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Global tropospheric halogen (Cl, Br, I) chemistry and its impact on

oxidants
Xuan Wang1, Daniel J. Jacob2, William Downs2, Shuting Zhai3, Lei Zhu4, Viral Shah2, Christopher D.
Holmes5, Tomás Sherwen6,7, Becky Alexander3, Mathew J. Evans6,7, Sebastian D. Eastham8, J. Andrew
5 Neuman9,10, Patrick Veres9,10, Theodore K Koenig10,11, Rainer Volkamer10,11, L. Gregory Huey12, Thomas J.
Bannan13, Carl J. Percival13,a, Ben H. Lee3, and Joel A. Thornton3
1
School of Energy and Environment, City University of Hong Kong, Hong Kong SAR, China
2
School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts, USA
3
Department of Atmospheric Sciences, University of Washington, Seattle, USA
4
10 School of Environmental Science and Engineering, Southern University of Science and Technology, Shenzhen, China
5
Department of Earth, Ocean, and Atmospheric Science, Florida State University, Tallahassee, Florida, USA
6
Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, York, UK
7
National Centre for Atmospheric Science, University of York, York, UK
8
Laboratory for Aviation and the Environment, Massachusetts Institute of Technology, Cambridge, Massachusetts, USA
9
15 NOAA Chemical Sciences Laboratory (CSL), Boulder, Colorado, USA
10
Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado, USA
11
Department of Chemistry, University of Colorado, Boulder, CO, USA
12
School of Earth and Atmospheric Science, Georgia Institute of Technology, Atlanta, Georgia, USA
13
School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Manchester, UK
a
20 Now at: Jet Propulsion Laboratory, California Institute of Technology, Pasadena, California, USA
Correspondence to: Xuan Wang ([email protected])

Abstract. We present an updated mechanism for tropospheric halogen (Cl + Br + I) chemistry in the GEOS-Chem global
atmospheric chemical transport model and apply it to investigate halogen radical cycling and implications for tropospheric
oxidants. Improved representation of HOBr heterogeneous chemistry and its pH dependence in our simulation leads to less
25 effective recycling and mobilization of bromine radicals, and enables the model to include mechanistic sea salt aerosol
debromination without generating excessive BrO. The resulting global mean tropospheric BrO mixing ratio is 0.19 ppt, lower than
previous versions of GEOS-Chem. Model BrO shows variable consistency and biases in comparison to surface and aircraft
observations in marine air, which are often near or below the detection limit. The model underestimates the daytime measurements
of Cl2 and BrCl from the ATom aircraft campaign over the Pacific and Atlantic, which if correct would imply a very large missing
30 primary source of chlorine radicals. Model IO is highest in the marine boundary layer and uniform in the free troposphere, with a
global mean tropospheric mixing ratio of 0.08 ppt, and shows consistency with surface and aircraft observations. The modeled
global mean tropospheric concentration of Cl atoms is 630 cm-3, contributing 0.8% of the global oxidation of methane, 14% of
ethane, 8% of propane, and 7% of higher alkanes. Halogen chemistry decreases the global tropospheric burden of ozone by 11%,
NOx by 6%, and OH by 4%. Most of the ozone decrease is driven by iodine-catalyzed loss. The resulting GEOS-Chem ozone
35 simulation is unbiased in the Southern Hemisphere but too low in the Northern Hemisphere.

1 Introduction

Halogen radicals (chlorine, bromine, iodine) have a broad range of implications for tropospheric oxidant chemistry. They originate
from sea salt aerosols (SSA), emitted halogen gases, and transport from the stratosphere, and cycle rapidly with inorganic non-
radical reservoirs (Platt and Hönninger, 2003; Finlayson-Pitts, 2003; Saiz-Lopez and von Glasow, 2012; Simpson et al., 2015;
40 Wang et al., 2019). Cl, Br, and I atoms provide sinks for volatile organic compounds (VOCs), dimethylsulfide (DMS), and mercury

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(Atkinson, 1997; Saiz-Lopez and von Glasow, 2012; Horowitz et al., 2017). Cycling between halogen radicals and their reservoirs
converts NOx to HNO3 and causes catalytic loss of ozone (von Glasow et al., 2004; Yang et al., 2005; Sherwen et al., 2016b).
Reaction of Clˉ with N2O5 in polluted environments at night produces ClNO2 that photolyzes in the daytime to return Cl atoms and
NO2, stimulating ozone production (Osthoff et al., 2008; Roberts et al., 2008). Acid displacement of Clˉ by HNO3 is a source of
45 NO3ˉ aerosol. Reviews by Saiz-Lopez and von Glasow (2012) and Simpson et al. (2015) describe this fundamental knowledge of
tropospheric halogen chemistry in more detail.

A number of global modelling studies have explored the importance of halogen chemistry in the troposphere (von Glasow et al.,
2004; Saiz-Lopez et al., 2006; Ordóñez et al., 2012; Long et al., 2014), but there remain large uncertainties in sources and chemical
50 mechanisms. Here we present a new mechanistic description of halogen tropospheric chemistry in the GEOS-Chem global model
that synthesizes previous GEOS-Chem developments (Parrella et al., 2012; Eastham et al., 2014; Schmidt et al., 2016; Sherwen et
al., 2016a;b; Sherwen et al., 2017; Chen et al., 2017; Wang et al., 2019; Zhu et al., 2019) and includes a number of updates. We
use the updated model to interpret recent observations of tropospheric halogens, describe halogen radical cycling, and quantify the
impacts on tropospheric oxidant chemistry. Shah et al. (2021) examines the impact of our simulated Br and Cl atom concentrations
55 in a new redox mechanism for atmospheric mercury.

2 Tropospheric halogen chemistry in GEOS-Chem

We describe here our updated representation of tropospheric halogen chemistry in version 12.9 of GEOS-Chem (http://www.geos-
chem.org), implemented as part of the general model mechanism for coupled ozone–NOx–VOCs–aerosol–halogen tropospheric
and stratospheric chemistry. Extensive referencing will be made to Sherwen et al. (2016b), who implemented the previous
60 representation of tropospheric halogen chemistry in GEOS-Chem (version 11-02), and to Wang et al. (2019), who described an
earlier version of the mechanism implemented here. GEOS-Chem stratospheric halogen chemistry is as described by Eastham et
al. (2014) and we will not discuss it further here.

