to its relatively long
45 lifetime (~23 days in the troposphere; Young et al., 2013), O3 can be transported across intra-
46 hemispheric scales. O3 mixing ratios over a region thus depend not only on local and regional
47 sources and sinks, but also on long-range transport. Further, the uneven density of O3 monitoring
48 locations around the globe leads to significant sampling gaps, especially near developing nations
49 (Gaudel et al., 2018). The troposphere over the remote oceans is among the least-sampled
50 regions, despite hosting 60–70 % of global tropospheric O3 burden (Holmes et al., 2013). Since
51 the early 1980’s, several aircraft campaigns have periodically addressed this paucity of remote
52 observations, most notably under the umbrella of the Global Tropospheric Experiment (GTE), a
53 major component of the National Aeronautics and Space Administration (NASA) Tropospheric
54 Chemistry Program ([Link]
55 Continuing this tradition, the Atmospheric Tomography mission (ATom,
56 [Link] was a NASA Earth Venture airborne field project to address the
57 sparseness of atmospheric observations over remote ocean regions by systematically sampling
58 the troposphere over the Pacific and Atlantic basins along a global-scale circuit (Fig. 1). ATom
59 deployed an extensive payload on the NASA DC-8 aircraft, measuring a wide range of chemical,
60 microphysical, and meteorological parameters in repeated vertical profiles from 0.2 km to over
61 13 km altitude, from the Arctic to the Antarctic over the Pacific and Atlantic Oceans, in four
62 separate seasons from 2016 to 2018. One of the main goals of ATom was to develop an
63 observation-based climatology of the composition of the remote atmosphere using airborne in
64 situ measurements from global-scale sampling flights.

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65 ATom built on a previous study, the HIAPER Pole-to-Pole Observations mission

66 (HIPPO, [Link] The goal of HIPPO was to measure
67 atmospheric distributions of important greenhouse gases and reactive species over the Pacific
68 Ocean, from the surface to the tropopause, five times during different seasons from 2009 to
69 2011. Together, ATom and HIPPO provide unique information about the altitudinal and
70 latitudinal composition of the remote troposphere over the Pacific, and over the Atlantic for
71 ATom.
72 Here we use existing ozonesonde and commercial aircraft observations of O3 at selected
73 locations along the ATom and HIPPO circuits to provide a climatological context for the
74 altitudinal, latitudinal, and seasonal distributions of O3 derived from the systematic airborne in
75 situ “snapshots”. Long-term O3 observations are obtained from decades of ozonesonde vertical
76 profiles (e.g., Oltmans et al., 2013; Thompson et al., 2017) and from ~60,000 flights using the
77 In-service Aircraft for a Global Observing System (IAGOS) infrastructure (Petzold et al., 2015;
78 [Link] Ozonesondes have typically been launched weekly for two decades or
79 more, depending on the site, and have sampled a wide range of air masses across the globe, from
80 O3-poor remote surface locations to the O3-rich stratosphere. IAGOS commercial aircraft have
81 provided daily measurements in the upper troposphere and lower stratosphere (UTLS) for the
82 past 25 years, especially over the northern midlatitudes between America and Europe.
83 Combined, the ozonesonde and IAGOS datasets offer robust measurement-based climatologies
84 that quantify the full expected range of atmospheric O3 variability with altitude and season.
85 The in-situ data from temporally-limited intensive field studies can be placed in context
86 by comparing them with long-term ozonesonde and commercial aircraft monitoring data. We
87 show that ATom and HIPPO measurements capture the spatial and, in some cases, the temporal
88 dependence of O3 in the remote atmosphere. Then, we use the geographically extensive ATom
89 and HIPPO vertical profile data to establish a more complete measurement-based benchmark for
90 O3 abundance and distribution in the remote marine atmosphere.
91
92 2. Measurements
93 2.1 ATom
94 The four ATom circuits occurred in July–August 2016 (ATom-1), January–February
95 2017 (ATom-2), September–October 2017 (ATom-3), and April–May 2018 (ATom-4), thus

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96 spanning all four seasons in both hemispheres over a two-year timeframe (Table S1). The
97 mission in total consisted of 48 science flights and 548 vertical profiles distributed nearly equally
98 along the global circuit. All four deployments completed roughly the same loop, starting and
99 ending in Palmdale, California, USA (Fig. 1). A notable addition during ATom-3 and -4 were
100 out-and-back flights from Punta Arenas, Chile to sample the Antarctic troposphere and UTLS.
101 O3 was measured using the National Oceanic and Atmospheric Administration (NOAA)
102 nitrogen oxides and ozone (NOyO3) instrument. The O3 channel of the NOyO3 instrument is
103 based on the gas-phase chemiluminescence (CL) detection of ambient O3 with pure NO added as
104 a reagent gas (Ridley et al., 1992; Stedman et al., 1972). Ambient air is continuously sampled
105 from a pressure-building ducted aircraft inlet into the NOyO3 instrument at a typical flow rate of
106 1025.0 ± 0.2 standard cubic centimeters per minute (sccm) in flight. Pure NO reagent gas flow
107 delivered at 3.450 ± 0.006 sccm is mixed with sampled air in a pressure (8.00 ± 0.08 Torr) and
108 temperature (24.96 ± 0.01 °C) controlled reaction vessel. NO-induced CL is detected with a dry-
109 ice-cooled, red-sensitive photomultiplier tube and the amplified digitized signal recorded using
110 an 80 MHz counter; pulse coincidence corrections at high count rates were applied, but are
111 negligible for the data presented in this work. The instrument sensitivity for measuring O3 under
112 these conditions is 3150 ± 80 counts per second per part per billion by volume (ppbv) averaged
113 over the entire ATom circuit. CL detector calibrations were routinely performed both on the
114 ground and during flight by standard addition of O3 produced by irradiating ultrapure air with
115 185 nm UV light and independently measured using UV optical absorption at 254 nm. All O3
116 measurements were taken at a temporal resolution of 10 Hz, averaged to 1 Hz, and corrected for
117 the dependence of instrument sensitivity on ambient water vapor content (Ridley et al., 1992).
118 Under these conditions the total estimated 1 Hz uncertainty at sea level is ± (0.015 ppbv + 2 %).
119 A commercial dual-beam photometer (2B Technologies model 211) based on UV optical
120 absorption at 254 nm also measured O3 on ATom, with an estimated uncertainty of ± (1.5 ppbv +
121 1 %) at a 2-second sampling resolution. Comparison of the 2B absorption instrument O3 data to
122 the NOyO3 CL instrument O3 data agreed to within combined instrumental uncertainties, lending
123 additional confidence to the NOyO3 CL instrument calibration. For the ATom project we use
124 NOyO3 instrument O3 data in the following analyses.
125 Data from two CO measurements were combined in this analysis. The Harvard quantum
126 cascade laser spectrometer (QCLS) instrument used a pulsed quantum cascade laser tuned at