2.1 Sources of tropospheric halogens

Table 1 lists the global sources and sinks of tropospheric gas-phase inorganic chlorine (Cly), bromine (Bry), and Iodine (Iy) in
65 GEOS-Chem. SSA emissions are from Jaegléet al. (2011). Open fire emissions of HCl are obtained by applying the emission
factors from Andreae (2019) for different vegetation types to the GFED4 (Global Fire Emissions Database version 4) biomass
burned inventory (van der Werf et al., 2017). The resulting global source of 0.5 Tg Cl a -1 is much smaller than in Wang et al.
(2019), who used older emission factors from Lobert et al. (1999). Fuel combustion, waste incineration, and dust are additional
sources of HCl and Clˉ but the emissions are highly uncertain and likely negligible from a global budget perspective (Wang et al.,
70 2019). We do not include them here. Organohalogen gases can produce halogen radicals by oxidation and photolysis. Emissions
of long-lived organohalogen gases (CH2Cl, CH2Cl2, CHCl3, CHBr3) are implicitly treated in the model by specifying latitudinally
and monthly surface air boundary conditions from CMIP6 (Historical greenhouse gas concentrations for climate modelling)
(Meinshausen et al., 2017). Emissions of short-lived bromocarbons (CH3Br, CH2Br2) and iodocarbons (CH3I, CH2I2, CH2ICl,
CH2IBr) are from Bell et al. (2002), Liang et al. (2010), and Ordóñez et al. (2012).
75

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The main global source of tropospheric Cly is mobilization of Clˉ from SSA. A total of 50 Tg Clˉ a-1 (2.4% of SSA emissions) is
mobilized to Cly in the model by acid displacement and other heterogeneous reactions. This number is smaller than our previous
estimate in Wang et al. (2019) (64 Tg Clˉ a-1), mainly due to slower ClNO2 generation from the N2O5 + Clˉ reaction (Section 2.3
and Text S1)). Organochlorines provide a tropospheric source of 3.3 Tg Clˉ a-1 as Cl atoms from photolysis and oxidation. Transport
80 from stratosphere adds 0.14 Tg Cl a-1 to tropospheric Cly. The source of Iy is estimated to be 2.7 Tg I a-1, mostly from the inorganic
iodine (HOI, I2) formed from the ocean surface reaction of O3 with iodide (I−), based on Carpenter et al. (2013) and MacDonald et
al. (2014), and as described by Sherwen et al. (2016b).

In GEOS-Chem versions before 12.9, SSA debromination was not included despite being known to be an important source for Bry
85 (Sander et al., 2003). This is because SSA debromination generated excessive BrO concentrations in comparison to observations,
which then drove excessive ozone depletion (Schmidt et al., 2016;Zhu et al., 2019). Revision of HOBr reactive uptake as source
of bromine radicals effectively corrects this problem (Section 2.2), allowing us to include mechanistically the SSA debromination
source. This provides the main global source of tropospheric Bry (20 Tg Br a-1), mostly through the HOBr/HOCl/HOI + Brˉ
heterogeneous reactions. Bromocarbon gases contribute only 0.54 Gg Br a -1 to Bry but still dominate the Bry source in the free
90 troposphere.

2.2 Chemical mechanism

Our tropospheric halogen chemistry mechanism synthesizes and updates previous GEOS-Chem mechanistic developments.
Chlorine chemistry in GEOS-Chem was first built in Eastham et al. (2014) for the stratosphere and extended to troposphere by
Schmidt et al. (2016), with updates by Sherwen et al. (2016b), Sherwen et al. (2017), Wang et al. (2019), and Wang et al. (2020).
95 Tropospheric bromine chemistry was first built by Parrella et al. (2012) with updates to heterogeneous reactions by Schmidt et al.
(2016), Chen et al. (2017), Wang et al. (2019), and Zhu et al. (2019). Iodine chemistry was built by Sherwen et al. (2016a) and
Sherwen et al. (2016b). Recent general model updates important for halogen chemistry include a new method of simulating cloud
chemistry in partly cloudy grid cells that accounts for limitation by entrainment of air into the cloud (Holmes et al., 2019) and an
improved cloudwater pH calculation that considers carboxylic acids and dust alkalinity (Moch et al., 2020; Shah et al., 2020).
100 Aqueous aerosol thermodynamics including calculation of aerosol pH and HCl/Clˉ partitioning are from ISORROPIA II
(Fountoukis and Nenes, 2007).

We update here the reactive uptake of HOBr by aerosols and cloud droplets (Table 2). This uptake which involves reactions with
Brˉ, Clˉ, and dissolved SO2 (S(IV) ≡ HSO3ˉ + SO32ˉ):

105 HOBr(aq) + Br − + H + → Br2 + H2 O (R1)

− +
HOBr(aq) + Cl + H → BrCl + H2 O (R2)
HOBr(aq) + HSO3− → HBr + HSO4− (R3)
HOBr(aq) + SO2− 2−
3 → HBr + SO4 (R4)

Reactions (R1) and (R2) with subsequent fast photolysis of Br2 and BrCl recycle bromine radicals from HOBr and further mobilize
110 Br- and Cl- to produce new radicals. In GEOS-Chem, the rates are applied to the following stoichiometry:

HOBr(aq) + 𝑌Br − + (1 − 𝑌) Cl− + H + → 𝑌Br2 + (1 − 𝑌)BrCl + H2 O (R5)

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where Y is the yield of Br2 and 1-Y is the yield of BrCl, which are calculated based on the laboratory study of Fickert et al. (1999)
and described in Table 2.

Total reactive uptake of HOBr from reactions (R3)-(R5) in aqueous aerosols and clouds is calculated with a standard first-order
115 reactive uptake coefficient γ (Jacob, 2000), calculated following Ammann et al. (2013):
1 1 −1
γ=( + ) (1)
Γ αb

Γ = 4𝐻𝐻𝑂𝐵𝑟 𝑅𝑇𝐼𝑟 𝑘 𝐼 𝑓(𝑟, 𝐼𝑟 )/𝑐 (2)

𝐼𝑟 = √𝐷𝑙 /𝑘𝐼 (3)
𝐼
𝑘 = 𝑘3𝐼 + 𝑘4𝐼 + 𝑘5𝐼 (4)

120 where HHOBr is the the Henry’s law constant of HOBr, T is temperature, R is the universal gas constant; Dl is the liquid phase
diffusion coefficient for HOBr; f(r, Ir) is the reacto-diffusive correction term, and kI is the first-order total reaction rate constant of
HOBr from pathways (R3-R5) computed as a function of the concentrations of Brˉ, Clˉ, H+, HSO3ˉ, and SO32ˉ. After computing
the overall loss of HOBr, we distribute the loss by pathways on the basis of the relative reaction rates 𝑘𝑖𝐼 . Reactions (R3) and (R4)
are important only in clouds because dissolution of SO 2 depends on the liquid water content.