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127 ∼2160 cm−1 to measure the absorption of CO through an astigmatic multi-pass sample cell with
128 76 m path length and detection using a liquid-nitrogen-cooled HgCdTe detector (Santoni et al.,
129 2014). In-flight calibrations were conducted with gases traceable to the NOAA World
130 Meteorological Organization (WMO) X2014A scale, and the QCLS observations have an
131 accuracy and precision of 3.5 and 0.15 ppb for 1 Hz data, respectively. CO was also measured by
132 the NOAA cavity ring-down spectrometer (CRDS, Picarro, Inc., model G2401-m) in the 1.57
133 μm region with a total uncertainty of 5.0 ppbv for 1 Hz data (Karion et al., 2013). The NOAA
134 Picarro was also calibrated to the NOAA CO-X2014A scale. The combined CO data (CO-X)
135 used here corresponds to the QCLS data, with the Picarro measurement used to fill calibration
136 gaps in the QCLS time series.
137 Water (H2O) vapor was measured using the NASA Langley Diode Laser Hygrometer
138 (DLH), an open-path infrared absorption spectrometer that uses a laser locked to a water vapor
139 absorption feature at ∼1.395 µm. Raw data are processed at the instrument’s native ∼100 Hz
140 acquisition rate and averaged to 1 Hz with an overall measurement accuracy within 5 %.
141
142 2.2 HIPPO
143 The HIPPO mission consisted of five seasonal deployments over the Pacific basin
144 between 2009 and 2011, from the North Pole to the coastal waters of Antarctica (Wofsy, 2011).
145 HIPPO deployments consisted of two transects, southbound and northbound, and occurred in
146 January 2009 (HIPPO-1), October–November 2009 (HIPPO-2), March–April 2010 (HIPPO-3),
147 June–July 2011 (HIPPO-4) and August–September 2011 (HIPPO-5). The platform used was the
148 NSF Gulfstream V (GV) aircraft. More details can be found in Table S1.
149 A NOAA custom-built dual-beam photometer based on UV optical absorption at 254 nm
150 was used to measure O3 (Proffitt and McLaughlin, 1983). The uncertainty of the 1 Hz O3 data is
151 estimated to be ± (1 ppbv + 5 %) for 1 Hz data. A commercial dual-beam O3 photometer (2B
152 Technologies model 205) based on UV optical absorption at 254 nm was also included in the
153 HIPPO payload. Comparison of the 2B O3 data to the NOAA O3 data showed general agreement
154 within combined instrument uncertainties on level flight legs. For the HIPPO project we use
155 NOAA O3 data in the following analyses.
156 Data from two CO measurements were combined in this analysis. The QCLS instrument
157 was the same instrument as used during ATom and described in section 2.1. CO was also

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158 measured by an Aero-Laser AL5002 instrument using vacuum UV resonance fluorescence (in
159 the 170–200 nm range) instrument with an uncertainty of ± (2 ppbv + 3 %) at a 2-second
160 sampling resolution. The combined CO data (CO-X) used here corresponds to the QCLS data,
161 with the Aero-Laser measurement used to fill calibration gaps in the QCLS time series.
162
163 2.3 IAGOS
164 IAGOS is a European Research Infrastructure that provides airborne in situ chemical,
165 aerosol, and meteorological measurements using commercial aircraft (Petzold et al., 2015). The
166 IAGOS Research Infrastructure includes data from both the CARIBIC (Civil Aircraft for the
167 Regular Investigation of the atmosphere Based on an Instrument Container; Brenninkmeijer et
168 al., 2007) and MOZAIC (Measurements of OZone and water vapor by Airbus In-service
169 airCraft; Marenco et al., 1998) programs, providing measurements from ~60,000 flights since
170 1994. We note the relative lack of IAGOS data over the Pacific compared to the Atlantic (shorter
171 temporal record, lower flight frequency, and much fewer flights with concomitant O3 and CO
172 measurements), and therefore limited the comparison to the Atlantic. Because commercial
173 aircraft cruise altitudes over the ocean are predominantly between 9 and 12 km, the comparison
174 between ATom and IAGOS is further limited to the UTLS (Fig. 1). More details are shown in
175 Table S1.
176 Identical dual-beam UV absorption photometers measured O3 aboard the IAGOS flights.
177 An instrument comparison demonstrated that the photometers (standard model 49, Thermo
178 Scientific, modified for aircraft use) showed good consistency in measuring O3 following an
179 inter-comparison experiment (Nédélec et al., 2015). The associated uncertainty is ± (2 ppbv + 2
180 %) at a 4-second sampling resolution (Thouret et al., 1998).
181 CO measurements were made using infra-red absorption photometers (standard model 48
182 Trace Level, Thermo Scientific, modified for aircraft use) with an uncertainty of ± (5 ppbv + 5
183 %) at a 30-second sampling resolution (Nédélec et al., 2003, 2015).
184
185 2.4 Ozonesondes
186 Ozonesondes have measured the vertical distribution of O3 in the atmosphere for decades,
187 and provide some of the longest tropospheric records that are commonly used to determine
188 regional O3 trends (Gaudel et al., 2018; Leonard et al., 2017; Oltmans et al., 2001; Tarasick et

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189 al., 2019a; Thompson et al., 2017). Ozonesonde launching sites are operated by the NOAA
190 ESRL Global Monitoring Division (GMD), NASA Goddard’s Southern Hemisphere Additional
191 OZonesondes (SHADOZ) program, the New Zealand National Institute of Water & Atmospheric
192 Research (NIWA), the National Meteorological Center of Argentina (SNMA) in collaboration
193 with the Finnish Meteorological Institute (FMI), or Environment and Climate Change Canada. A
194 more detailed description of each ozonesonde site and corresponding dataset can be found in
195 Tables S1 and S2. All sites use electrochemical concentration cell (ECC) ozonesondes that rely
196 on the potassium iodide electrochemical detection of O3, and which provide a vertical resolution
197 of about 100 m (Komhyr, 1969). The associated uncertainty is usually ± (5–10 %) (Tarasick et
198 al., 2019a; Thompson et al., 2019; Witte et al., 2018).
199
200 2.5 Data analysis
201 In this analysis, ATom flight tracks were divided into the Atlantic and Pacific basins, and
202 further subdivided into five regions within those basins: tropics, and northern and southern
203 middle- and high-latitudes. Vertical profiles presented graphically in this paper show O3 median
204 values and the 25th to 75th percentile range within the 0–12 km tropospheric column sampled by
205 the DC-8 aircraft. These medians were obtained by averaging with equal weight the individual
206 profiles within each region over 1 km altitude bins.
207 HIPPO flight tracks are illustrated in Figure 1. The flight segments used for comparison
208 with ATom were binned into the same Pacific latitude and longitude bands as for ATom. HIPPO
209 vertical profile data are derived using the same methodology as for ATom.
210 All IAGOS flight tracks over the northern and tropical Atlantic are represented in Figure
211 1 in green. The latitude bands used to parse IAGOS data are consistent with the ones used for
212 ATom. The longitude bands are 50° W to 20° W in the tropics, 50° W to 10° W in the northern
213 midlatitudes, and 110° W to 10° W in the northern high-latitudes. Variations of the longitude
214 band widths do not significantly affect the O3 distributions measured by IAGOS. Data from all
215 flights from 1994 to 2017 were included in the IAGOS dataset considered here, and were then
216 divided into two altitude bins (8–10 km and 10–12 km) in order to better understand the
217 influence of different O3 sources (e.g., anthropogenic, stratospheric) on these two layers of the
218 atmosphere.

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219 We compare the ozonesonde measurements to ATom and HIPPO aircraft data sampled
220 within 500 km of each ozonesonde launching site, since we expect a robust correlation in the free
221 troposphere within this distance (Liu et al., 2009). We used the surface coordinates of the
222 ozonesonde sites because the in-flight coordinates of ozonesondes are not available at all sites.
223 For comparison with ozonesonde long term records, we consider three regions of the
224 atmosphere: boundary layer (0–2 km), free troposphere (2–8 km), and UTLS (8–12 km). For
225 each layer, we compared monthly O3 distributions from ozonesondes with the corresponding
226 seasonal O3 distributions from aircraft measurements using the skill score (Sscore) metric (Perkins
227 et al., 2007). The Sscore is calculated by summing the minimum probability of two normalized
228 distributions at each bin center, and therefore measures the overlapping area between two
229 probability distribution functions. If the distributions are identical, the skill score will equal 100
230 % (see Fig. S1 for further examples). Note the Sscore is positively correlated with the size of the
231 bin used to compare distributions. Here we chose a bin size of 5 ppbv, which is larger than the
232 combined precision of ATom, HIPPO, and IAGOS measurements, but small enough to separate
233 distinct air masses and their influence on O3 distribution. Variables such as the distance to each
234 ozonesonde launching site (500 km in this study), the bin size of the O3 distributions (5 ppbv in
235 this study), and the length of each ozonesonde record (full length in this study) can shift the
236 vertically-averaged Sscore value by up to 8 % (Table S3). We therefore treat this 8 % as a rough
237 estimate of the precision of the Sscore values presented here.
238 All three techniques (chemiluminescence, UV absorption, and ECC) used to measure O3
239 for the datasets analyzed in this work have been shown to provide directly-comparable accurate
240 measurements with well-defined uncertainties (Tarasick et al., 2019a).
241
242 2.6 Back trajectory analysis
243 Analysis of back trajectories for air masses sampled during airborne missions is useful to
244 examine the air mass source regions and causes for O3 variability over the Pacific and Atlantic
245 Oceans. We calculated ten-day back trajectories using the Traj3D model (Bowman, 1993;
246 Bowman and Carrie, 2002) and National Centers for Environmental Prediction (NCEP) global
247 forecast system (GFS) meteorology. Trajectories were initialized each minute along all of the
248 ATom flight tracks.
249

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250 3. Comparison of ATom and HIPPO O3 distributions to longer-term observational

251 records
252 Here we use existing ozonesonde and IAGOS observations of O3 at selected locations
253 along the ATom and HIPPO circuits to provide a climatological context for O3 distributions
254 derived from the systematic airborne in situ “snapshots”. We quantify how much of O3
255 variability, occurring on timescales ranging from hours to decades, was captured by the
256 temporally-limited HIPPO and ATom missions.
257
258 3.1. Comparison to ozonesondes
259 ATom and HIPPO explored the fidelity with which airborne missions represent O3
260 climatology in the remote troposphere. Here, we show that aircraft-measured median O3 follows
261 the seasonal ozonesonde-measured median O3 cycle at most of the sites studied here, and at
262 almost all altitudes – with a few exceptions (Figs. 2 and 3). Figure 2 plots the monthly median O3
263 measurements from the tropical ozonesonde sites in three altitude bins, along with the median
264 values obtained from HIPPO and ATom measurements. Figure 3 plots the same for the
265 extratropical sites. Figure 4 correlates the median O3 measured by aircraft in Figures 2 and 3
266 with those measured by ozonesondes. At the Eureka site, the winter and spring ATom
267 deployments recorded a significantly lower median O3 compared to the corresponding
268 ozonesonde monthly median O3 in the 0–2 km range (Fig. 3). Eureka is frequently subject to
269 springtime O3 depletion events at the surface due to atmospheric bromine chemistry, which is
270 well recorded by the ozonesonde record (Fig. 3; Tarasick and Bottenheim, 2002). Sampling
271 during O3 depletion events significantly lowered the ATom winter and springtime O3
272 distributions near this site. In the 2–8 km range, there is a very good seasonal agreement between
273 ATom/HIPPO and the ozonesondes (Fig. 4b). Most seasonal differences are found above 8 km
274 (e.g., ATom in February at Trinidad Head and in May at Eureka; Fig. 3) and can be linked to the
275 occurrence – or absence – of stratospheric air sampling during ATom and HIPPO. However, it is
276 straightforward to remove stratospheric airmasses from airborne data using filters based on
277 meteorology (potential vorticity) or composition (H2O/O3) (e.g., Cohen et al., 2018). In the
278 absence of stratospheric air mixing (< 8 km in Fig. 4), ATom/HIPPO successfully capture a large
279 fraction of O3 climatology everywhere (Figs. 4b and 4c).
280