125 Wang et al. (2019) previously calculated 𝑘5𝐼 based on experimental results over limited and inconsistent pH ranges (pH = 1.9-2.4
for HOBr+Brˉ, pH = 6.4 for HOBr+Clˉ (Beckwith et al., 1996; Liu and Margerum, 2001)). This generated excessive BrO
concentrations in comparison to observations. Here we revise the calculation of 𝑘5𝐼 to consider the entire range of aerosol and cloud
pH, as recommended by Roberts et al. (2014), resulting in much slower rate. We also adopt a new value for 𝑘3𝐼 from a recent
laboratory study (Liu and Abbatt, 2020). Details of these updates are in Table 2. The overall result is to have less efficient
130 heterogeneous recycling and mobilization of bromine radicals in both aerosols and clouds.

Wang et al. (2019) found the heterogeneous reaction of HOCl with Clˉ to be the dominant global tropospheric source of Cl 2 in
GEOS-Chem:

HOCl(aq) + Cl− + H + → Cl2 + H2 O (R6)

Here we add competing reactions between HOCl and S(IV):

135 HOCl(aq) + HSO3− → HCl + HSO4− (R7)

HOCl(aq) + SO2−
3 → HCl + SO2−
4 (R8)

with reaction rate coefficients k7 = 2.8×105 M-1s-1 and k8 = 7.6×108 M-1s-1 from Liu and Abbatt (2020) and Fogelman et al. (1989),
respectively. (R7) and (R8) are relatively slow and have minor overall impact on the Cl y chemistry.

140 Aerosol aqueous-phase reaction of N2O5 with Clˉ produces ClNO2 that photolyzes in the daytime to return Cl atoms and NO2. The
reaction competes with N2O5 hydrolysis, with the following first-order loss representation for N2O5:

𝜑Cl−,(1−φ)H2 O
N2 O5 → φClNO2 + (2 − φ)NO3− + 2(1 − φ)H + (R9)

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McDuffie et al. (2018a;b) evaluated different model expressions for the reactive uptake coefficient γN2O5 and the ClNO2 yield φ ,
and recommended lower values than previously used in GEOS-Chem by Wang et al. (2019) to account for the effect of organic
145 coating of particles. We previously implemented this update in Wang et al. (2020) and it is now part of GEOS-Chem version 12.9.

Additional updates to the GEOS-Chem halogen mechanism in version 12.9 include a new scheme to calculate the reactive uptake
coefficients γ on ice crystals following recommendations by the International Union of Pure and Applied Chemistry (IUPAC)
(Crowley et al., 2010) as listed in Table 3. We calculate the effective radius of ice crystals based on air temperature following
150 Heymsfield et al. (2014) and Holmes et al. (2019), and increase the resulting surface area by a factor of 2.25 to account for irregular
shape (Schmitt and Heymsfield, 2005). We also include the temperature dependence for BrNO 3 hydrolysis in Deiber et al. (2004)
(Text S1), and minor updates for HOI, IONO, and IONO2 heterogeneous reactions (Text S2).

3 Global budget and distribution of tropospheric halogens

Figure 1 shows the global budgets and cycling of tropospheric inorganic chlorine (1a), bromine (1b), and iodine (1c) in our model
155 simulation. Figure 2 shows the annual mean global distributions of Cl atoms, BrO, and IO. Figure 3 shows the global mean vertical
distribution of the halogen speciation for reactive chlorine (Cl* ≡ Cl y – HCl), Bry, and Iy. GEOS-Chem is driven here by 2016
GEOS-FP (forward processing) assimilated meteorological fields from the NASA Global Modeling and Assimilation Office
(GMAO) with native horizontal resolution of 0.25°x 0.3125°and 72 vertical levels from the surface to the mesosphere. Our model
simulation is conducted at 4°x 5°horizontal resolution and meteorological fields are conservatively degraded to that resolution.
160 The model is spun up for 1 year for initialization.

3.1 Chlorine

The dominant global source of Cly is acid displacement from SSA to HCl. The global rate of HCl generation from acid displacement
is 46 Tg Cl a-1 and close to the observationally based estimate of 50 Tg Cl a-1 by Graedel and Keene (1995). HCl is the largest
reservoir of tropospheric Cly, with a global mean tropospheric mixing ratio of 45 ppt. Most of HCl is removed by deposition, and
165 only a small fraction (7.3 Tg Cl a-1) reacts with OH and contributes to reactive chlorine Cl* (≡ Cly – HCl). Cl* can be also generated
from Clˉ in clouds and aerosols by heterogeneous reactions with principal contributions from HOBr+Clˉ (2.6 Tg Cl a-1), HOCl+Clˉ
(1.5 Tg Cl a-1), HOI/IONOx + Clˉ (0.8 Tg Cl a-1), and N2O5+Clˉ (0.68 Tg Cl a-1). This heterogeneous source of 6.3 Tg Cl a -1 is
lower than our previous estimate of 12 Tg Cl a-1 in Wang et al. (2019), since the updated mechanisms for HOBr+Clˉ (Section 2.3)
and N2O5+Clˉ (Section 2.4 and Wang et al. (2020)) reactions are slower. We calculate a tropospheric lifetime of 2.3 hours for Cl*.
170 Loss of Cl* is mainly through the reaction of Cl with methane (44%) and other organic compounds.

Distributions of Cl* in the troposphere are generally similar to Wang et al. (2019). As shown in Figure 2, tropospheric Cl atom
concentrations are highest at the surface, reflecting the source from SSA, and in the upper troposphere due to transport from the
stratosphere as well as cold temperature slowing down the Cl + methane reaction. In surface air, Cl atom concentrations are usually
175 highest along polluted coastlines where the large sources of HNO 3, H2SO4, and N2O5 from anthropogenic emissions drive acid
displacement and ClNO2 production. Figure 3 shows the global zonal mean vertical distribution of Cl* species. Boundary layer
Cl* is dominated on a zonal mean basis by ClNO2 formed from N2O5+Clˉ in polluted air. High mixing ratios of ClNO3 in the upper
troposphere are related to transport from the stratosphere and its slow hydrolysis. The BrCl mixing ratio is much lower than in the

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previous GEOS-Chem studies of Sherwen et al. (2016b) and Zhu et al. (2019) because of slower update kinetics of HOBr in aerosol
180 and cloud water.