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281 Figures 5 and 6 show vertical profiles of O3 distributions by season at each ozonesonde
282 site, along with comparisons to HIPPO and ATom vertical profiles. Our analysis reveals that O3
283 distributions derived from the ATom and HIPPO seasonal “snapshots” capture 30–71 % of the 1
284 km-vertically binned O3 distribution established by long-term ozonesonde climatologies. For the
285 nine ozonesonde sites considered here, ATom and HIPPO captured on average 53 %, 54 %, and
286 38 % of the O3 distribution in the 0–2 km, 2–8 km, and 8–12 km altitude bins, respectively.
287 Larger differences between ATom/HIPPO and the ozonesonde records in the UTLS (8–
288 12 km) can be ascribed to O3 variability from stratospheric–tropospheric exchanges, which are
289 not always captured by the ATom and HIPPO missions. This increased O3 variability in the
290 UTLS is well-described by the long term ozonesonde records at Lauder, Trinidad Head, Eureka,
291 Ushuaia, and Marambio (Figs. 3 and 6). In these middle- and high-latitude locations in both
292 hemispheres, O3 variability is especially pronounced during winter and spring, time periods
293 favorable to more frequent stratospheric air mixing (Greenslade et al., 2017; Lin et al., 2015;
294 Tarasick et al., 2019b). Furthermore, the probability of sampling stratospheric air masses at
295 ATom and HIPPO ceiling altitude (12–14 km) increases with latitude, resulting in a lower Sscore
296 between the ATom/HIPPO and ozonesonde datasets at the extra-tropical sites than at the tropical
297 sites (Figs. S2a and S2b).
298 In the boundary layer (0–2 km) of the remote troposphere, O3 variability is predominantly
299 impacted by loss mechanisms. Ozonesonde records show instances of O3 mixing ratios lower
300 than 10 ppbv throughout the year in the boundary layer at the nine sites studied here (Figs. 2 and
301 3). The lowest O3 mixing ratios are a result of (a) photochemical destruction over the oceans in
302 the tropics (Monks et al., 1998, 2000; Thompson et al., 1993), (b) O3-destroying halogen
303 emissions in polar regions in springtime (e.g., Fan and Jacob, 1992), and (c) transport of O3-poor
304 oceanic air over the midlatitude sites (e.g., Neuman et al., 2012).
305 ATom and HIPPO best describe the O3 distribution in the free troposphere (2–8 km; Figs.
306 S2a and S2b). This suggests that airborne campaigns can capture global baseline O3 values,
307 along with the long-range transport of O3 pollution plumes often lofted to this altitude range and
308 responsible for O3 variability.
309
310 While ATom consisted of one transect per ocean per season, HIPPO covered the Pacific
311 twice per seasonal deployment (southbound and northbound). The 1 km-binned Sscore is on

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312 average higher when two combined seasonal HIPPO flights (southbound and northbound) were
313 available to compare to ozonesonde records, as opposed to when comparing O3 profiles from
314 individual HIPPO transects with ozonesonde records (Fig. S2c). In addition, two seasonal flights
315 during HIPPO reduced the occurrence of low Sscore values. This Sscore decrease from flying only
316 one Pacific transect only during ATom was traded for the increase of vertical profiles over the
317 Atlantic Basin, which were not sampled during HIPPO. Future airborne missions with multiple
318 seasonal vertical profiles over large-scale regions would be ideal to better depict the full range of
319 tropospheric O3 variability.
320
321 3.2. Comparison to IAGOS
322 IAGOS O3 and CO observations in the northern Atlantic UTLS provide a measurement-
323 based climatology at commercial aircraft cruise altitudes for comparison to ATom. Simultaneous
324 measurements of O3 and CO are of particular interest because CO provides a long-lived tracer of
325 continental emissions, which helps to differentiate O3 sources (Cohen et al., 2018). We note that
326 while IAGOS measurements encompass hundreds of seasonal flights (depending on the region),
327 ATom sampled within each latitude band and season on one or two flights only (Fig. 1). Thus,
328 variability in the UT that occurred on timescales longer than a day were not captured by ATom.
329 Consequently, it is not surprising to see that ATom systematically under-sampled tropospheric
330 O3 (and CO) variability compared to IAGOS at all latitudes in the northern Atlantic (Figs. 7 and
331 8). ATom captured on average 40 % of the O3 variability measured by IAGOS in the Atlantic
332 UTLS (Fig. 7), on par with the Sscore of 38 % obtained when comparing ATom and HIPPO to
333 ozonesonde data (see section 3.1).
334
335 In the middle- and high-latitudes, the shapes of the O3 vs. CO scatterplots from IAGOS
336 data demonstrate that distinct sources contribute to O3 levels in the UTLS (Figs. 8a and 8b;
337 Gaudel et al., 2015). The high O3 (>150 ppbv) – low CO (<100 ppbv) range corresponds to
338 intrusions of stratospheric air, which were mostly sampled in the spring season during ATom,
339 supporting previous observations of increased stratospheric air mixing during this season (Lin et
340 al., 2015; Tarasick et al., 2019b). The low O3 (<50 ppbv) – low CO (<100 ppbv) range
341 corresponds to the tropospheric baseline air, whereas the intermediate O3 (50–120 ppbv) – high
342 CO (>100 ppbv) range generally represents the influence of air masses transported from