3.2 Bromine

The largest source of Bry is from SSA debromination in the marine boundary layer (MBL), mainly contributed by HOBr+Brˉ and
O3+Brˉ producing Br2 and HOBr, respectively. Bromocarbon photochemistry dominates the source of Bry in the free troposphere.
Uptake of HBr by SSA is the major sink of Br y. The global tropospheric loading of BrO in the model is 2.1 Gg Br, corresponding
185 to a mean tropospheric mixing ratio of 0.19 ppt (0.38 ppt in daytime). This value is much lower than the most recent GEOS-Chem
estimate of 8.0 Gg by Zhu et al. (2019), because of the updated HOBr heterogeneous chemistry described in Section 2.3. The newly
added pH-dependences in Table 2 decrease the rate of reaction (R5), resulting in much slower recycling of HOBr in cloud and
aerosol water. HOBr is now more likely to react with S(IV) via reactions (R3) and (R4), forming HBr which then gets taken up by
SSA. In Zhu et al. (2019), 82% of HOBr heterogeneous reactions were with Brˉ and Clˉ, and only 18% were with S(IV). Due to
190 the update in Section 2.3, 59% of HOBr heterogeneous reactions are with Brˉ and Clˉ, and 41% are with S(IV). The higher fraction
of Bry as HBr decreases the tropospheric lifetime of Br y because HBr is more water-soluble than other Bry species. We calculate
tropospheric lifetimes of 7.9 hours for Br y and 6.8 minutes for BrOx (≡ Br+BrO).

Distributions of BrO in Figure 2 are similar to Zhu et al. (2019) except for lower mixing ratios. High surface BrO mixing ratios
195 are usually associated with high SSA emissions. BrO mixing ratios are low over the Southern Ocean despite high SSA emission
because SSA alkalinity is not completely depleted and hence reaction (R5) is ineffective. BrO decreases from the surface to the
middle troposphere, reflecting the SSA source, and then increases in the upper troposphere because of efficient heterogeneous
recycling of HBr in ice clouds (Table 3). Figure 3 shows the global mean vertical distribution of Br y species, which is very different
from Sherwen et al. (2016b) where the Bry concentration increased with altitude. This is due to the inclusion of SSA debromination
200 in our simulation. Our Bry mixing ratio in the MBL is still only slightly higher than that in Sherwen et al. (2016b) because of the
much lower Bry lifetime resulting from the slower HOBr heterogeneous reactions, as mentioned above.

3.3 Iodine

The Iy source totals 2.7 Tg I a-1 with most (2.1 Tg I a-1) originating from ocean volatilization of HOI and I 2 (Carpenter et al.,
2013;MacDonald et al., 2014). The sink of Iy is from deposition (1.8 Tg I a-1) and uptake by aerosols (0.91 Tg I a-1). The global
205 tropospheric loading of IO in the model is 1.4 Gg I, corresponding to a mean tropospheric mixing ratio of 0.08 ppt. As shown in
Figure 2 and 3, concentrations of all I y species are highest in the MBL, consistent with the dominant emission from the ocean.
Surface IO mixing ratios are highest over tropical oceans, where both organic and inorganic iodine emissions are high due to the
high temperature. Concentrations of IO and most Iy species are the lowest in middle troposphere where I y speciation is mostly as
HOI, which can be removed via wet deposition efficiently. IO is higher in the upper troposphere where its cycling is mainly with
210 IONO2 and wet deposition is less efficient. We calculate tropospheric lifetimes of 1.6 days for I y and 1.7 minutes for I+IO* (≡
IO+OIO+2I2O2+2I2O3+2I2O4). Our results are consistent with Sherwen et al. (2016b) since the iodine chemistry is largely
unchanged. Our only significant update has been to conserve mass in iodine heterogeneous reactions (Text S2) but this has little
impact.

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4 Comparison to observations

215 Here we compare the model simulation for 2016 to observations for gas-phase halogen species collected from surface and aircraft
campaigns. The observations are in different years but we assume that interannual variability is small compared to other sources
of error. More extensive evaluations of previous model versions with observations for organohalogens, HCl/Clˉ acid displacement,
and iodine species can be found in Sherwen et al. (2016b), Wang et al. (2019), and Sherwen et al. (2016a) respectively, and our
model results are not significantly different for purpose of these comparisons.

220 4.1 Bromine monoxide (BrO)

Figure 4 compares surface measurements of BrO concentrations in marine air during daytime with corresponding model values.
The model is generally consistent with these observations in showing surface air BrO mixing ratios in the range 0–3 ppt. BrO over
the tropical North Atlantic is higher (1-3 ppt) than other oceans (<1 ppt and below measurement detection limits) in both the model
and observations. This is due in the model to high SSA emissions and efficient acidification of SSA from continental outflow of
225 HNO3 and SO2, resulting in rapid debromination. Figure 5 compares modeled vertical profiles with aircraft BrO observations over
the tropics from the CONTRAST (Chen et al., 2016; Koenig et al., 2017), CAST (Le Breton et al., 2017), TORERO (Volkamer et
al., 2015), and ATom (Wofsy et al., 2018; Veres et al., 2019) aircraft campaigns. Details of the instrument and uncertainty of these
observations are listed in Table 4. The median profiles of BrO measured by CIMS during CONTRAST, CAST, and ATom are all
around or below their detection limits. In contrast, observations during CONTRAST and TORERO measured by DOAS show
230 higher BrO mixing ratios (> 1 ppt). There are two independent BrO measurements during CONTRAST. The DOAS measurement
by Koenig et al. (2017) are portions of five flights during CONTRAST, and show higher values than the CIMS measurement by
Chen et al. (2016). The model provides a reasonable fit to CONTRAST CIMS BrO with mean bias of 0.03 ppt, but is low compared
to the DOAS observations. Observed BrO mixing ratios are low almost everywhere during the ATom campaign and show no
obvious vertical variation from MBL to free troposphere. Modeled BrO is generally consistent with ATom observations in the
235 lower troposphere but is much higher in the upper troposphere where transport from the stratosphere becomes important in the
model. On the other hand, the model is lower than the TORERO observations in the upper troposphere. The higher BrO mixing
ratios in the lowermost stratosphere in the model during ATom and in both model and observations during TORERO are consistent
with balloon-borne measurements at 45oN by Stachnik et al. (2013) showing 5 ppt BrO at 15km altitude, but the lower BrO mixing
ratios in the observations during ATom and in both model and observations during CONTRAST CIMS are consistent with aircraft
240 measurements over the eastern Pacific by Werner et al. (2017) showing < 1 ppt at 12-15km altitudes.