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343 continental regions. During ATom, high O3 and low CO in the middle- and high-latitude UTLS
344 were typical of stratospheric and baseline tropospheric air mixing.
345
346 O3 measured during IAGOS rarely exceeds 150 ppbv in the northern tropical Atlantic
347 UTLS (Fig. 8c). This is expected because the tropical tropopause is typically situated between 13
348 and 17 km altitude and IAGOS flights typically cruise below 12 km. Therefore, instances of
349 stratospheric intrusions at IAGOS flight altitudes are limited. O3 measured during ATom in the
350 tropical Atlantic above 8 km was generally positively correlated with CO, showing the
351 contribution of tropospheric O3 production from continental sources reaching high altitudes.
352 Given this variability, the ATom data do not capture the extrema of UTLS O3 variability in the
353 IAGOS measurements (Figs. 7 and 8). However, the most frequently measured O3 and CO
354 values from ATom overlap with the most frequently measured O3 and CO values from IAGOS
355 (contours in Fig. 8), suggesting that ATom captured the mode of the O3 and CO distributions
356 from IAGOS in the northern Atlantic UTLS.
357
358 4. O3 distributions in the remote troposphere from ATom and HIPPO
359 We have established the fidelity of ATom and HIPPO O3 data by comparison to
360 measurement-based climatologies of tropospheric O3 from well-established ozonesonde and
361 commercial aircraft monitoring programs. In the following sections we exploit the systematic
362 nature of the ATom and HIPPO vertical profiles to provide a global-scale picture of tropospheric
363 O3 distributions in the remote atmosphere. Figure 9 presents the altitudinal, latitudinal, and
364 seasonal distribution of tropospheric O3 during ATom and HIPPO. Higher O3 was measured
365 during ATom & HIPPO in the Northern Hemisphere (NH) than in the Southern Hemisphere
366 (SH), both in the Pacific and in the Atlantic. This holds true throughout the tropospheric column
367 from 0 to 8 km, both in the middle- and high-latitudes (Fig. S3). In the midlatitudes below 8 km,
368 median O3 ranged between 25 and 45 ppbv in the SH, and between 35 and 65 ppbv in the NH. In
369 the high latitudes below 8 km, median O3 ranged between 30 and 45 ppbv in the SH, and
370 between 40 and 75 ppbv in the NH. Notable features in the global O3 distribution are discussed
371 in more detail in the following sections. Figure 10 presents the vertically-resolved distribution of
372 tropospheric O3 from 0–12 km for the Atlantic (ATom in green) and for the pacific (ATom in
373 pink, HIPPO in blue). Sscore values resulting from the comparison of HIPPO and ATom Pacific

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374 distributions are shown with blue diamonds, and from the comparison of ATom Atlantic and
375 Pacific distributions with pink squares. Figure 11 is derived from Figure 10 and gives the Sscore
376 values against altitude in the first panel, as well as the relative difference of median O3 from 0 to
377 8 km in the second panel. Figure
378
379 4.1. Tropics
380 Vertical distribution. O3 is at a minimum in the tropical marine boundary layer (MBL),
381 especially over the Pacific (Fig. 10a). The lowest measured O3 in this region was 5.4 ppbv in
382 May during ATom, and 3.5 ppbv in January during HIPPO. The tropical MBL is a net O3 sink
383 owing to very slow O3 production rates – NO levels averaged 22 ± 12 pptv in the Pacific and
384 Atlantic MBL during ATom – and rapid photochemical destruction rates of O3 in a sunny, humid
385 environment (Kley et al., 1996; Parrish et al., 2016; Thompson et al., 1993). Deep stratospheric
386 intrusions into the Pacific MBL were not observed in ATom or HIPPO, in contrast to reports
387 from previous studies (e.g., Cooper et al., 2005; Nath et al., 2016). In the tropics, marine
388 convection within the intertropical convergence zone (ITCZ) is associated with relatively low O3
389 values throughout the tropospheric column, with median O3 mixing ratios less than 25 ppbv
390 below 4 km altitude in the tropical Pacific (Fig. 10a; Oltmans et al., 2001). The relative
391 difference between ATom Atlantic and Pacific median O3 in the tropics below 8 km is
392 consistently higher than a factor of 1.5, with an average Sscore of 43 % (Figs. 10a and 11b). We
393 ascribe this difference to O3 production from biomass burning (BB) emissions in the continental
394 regions surrounding the tropical Atlantic; back trajectories from the ATom flight tracks show the
395 tropical Atlantic is strongly affected by transport from BB source regions in both Africa and
396 South America (Fig. S4; Jensen et al., 2012; Sauvage et al., 2006; Stauffer et al., 2018;
397 Thompson et al., 2000). Although ATom and HIPPO data show evidence for extensive and
398 widespread BB influence on O3 in the Pacific as well, O3 mixing ratios are consistently more
399 elevated throughout the tropospheric column in the Atlantic. One reason is closer proximity of
400 the mid-ocean Atlantic flight tracks to O3 precursor source regions. In addition, the positive
401 correlation of O3 enhancements with black carbon (Katich et al., 2018) and reactive nitrogen
402 species (Thompson et al., personal communication) indicate BB influence. These findings
403 confirm studies that previously highlighted the impact of African BB emissions on O3 production
404 in the tropical Atlantic (e.g., Andreae et al., 1994; Fishman et al., 1996; Jourdain et al., 2007;

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405 Williams et al., 2010). Lightning NOx also play a role in the buildup of O3 over the tropical
406 Atlantic at certain times of year (Moxim and Levy, 2000; Pickering et al., 1996).
407 Seasonality. The seasonal variation of vertical profiles of O3 in the tropics is lower
408 throughout the column compared to the extra-tropics (Fig. 12), in part due to less stratospheric
409 influence at the highest tropical altitudes. The remoteness of the tropical Pacific flight paths from
410 continental pollution sources also drives the lower seasonal variability here compared to the
411 tropical Atlantic, where BB influence peaks in June–August and October–November,
412 characterized by high O3 (> 75 ppbv) and high CO (>100 ppbv) (Fig. 13f), significantly increases
413 the O3 vertical distribution compared to the other seasons (Figs. 12c, 12h, and 12m). Finally,
414 photochemistry, which regulates O3 net balance in the troposphere, is less seasonally variable in
415 the tropics than in the extra-tropics, where the photolysis frequency of O3 (j(O3)) and
416 photochemical production of O3 fluctuate annually with solar zenith angle.
417 O3 minima and maxima. Coincident O3 and CO enhancements were observed in the
418 tropical Atlantic for each ATom circuit (Figs. 9 and 13f), suggesting a year-round influence of
419 continental emissions and distinctive dynamics in this region (Krishnamurti et al., 1996;
420 Thompson et al., 1996). In the tropical Pacific, the April–May period stands out due to an O3 and
421 CO enhancement episode during HIPPO (Fig. 9) that was attributed to the transport of
422 anthropogenic and BB emissions from southeast Asia (Shen et al., 2014).
423 Deep convection in the tropics brings O3-poor (<15 ppbv) air to the upper troposphere (Kley et
424 al., 1996; Pan et al., 2015; Solomon et al., 2005). However, the spatial extent of these events
425 remains poorly constrained. Results from ATom and HIPPO suggest that deep convection can
426 loft O3-poor air at least up to 12 km (the altitude ceiling of this study) in the tropical Pacific, and
427 occurred more frequently between January and May (Figs. 12c and h). During the rest of the
428 year, O3-poor air was typically confined below 4 km. Conversely, O3-poor air is confined to the
429 first 2 km in the tropical Atlantic (Fig. S5). Meteorological analysis of tropical ozonesondes
430 shows that subsidence of higher-O3 air aloft over the Atlantic is one reason O3-poor air is found
431 only in the boundary layer (Thompson et al., 2000, 2012).
432
433 4.2. Middle- and high-latitudes
434 Vertical distribution. In the middle- and high-latitudes, tropospheric O3 was generally at
435 a minimum in the MBL and increased with altitude. Above 8 km, increasing O3 with altitude

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436 (Figs. 10b–e) and its persistent anticorrelation with CO (Fig. 13) points to stratospheric air
437 sampling as the cause for higher O3 variability in the extra-tropical UTLS, especially at high
438 latitudes where the tropopause is lower and wave breaking of the polar jet streams can lead to
439 stratospheric intrusions. As a result, the Sscore decrease above 8 km, summarized in Figure 11a, is
440 ascribed to variability in the influence of stratospheric air. ATom detected little change in the O3
441 distribution over the Pacific Ocean since HIPPO, with a Sscore averaging 74 % in the 0–8 km
442 range. The relative difference between median O3 values from HIPPO and ATom in the Pacific
443 is generally lower than 20 % (Fig. 11b). Similarly, the relative difference between median O3
444 mixing ratios between ATom Atlantic and Pacific below 8 km is consistently lower than 20 %,
445 with an average Sscore of 75 % between (Fig. 11b). The southern high-latitudes are the only
446 region where the Sscore below 8 km occasionally fell below 60 % (Fig. 10e). However, a lower
447 Sscore was expected there as the Atlantic vertical profile is based on only two seasonal flights to
448 Antarctica, whereas there were four seasonal flights in the Pacific. Additionally, HIPPO was less
449 spatially extensive – resulting in fewer data points – in this latitude bin compared to ATom (Fig.
450 1), which could explain the low Sscore values when comparing the two missions (Fig. 10e).
451 Nevertheless, the similar O3 distribution in the extra-tropical free troposphere above the two
452 oceans is consistent with an O3 lifetime sufficiently long for rapid zonal transport to smooth out
453 variations in baseline O3 distribution in the remote troposphere, across a relatively wide range of
454 longitudes (Figs. 10b–e). The comparison of O3 seasonal cycles at remote ozonesonde launching
455 sites of the northern midlatitudes yields similar results and further supports this conclusion
456 (Parrish et al., in review). Studies of the spatial representativeness of tropospheric O3 monitoring
457 networks have concluded that tropospheric O3 distributions varied significantly with longitude,
458 especially in the northern middle- and high-latitudes over continents (Liu et al., 2013; Tilmes et
459 al., 2012). ATom findings stem from O3 measurements predominantly over the oceans, possibly
460 yielding a different picture of O3 longitudinal distribution away from regional precursor
461 emissions.
462 Seasonality. The extra-tropical vertical profiles of O3 vary seasonally during ATom and
463 HIPPO. The summer season in the middle- and high-latitudes was remarkable over both oceans
464 and hemispheres for the steep O3 gradients in the tropospheric column (Fig. 12 in black). In the
465 MBL, median O3 was consistently under 25 ppbv in the summer, whereas O3 was over 25 ppbv
466 in other seasons. Low O3 in the MBL in summer reflects the enhanced O3 photochemical

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467 destruction in this NOx-limited region. Photochemical destruction decreases in dry air in the
468 upper troposphere, thus leading to the steep O3 gradients observed here. The summer O3
469 minimum was especially apparent in the high latitudes of the southern Pacific during ATom and
470 extended well above the MBL into the free troposphere (Fig. 12 in black).
471 O3 mixing ratios were highest in the tropospheric column during springtime in both
472 hemispheres, and over both oceans (Fig. 12 in gold). A notable exception occurred during
473 springtime in the high latitudes of the NH, where several O3 depletion events were sampled in
474 the lower legs of the Arctic transit. During these events, O3 mixing ratios lower than 10 ppbv
475 were measured, resulting in a lower 25th percentile of O3 distribution at the lowest altitude
476 compared to the other seasons (Fig. 12e in gold). A tropospheric O3 springtime maximum has
477 often been reported in the NH (e.g., Monks, 2000) when meteorology favors efficient transport
478 of O3 and precursors from continental air from North America and Eurasia (Owen et al., 2006;
479 Zhang et al., 2017, 2008). Another contributing factor is the increased frequency of stratospheric
480 air mixing in spring that significantly contributes to higher O3 levels (Lin et al., 2015; Tarasick et
481 al., 2019b). Further, the tropospheric O3 springtime maximum in the SH is often attributed to BB
482 emissions reaching a peak ((Fishman et al., 1991; Gaudel et al., 2018), but stratospheric air
483 mixing also occurs (Diab et al., 1996, 2004; Greenslade et al., 2017). Here, the O3/CO
484 relationship in spring shows that the enhanced stratospheric mixing with tropospheric air during
485 this season, both in the northern and southern middle- and high-latitudes, contributes to the
486 increase in column O3 (Fig. 13).
487 Fall and winter seasons shared similar features in the middle- and high-latitudes: no
488 strong O3 gradient was measured in the free troposphere, and O3 values varied over similar
489 ranges – about 40 ppbv in the NH and about 30 ppbv in the SH – during the two seasons (Fig. 12
490 in red and blue).
491 O3 enhancements. The linear increase of O3 with CO >100 ppbv highlights the
492 contribution of natural and anthropogenic pollution plumes lofted from continental areas into the
493 remote troposphere.
494 In the NH, these events occur almost year-round (Figs. 13b–c and 13g–h). Higher CO
495 enhancements in the Pacific (Figs. 13g–h) than in the Atlantic (Figs. 13b–c) have been observed
496 before and attributed to sampling bias (Clark et al., 2015). Here, our findings suggest a year-
497 round influence of continental emissions on the Pacific atmosphere despite its remoteness.