To summarize, there is much ambiguity in the comparisons of model results to observed BrO concentrations, as might be expected
since most observations are near their detection limits and with large uncertainties (Table 4). There is no evidence of systematic
model bias but more sensitive observations would be needed to be conclusive.

245 4.2 Inorganic chlorine gases (Cly)

Figure 6 compares modeled surface HCl mixing ratios to observations at coastal sites and over oceans. The model captures the
spatial variability of the HCl mixing ratios across locations, which largely reflects the strong acid displacement at northern
midlatitudes. As previously shown by Wang et al. (2019), acid displacement is key to reproducing the observations. Figure 7
compares surface modeled maximum ClNO2 to observations at island and coastal environments. Observations of ClNO2 are usually

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250 reported as maxima instead of means, and are made in nighttime urban environments, which are difficult to compare to our global
model because of the coarse grid resolution and nighttime stratification of the surface layer. Despite these drawbacks, the model
still offers a credible simulation of the 24-h maximum ClNO2.

The WINTER aircraft campaign provided data for multiple Cl y gases including HCl, ClNO2, HOCl, and Cl2. The measurements
255 were made over the eastern US and offshore during February–March 2015 by I-TOF-CIMS (Lee et al., 2018), as summarized in
Table 4. Figure 8 compares the observed median vertical profiles of HCl, ClNO 2, HOCl, and Cl2 during WINTER to the model
sampled along the flight tracks for the corresponding period. Modeled HCl is lower than the observations but mostly within the
calibration uncertainty (±30%). Modeled HOCl largely underestimates WINTER observations. Wang et al. (2019) found that such
underestimation is over both land and ocean and mainly in daytime when HOCl has very short lifetime against photolysis (a few
260 minutes). This may suggest a large photochemical source needed to decrease the model bias. Recent work also identified to the
potential for IOx- ion chemistry to lead to measurement interferences (Dörich et al., 2021), of the detection of acid gases which
could impact the measured HOCl:HCl ratio. Furthermore, rapid interconversion of halogen species on inlet walls have been
reported that could also impact the measured HOCl:HCl ratio (Neuman et al., 2010).

265 Figure 9 compares modelled vertical BrCl, Cl2, and ClNO2 mixing ratios to observations during the ATom aircraft campaigns.
Both modeled and observed chlorine gases are low in most regions (< 1ppt). Most ATom measurements were made in daytime,
when modeled BrCl, Cl2, and ClNO2 are close to zero due to their very short lifetimes against photolysis. Modeled BrCl and Cl 2
underestimate observed values especially in lower troposphere. The observed median mixing ratios of all these species at all
altitudes are either below or around the measurement detection limits (Table 4). The underestimates of HOCl during WINTER,
270 and BrCl, Cl2 during ATom at daytime may suggest a large photochemical source that can produce chlorine radicals from Clˉ.

4.2 Iodine monoxide (IO)

Figure 10 compares surface measurements of IO over islands and oceans during daytime with corresponding model values. The
model is generally consistent with these measurements with an overall bias of -10%. Both modeled and observed IO mixing ratios
are highest over tropical oceans and lowest at high latitudes, reflecting the distribution of both organic and inorganic iodine
275 emissions. Figure 11 compares modeled vertical profiles with aircraft IO observations over the eastern Pacific from TORERO
(Volkamer et al., 2015). The model is in general agreement with the observations and able to reproduce the observed vertical
variation with a mean bias of -0.09ppt. Both observed and modeled IO mixing ratios are high in MBL, reflecting the marine sources
of iodine, and vary little in the free troposphere. Recently, Koenig et al. (2020) reported IO and Iy mixing ratios of 0.08 and 0.53
ppt at 12 km during the CONTRAST campaign over western tropical Pacific. Our modeled values are 0.07 and 0.43 ppt for IO and
280 Iy respectively at that location.

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5 Global implications for tropospheric oxidant chemistry

We now examine the implications of tropospheric halogen chemistry as described by our mechanism on the concentrations of
tropospheric VOCs, ozone, NOx, and OH. Shah et al. (2021) examined the implications for mercury chemistry.

5.1 Volatile organic compounds (VOCs)

285 Cl atoms are strong VOC oxidants, but their importance is limited by their small supply. The global mean tropospheric Cl atom
concentration in our model is 630 cm -3, consistent with the upper limit of 1000 cm-3 inferred by Singh et al. (1996) from global
modeling of C2Cl4 observations. Within the MBL, the global mean concentration is 840 cm-3. similar to a recent estimate using
isotopic observations of methane and CO by Gromov et al. (2018) (900 cm-3). Oxidation by Cl atoms in troposphere drives a loss
rate of 3.6 Tg a-1 for methane in our model, contributing 0.8% of the total methane chemical loss. It additionally contributes 14%
290 of the global chemical loss for ethane, 8% for propane, and 7% for higher alkanes. Oxidation of VOCs by Br atoms in GEOS-
Chem is significant only for acetaldehyde, where it accounts for 2.0% of the global loss, and up to 18% of the loss in the MBL of
high-SSA regions (tropical oceans, North Atlantic). Badia et al. (2019) previously estimated a 9% contribution of Br atoms to
acetaldehyde oxidation in the tropospheric column over the eastern tropical Pacific.