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498 Modeled back trajectories show that most air masses sampled in the NH during ATom were
499 influenced by long-range transport of continental emissions from Asia, Africa, and North
500 America (Fig. S6). Previous studies have shown anthropogenic and BB emission outflow from
501 Asia significantly contributed to O3 pollution events measured over the northern Pacific or in
502 California (e.g., Heald et al., 2003; Jaffe et al., 2004; Lin et al., 2017). Intercontinental transport
503 of anthropogenic emissions from Europe can also contribute to the Asian outflow of
504 anthropogenic pollution (e.g., Bey et al., 2001; Liu et al., 2002; Newell and Evans, 2000).
505 Finally, O3 enhancements in the northern Atlantic were frequently observed and attributed to
506 midlatitude anthropogenic and boreal forest fire emissions (e.g., Honrath et al., 2004; Martín et
507 al., 2006; Trickl et al., 2003).
508 In the SH, polluted air is encountered more often in spring and summer over the Atlantic,
509 but springtime CO is greater than in other seasons over the Pacific (Figs. 13d–e and 13i–j).
510 During spring, median O3 above 50 ppbv was measured throughout the free troposphere in the
511 southern midlatitudes (Fig. 12). Several air masses intercepted during these flights originated
512 from regions that were intensively burning at the time, notably equatorial and southern Africa,
513 Australia, and southern South America, contributing to the observed enhanced O3 and CO (Fig.
514 S4).
515
516 5. Conclusion
517 We present tropospheric O3 distributions measured over remote regions of the Pacific and
518 Atlantic Oceans during two airborne chemical sampling projects: the four deployments of ATom
519 (2016–2018) and the five deployments of HIPPO (2009–2011). The data highlight several
520 regional- and large-scale features of O3 distributions, and provide valuable new insight into O3
521 distributions in remote regions. The main findings are as follows:
522 - ATom and HIPPO provide a unique perspective on vertically-resolved global baseline O3
523 distributions over the Pacific and Atlantic basins, and expand upon spatially-limited O3
524 climatologies from long-term datasets to highlight large-scale features necessary for
525 model output and satellite retrieval validation.
526 - ATom and HIPPO O3 data are consistent – where they overlap – with measurement-
527 based climatologies of tropospheric O3 from well-established ozonesonde and
528 commercial aircraft monitoring programs. ATom and HIPPO seasonal median O3 showed

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529 high correlation (R2 > 0.7) with corresponding seasonal median O3 from ozonesondes,
530 giving confidence in the accurate depiction of the emerging global O3 climatology by
531 these diverse research activities.
532 ATom and HIPPO captured 30–71 % of O3 variability measured by ozonesondes
533 launched in the vicinity of the aircraft flight tracks, and had the same mode of the O3
534 distribution as determined by IAGOS in the northern Atlantic UTLS.
535 - Higher O3 loading in the NH compared to the SH is consistent with the heterogeneous
536 distribution of O3 precursor emissions around the globe, mostly concentrated in the NH.
537 ATom Atlantic vs. Pacific comparison reveals a similar O3 distribution in the free
538 troposphere up to ~8 km in the middle- and high-latitudes, but not in the tropics. In the
539 tropics, median O3 mixing ratios are about twice as high in the Atlantic than in the
540 Pacific, due to a well-documented mixture of dynamical patterns interacting with the
541 transport of continental air masses.
542 - The comparison of seasonal O3 vertical profiles does not reveal a marked seasonality in
543 the tropics, but instead highlights the influence of specific events, most notably BB
544 emissions from Africa and South America. In the extra-tropics, the summer season is
545 characterized by a steeper tropospheric O3 gradient driven by very low O3 abundance in
546 the MBL. Fall and winter seasons generally lead to near-constant O3 mixing ratios from
547 the surface to the upper troposphere, while the highest O3 abundance is recorded during
548 the spring season when more frequent and intense stratospheric intrusions and transport
549 of air masses from continental regions occur.
550 - Overall, this paper highlights the value of the ATom and HIPPO datasets, which cover
551 spatial scales commensurate with the grid resolution of current Earth system models, and
552 further useful as a priori estimates for improved retrievals of tropospheric O3 from
553 satellite remote sensing platforms. ATom and HIPPO datasets should be critical for
554 improving the scientific community’s understanding of O3 production and loss processes,
555 and the influence of anthropogenic emissions on baseline O3 in remote regions. They
556 provide a timely addition to the Tropospheric Ozone Assessment Report (TOAR) effort
557 to characterize the global-scale O3 distribution, and addresses some of the measurement
558 gaps identified therein.
559

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560 Acknowledgments
561 We thank the ATom leadership team, science team, and DC-8 pilots and crew for contributions
562 to the ATom measurements. The authors acknowledge support by the U.S. NASA’s Earth
563 System Science Pathfinder Program under award NNH15AB12I, NNX15AJ23G and
564 NNX15AH33A, and by the U.S. National Oceanic and Atmospheric Administration (NOAA)
565 Health of the Atmosphere and Atmospheric Chemistry, Carbon Cycle, and Climate Programs.
566 SHADOZ ozonesondes are supported by the Upper Atmosphere Research Program of NASA.
567 Ozonesoundings at Marambio have been supported by the Finnish Antarctic research program
568 (FINNARP). We thank J. A. Neuman, H. Angot, and O. Cooper for helpful discussions and
569 careful editing of this manuscript. The IAGOS program acknowledges the European
570 Commission for its support of the MOZAIC project (1994-2003) the preparatory phase of
571 IAGOS (2005-2013) and IGAS (2013-2016); the partner institutions of the IAGOS Research
572 Infrastructure (FZJ, DLR, MPI, KIT in Germany, CNRS, Météo-France, Université Paul Sabatier
573 in France, and University of Manchester, UK); the French Atmospheric Data Center AERIS for
574 hosting the database; and the participating airlines (Lufthansa, Air France, China Airlines, Iberia,
575 Cathay Pacific, Hawaiian Airlines) for transporting the instrumentation free of charge.
576
577
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952

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Figure 1 The location and flight tracks of all O3 monitoring platforms used in this work are
illustrated with different markers and colors. The ATom flight track is in black, the HIPPO flight
track is in blue, IAGOS flight paths are in green, and the ozonesonde launching sites are indicated
by the red markers. The dotted grey lines define the latitudinal bands over which individual ATom
and HIPPO profiles were averaged to derive a regional O3 distribution: the tropics (20° S – 20°
N), the midlatitudes (55° S – 20° S; 20° N – 60° N), and the high-latitudes (90° S – 55° S; 60° N
– 90° N). Only data from remote oceanic flight segments of ATom and HIPPO missions were used
in this work.