5.2 Ozone, NOx, and OH

295 Figure 12 shows the effects of halogen chemistry on tropospheric OH, NO x, and ozone concentrations, as obtained by difference
with a sensitivity simulation excluding all halogen reactions in the troposphere (“no halogen”). Halogen chemistry decreases the
global tropospheric ozone burden by 11% in our model, which is smaller than the 18.6% in Sherwen et al. (2016b). Global ozone
chemical production decreases by 2% while ozone lifetime decreases by 10%. The decrease in ozone production is due to a 5.6%
global decrease in NOx as a result of formation and hydrolysis of halogen nitrates XNO3 (X ≡ Cl, Br, I):

300 𝑋O + NO2 + M → 𝑋NO3 + M (R17)

𝑋NO3 + H2 O → HO𝑋 + HNO3 (R18)

Globally, such NOx loss is mostly through ClNO3 and BrNO3 hydrolysis, with negligible contribution from INO 3. As shown in
Figure 12, surface NOx increases over the continents and this is due to ClNO2 chemistry. We previously showed in Wang et al.
(2019) that Clˉ originating from SSA can be transported far inland by acid displacement of HCl and subsequent HCl uptake by
305 sulfate-nitrate-ammonium (SNA) aerosols. Halogen chemistry in our model lowers global tropospheric concentrations of OH and
HO2 by 4.1% and 3.4% respectively. Decrease in OH is mainly due to the decrease of ozone, which reduces primary OH production
from ozone by 9.8%. The increase in OH over continental regions (Figure 12) is due to ClNO 2 chemistry.

Table 5 summarizes the global annual budget of tropospheric ozone in the standard model and in the no halogen simulation. The
310 budget of ozone is shown as that of odd oxygen (O x ≡ O3 + O + O(1D) + NO2 + 2NO3 + peroxyacylnitrates + HNO3 + HNO4 +
3N2O5 + organic nitrates + Criegee intermediates + XO + HOX + XNO2 + 2XNO3 + 2OIO + 2I2O2 + 3I2O3 + 4I2O4 + 2Cl2O2 +
2OClO where X ≡ Cl, Br, I) to account for the rapid cycling between O x species. The 11% shorter ozone lifetime as a result of
halogen chemistry is due to catalytic ozone loss cycles driven by iodine (7.6%), bromine (2.6%) and chlorine (0.3%). Figure 13
shows the relative contributions of different reaction routes to ozone chemical loss in troposphere. Halogens contribute about 19%

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315 of ozone loss in the MBL, decreasing to 8% at 2-4 km altitude and then increasing to 24% in the upper troposphere. Halogen-
catalyzed ozone loss is mainly driven by the sequence (X ≡ I, Br, Cl):

𝑋 + O3 → 𝑋O + O2 (R19)
𝑋O + HO2 → HO𝑋 + O2 (R20)
HO𝑋 + ℎ𝑣 → 𝑋 + OH (R21)

320 Bates and Jacob (2020) introduced an expanded odd oxygen family, O y≡Ox+Oz, to include both Ox and an additional subfamily,
Oz, consisting of HOx and its reservoirs (Oz ≡ 0.5×(H + OH + organic peroxy radicals + HNO2 + HNO3 + HNO4 +
peroxyacylnitrates + organic nitrates + X + XO + XNO2 + XNO3 + OIO + OClO + ClOO) + H2O2 + organic peroxides + X2 +
HOX + I2O2 +I2O3 + I2O4 + Cl2O2 where X ≡ Cl, Br, I). Table 4 also summarizes the budget of O z. The global tropospheric Oz
burden decreases by 4% due to the halogen chemistry, which is mainly because of the lower production from O x. Following Bates
325 and Jacob (2020), we define the chain length N, or Ox production efficiency per unit Oz, as the number of times a unit of Oz is
converted to Ox before it is removed to terminal sinks:

Rate of conversion from Oz to Ox

𝑁= (6)
(Rate of Oz loss to H2 O)+(Rate of Oz deposition)

In the conventional Ox budget analysis, conversion from Ox to Oz through O(1D) + H2O, is viewed as a sink for Ox; but if N > 1 it
is actually a net source. By considering this, Bates and Jacob (2020) introduced an effective ozone lifetime as:

1
330 𝜏= (7)
𝑘𝑂𝑥 𝑙𝑜𝑠𝑠 𝑡𝑜 𝑂2 +𝑘𝑂𝑥 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 +(1−𝑁)𝑘𝑂𝑥 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑡𝑜 𝑂𝑧

where ki is the pseudofirst‐order loss rate constant for process i. As shown in Table 4, N increases from 1.40 to 1.47 by including
halogen chemistry, thus amplifying ozone production efficiency from O(1D) + H2O. This is because of the decrease of HO2 which
slows down the loss rate of HOx. The effective ozone lifetime decreases by 15%, from 71 to 60 days, because the halogen-driven
catalytic pathways represent true ozone sinks by converting O 3 to O2.
335
Figure 13 compares modeled ozone concentrations with and without halogen chemistry to ozonesonde observations from the World
Ozone and Ultraviolet Data Center (WOUDC, http://www.woudc.org). We only use data from Electrochemical Concentration Cell
(ECC) and do not apply WOUDC-suggested correction factors, following Hu et al. (2017). There are a total of 48 stations in 2016
(supplemental Table S1) and we average the data into six latitudinal bands. Halogen chemistry does not degrade the simulation in
340 the Southern Hemisphere, where the model bias is small, but worsens the underestimate in the Northern Hemisphere. Similar
results are found in Figure 14, which compares modeled surface ozone mixing ratios to observations at surface sites. There is no
significant seasonal variation for the impacts of halogen chemistry on surface ozone at these sites. The last extensive evaluation of
the global tropospheric ozone simulation in GEOS-Chem was done by Hu et al. (2017) and found no significant bias, but it used
v10.1 of the model and there have been many changes to the model since then. In particular, the introduction of NO y reactive
345 uptake by clouds in version 12.6 (Holmes et al., 2019) drove a 7% decrease in global tropospheric ozone. Correcting this
underestimate should be a topic of further research.

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6 Conclusions

We presented a new comprehensive representation of tropospheric halogen chemistry in the GEOS-Chem model that synthesizes
and updates previous model developments. We used it to analyze the sources and cycling of halogen radicals, evaluate against
350 observations of halogen radicals and their reservoirs, and examine the implications for tropospheric oxidant chemistry.

The model includes an improved representation of heterogeneous chemistry in aerosols and clouds, including in particular the
reactions of HOBr, leading to less effective recycling and mobilization of bromine radicals. This allows us to include in the model
the known source of bromine radicals from debromination of sea salt aerosols (SSA) without generating excessive BrO
355 concentrations. Simulation of cloud processing is improved to include a more accurate computation of cloudwater pH (Shah et al.,
2020) and cloud entrainment (Holmes et al., 2019). ClNO2 production by the heterogeneous N2O5 + Clˉ reaction is updated to a
slower rate to account for organic coating of particles (McDuffie et al., 2018a;b).

Cycling of chlorine and iodine radicals is similar to previous versions of GEOS-Chem (Wang et al., 2019; Sherwen et al., 2016)
360 but cycling of bromine radicals is very different. We find a mean tropospheric BrO mixing ratio of 0.19 ppt, much lower than
previous GEOS-Chem estimates and reflecting the less effective heterogeneous recycling of bromine radicals. BrO is highest in
the marine boundary layer (MBL) where SSA debromination is the main source, and in the upper troposphere, due to
photodecomposition of bromocarbons and transport from the stratosphere. Model results are consistent with MBL observations of
BrO from coastal sites and ship cruises, though observations are often below the detection limit. Comparisons to vertical profiles
365 from aircraft campaigns paints an inconsistent picture, with model BrO being lower than the CAST CIMS, CONTRAST DOAS,
and TORERO DOAS measurements over the tropical Pacific, but higher than the ATom CIMS measurements at high altitudes on
Pacific and Atlantic transects. The TORERO and CONTRAST DOAS data show increasing BrO concentrations in the upper
troposphere but the ATom CIMS data do not. The aircraft observations are again below or close to detection limits. A more
confident evaluation of tropospheric bromine radical chemistry will require more sensitive observations of BrO and its reservoirs
370 in the future.

Our simulation shows a global mass-weighted mean Cl atom concentration of 630 molecules cm -3 in the troposphere. Oxidation
by Cl atoms accounts for 0.8% of the global loss of atmospheric methane and has larger effects on the global losses of ethane
(14%), propane (8%), and higher alkanes (7%). Reactive chlorine (Cl* ≡ Cly – HCl) is mainly generated from HCl + OH (7.3 Tg
375 Cl a-1), heterogeneous reactions of Clˉ in clouds (6 Tg Cl a-1) and oxidation of organochlorines (3.3 Tg Cl a -1). Comparisons of
model results to observations in marine surface air and aircraft campaigns in this study and our previous work (Wang et al., 2019)
show that the model is in general consistent with the range and distributions of observed HCl and ClNO2 concentrations. The model
cannot reproduce the high daytime BrCl, and Cl2 concentrations observed during ATom, and matching those values would require
a fast Cl* source. Whether this can be compatible with other ATom observations of VOCs and radicals needs future investigation.
380 Our simulated IO mixing ratios are consistent with marine observations in surface air and from aircraft, showing high values in the
tropical MBL and low uniform values in the free troposphere. Our simulated global mean tropospheric IO concentration is 0.08
ppt.

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Halogen chemistry decreases the global burden of tropospheric ozone in GEOS-Chem by 11%. This reflects a 2% decrease in
385 ozone production due to the sink of NO x from formation and hydrolysis of ClNO3 and BrNO3, and a 11% increase in ozone
chemical loss due to catalytic cycles involving iodine (8%) and bromine (3%). The global mean tropospheric OH concentration
decreases by 4.1%, mostly due to the decrease in ozone. Tropospheric ozone concentrations in GEOS-Chem show no significant
bias in the Southern Hemisphere relative to ozonesonde data, but a low bias in the Northern Hemisphere that is also present in the
absence of halogen chemistry. Addressing this low bias should be a priority for future research.

390 Data availability. The model code is available at GEOS-Chem repository (http://www.geos-chem.org). ATom data are publicly
available through the Oak Ridge National Laboratory DAAC (https://daac.ornl.gov/ATOM/campaign/data.html). Data from the
WINTER, CONTRAST, and TORERO campaigns are publicly available at the EOL data archive (https://data.eol.ucar.edu/). Data
of CAST are publicly available at the CEDA archive (https://catalogue.ceda.ac.uk/uuid/565b6bb5a0535b438ad2fae4c852e1b3).
All links mentioned here were last accessed on 1 April 2021.

395 Author contributions. XW and DJJ designed the study and prepared the paper with input from all co-authors. XW developed the
updated halogen code, performed the simulations, and conducted the analysis. WD merged the halogen code with other updates of
GEOS-Chem in version 12.9. XW, SZ, LZ, VS, CDH, TS, BA, MJE, and SDE contributed to the GEOS-Chem model development.
JAN, PV, TKK, RV, LGH, ML, TJB, CJP, BHL, and JAT conducted and processed the aircraft halogen measurements.

Acknowledgments. This work was supported by the City University of Hong Kong New Research Initiatives (grant no. 9610470)
400 and by National Natural Science Foundation of China (grant no. 42005083). Work at Harvard was supported by the EPA STAR
Program (grant no. 84001401). The authors thank Michael Le Breton for CAST measurements and Kelvin H. Bates for helpful
discussions.

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Table 1. Global sources and sinks of tropospheric gas-phase phase inorganic chlorine (Cly), bromine (Bry), and iodine (Iy)a.

Cly (Tg Cl a-1) Bry (Tg Br a-1) Iy (Tg I a-1)

Total source 54 21 2.7
Sea Salt 50 20 -
Acid displacement b 46 - -
HOX + Xˉ 2.4 12 -
XNO2 + Xˉ 0.05 < 0.01 -
OH/O3 + Xˉ 0.53 8.6 -
XNO3 + Xˉ 0.15 0.11 -
N2O5 + Clˉ 0.68 - -
HOI and I2 ocean emission NA NA 2.1
Organohalogens c 3.3 0.54 0.58
CH3X + OH/hv 2.0 0.05 0.26
CH2X2 +OH/hv 0.88 0.06 0.11
CHX3 + OH/hv 0.30 0.40 -
CH2IX + OH/hv 0.04 0.03 0.21
Stratosphere d 0.14 0.01 < 0.01
Open fires 0.50 - -
Total sink 54 21 2.7
Deposition 54 1.4 1.8
Dry 29 0.70 0.93
Wet 25 0.70 0.84
Net uptake by aerosols NA e 20 0.91
Tropospheric mass (Gg) 231 19 12
Lifetime (hours) 38 7.9 39
675 a Annual
totals for 2016 computed from GEOS-Chem. Dashes indicate negligibly small terms. Gas-phase inorganic chlorine is defined as Cly ≡
Cl + 2×Cl2 + 2×Cl2O2 + ClNO2 + ClNO3 + ClO + ClOO + OClO + BrCl + ICl + HOCl + HCl. Gas-phase inorganic bromine is defined as Bry ≡
Br + 2×Br2 + BrNO2 + BrNO3 + BrO + BrCl + IBr + HOBr + HBr. Gas-phase inorganic iodine is defined as Iy ≡ I + 2×I2 + 2×I2O2 + 2×I2O3 +
2×I2O4 + OIO + INO + INO2 + INO3 + IO + ICl + IBr + HOI + HI. We use X to denote any of Cl, Br, or I.
b Acid displacement, significant only for HCl. The Table gives the net production minus loss of HCl from acid aerosol displacement by HNO
3
680 and H2SO4, minus HCl uptake by sea salt alkalinity.
c CH X and CHX denote unmixed halogens, such as CH Cl or CHBr .CH IX denotes the mixed iodocarbons CH ICl and CH IBr.
2 2 3 2 2 3 2 2 2
d Net stratospheric input to the troposphere.
e For Cl the uptake is included as an offsetting term in the acid displacement source (footnote b).
y