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Figure 2 Comparison of ATom (black squares) and HIPPO (blue diamonds) monthly median O3
with ozonesonde (red circles) records from the four tropical sites. Markers indicate the median and
the bars indicate the 25th and 75th percentiles. The three rows, from bottom to top, correspond to
the boundary layer (0–2 km), the free troposphere (2–8 km), and the UTLS (8–12 km). The pink
dots show every O3 data point measured by ozonesondes for the timeframes indicated in Table S2.

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Figure 3 Same as in Figure 2 but for ozonesonde launching sites located in the middle- and high-
latitudes. O3 data obtained from the IAGOS program (green triangles) during descents into San
Francisco Bay-area airports were also added to the Trinidad Head site for comparison.

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Figure 4 ATom (black circles) and HIPPO (blue diamonds) combined monthly median O3 vs.
monthly median O3 from ozonesondes at the nine sites considered in this study. The three panels

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indicate the correlations for a) the UTLS (8–12 km), b) the free troposphere (2–8 km), and c) the
boundary layer (0–2 km). The orthogonal regression fits are two-sided but not weighted.

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Figure 5 Seasonal comparison of 1 km-vertically-binned ATom (colored squares) and HIPPO

(blue diamonds) median O3 with ozonesonde (red circles) records at four sites in the tropics (Suva
in Fiji, Pago-Pago in American Samoa, Hilo in Hawaii, and Ascension Island). Markers indicate
the median and the bars are the 25th and 75th percentiles. The Sscore is a metric of how well ATom

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and HIPPO 1 km-binned O3 probability distribution functions (PDFs) overlap with the
corresponding 1 km-binned O3 PDFs from ozonesondes. The Sscore shown with squares compares
ATom with ozonesondes, and the Sscore shown with blue diamonds compares HIPPO with
ozonesondes. The pink dots show every O3 data point measured by ozonesondes for the timeframes
indicated in Table S2.

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Figure 6 Same as in Figure 5 but for ozonesonde launching sites located in middle- and high-
latitudes (Lauder in New Zealand, Trinidad Head in the USA, Eureka in Canada, Ushuaia in
Argentina, and Marambio in Antarctica). O3 data obtained from the IAGOS program (green
triangles) during descents into San Francisco Bay-area nearby airports were also added to the
Trinidad Head site for comparison.

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Figure 7 Seasonal comparison of 1 km-binned ATom (colored squares) median O3 with IAGOS
(green triangles) in the northern Atlantic UTLS. Markers indicate the median and the bars are the
25th and 75th percentiles. The three different rows indicate the latitudinal bands. The four columns

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indicate the seasons. The green dots show every O3 data point measured by IAGOS flights for the
timeframe indicated in Table S1.

Figure 8 IAGOS and ATom seasonal O3 vs. CO scatterplots, with insets showing the most
frequent O3 values measured during IAGOS and ATom. ATom seasonal deployments are

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colored according to the legend. The frequency gradient of O3 counts is illustrated by the color
scales (green for IAGOS, magenta for ATom). ATom measurements have been combined for the
frequency gradients shown in the insets. The probability of high frequency refers to the
probability of finding frequently measured O3 values within the contour boundaries

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Figure 9 Global-scale distribution of tropospheric O3 for each ATom and HIPPO seasonal
deployment. The rows separate the seasonal deployments, while the columns indicate the mission
and the ocean basin. The O3 color-scale ranges from 20 to 120 ppbv, and all values outside of this

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range are shown with the same extremum color (red for values > 120 ppbv, blue for values < 20
ppbv). HIPPO deployments in June and August were combined together.

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Figure 10 Vertically-resolved O3 distributions from 0–12 km are plotted for the Atlantic (ATom
in green) and for the Pacific (ATom in pink, HIPPO in blue). The five broad latitude regions
correspond to the data parsing illustrated by Fig. 1. Markers indicate median O3, and bars are the

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25th and 75th percentiles, per 1 km altitude bin. Note the log scale on the x-axis. Sscore values
resulting from the comparison of HIPPO and ATom Pacific distributions are shown with blue
diamonds, and from the comparison of ATom Atlantic and Pacific distributions with pink squares.

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Figure 11 All Sscore values from Fig. 10 are shown in panel a) and plotted against altitude. The
HIPPO and ATom comparison in the Pacific basin is shown with blue diamonds, and a comparison
of the Atlantic and Pacific basins during ATom is shown with filled pink squares for the extra-

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tropics and open pink squares for the tropics. The relative difference of median O3 from 0 to 8 km
given in Fig. 10 is shown in panel b), with the same color and marker code as in panel a). The
dotted grey lines indicate a relative difference of 20 %.

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Figure 12 Seasonal variability of regional O3 distribution in the Pacific (HIPPO in the first and
ATom in the second row) and in the Atlantic (ATom in the third row). The colors designate the

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local seasons with red as winter, gold as spring, black as summer, and blue as fall (corresponding
months are indicated for the tropics, with lighter colors). The markers and associated bars
correspond to the median, 25th and 75th percentiles, respectively, of O3 distribution in every 1 km
altitude bin. Note the logarithmic scale on the x-axes in all panels, and the changing scale with
latitudinal bin.

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Figure 13 O3 vs. CO plots using combined ATom and HIPPO data. Each panel denotes a
different latitudinal band in each basin. Seasonal deployments are colored according to the
legend. Note the logarithmic scale on the y-axes in all panels, and the changing scale with
latitudinal bin

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