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685 Table 2. First-order reaction rate constants (kI) for HOBr heterogeneous reactions in aerosol and liquid cloud water.

Reaction First-order reaction rate constant (kI) a Reference b

𝑘 𝐼 = 𝑘 𝐼𝐼 [HSO−3] (1)
R3 HOBr + HSO− −
3 → HBr + HSO4
𝑘 𝐼𝐼 =2.6 ×107 M-1s-1
𝑘 𝐼 = 𝑘 𝐼𝐼 [SO2−
3 ] (2)
R4 HOBr + SO2− 2−
3 → HBr + SO4
𝑘 𝐼𝐼 = 5 × 109 M-1s-1
𝑘 𝐼 = 𝑘1𝐼𝐼 [Br − ] + 𝑘2𝐼𝐼 [Cl− ] (3)
[Br − ]
𝑌 = 0.41log10 ( ) + 2.25 for [Br − ]/[Cl− ] < 5 × 10−4
[Cl− ]
𝑌 = 0.90 for [Br − ]/[Cl− ] ≥ 5 × 10−4
1.6 × 108 M−1 s−1 for pH ≤ 2 (4)
HOBr(aq) + 𝑌Br − + (1 − 𝑌)Cl− + H + 𝑘1𝐼𝐼 = { 𝑘ter [H+ ] for 2 > pH < 6
R5
→ 𝑌Br2 + (1 − 𝑌)BrCl + H2 O 1.6 × 104 M−1 s −1 for pH ≥ 6
𝑘ter = 1.6 × 1010 M-2s-1
2.3 × 104 M−1 s−1 for pH ≤ 6 (5)
𝑘2𝐼𝐼 = {𝑘ter [H + ] for pH > 6 and pH < 9
23 M−1 s−1 for pH ≥ 9
𝑘ter = 2.3 × 1010 M-2s-1
d[HOBr]
a Thisfirst-order rate constant describes the first-order HOBr loss rate − = 𝑘 𝐼 [HOBr] which is used in equations (1)-(4) to calculate the
dt
HOBr reactive uptake coefficient γ.
b References: (1) Liu and Abbatt (2020); (2) Troy and Margerum (1991); (3) Fickert et al. (1999); (4) Roberts et al. (2014), k
ter value is from
Beckwith et al. (1996); (5) Roberts et al. (2014), kter value is from Liu and Margerum (2001).
690

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Table 3. Heterogeneous halogen reactions on ice crystals a

Reaction Reactive uptake coefficient (γ)

γ = γgs θ(HCl); γgs = 0.25
𝐾𝐿𝑎𝑛𝑔𝐶,𝐻𝐶𝑙[HCl]g
θ(HCl) = ;
1+𝐾𝐿𝑎𝑛𝑔𝐶,𝐻𝐶𝑙 [HCl]g +𝐾𝐿𝑎𝑛𝑔𝐶,𝐻𝑁𝑂3[HNO3 ]g

𝐾𝐿𝑖𝑛𝐶,𝐻𝐶𝑙 𝐾𝐿𝑖𝑛𝐶,𝐻𝑁𝑂3
R10 HOBr + HCl → BrCl + H2 O 𝐾𝐿𝑎𝑛𝑔𝐶,𝐻𝐶𝑙 = ; 𝐾𝐿𝑎𝑛𝑔𝐶,𝐻𝑁𝑂3 =
𝑁𝑚𝑎𝑥,𝐻𝐶𝑙 𝑁𝑚𝑎𝑥,𝐻𝑁𝑂3

−5 (4600/𝑇)
𝐾𝐿𝑖𝑛𝐶,𝐻𝐶𝑙 = 1.3 × 10 𝑒 ; 𝑁𝑚𝑎𝑥,𝐻𝐶𝑙 = 3 × 1014 molecules cm−2
𝐾𝐿𝑖𝑛𝐶,𝐻𝑁𝑂3 = 7.5 × 10−5 𝑒 (4585/𝑇) ; 𝑁𝑚𝑎𝑥,𝐻𝑁𝑂3 = 2.7 × 1014 molecules cm−2
γ = γgs θ(HBr); γgs = 4.8 × 10−4 𝑒 (1240/𝑇)
R11 HOBr + HBr → Br2 + H2 O
θ(HBr) = 4.14 × 10−10 [HBr]g 0.88

R12 HOCl + HCl → Cl2 + H2 O γ = γgs θ(HCl) ; γgs = 0.22

R13 BrNO3 + H2 O → HOBr + HNO3 γ = 5.3 × 10−4 𝑒 (1100/𝑇)
1 𝑐
γ = 1/( + )
αs 4𝑘𝑠 𝐾𝑙𝑖𝑛𝐶,𝐶𝑙𝑁𝑂3 [H2 O]s
αs = 0.5; 𝑘𝑠 𝐾𝑙𝑖𝑛𝐶,𝐶𝑙𝑁𝑂3 = 5.2 × 10−17 𝑒 (2032/𝑇)
R14 ClNO3 + H2 O → HOCl + HNO3
[H2 O]s = 10−15 − 3𝑁𝑚𝑎𝑥,𝐻𝑁𝑂3 θ(HNO3 )
𝐾𝐿𝑎𝑛𝑔𝐶,𝐻𝑁𝑂3 [HNO3 ]g
θ(HNO3 ) =
1 + 𝐾𝐿𝑎𝑛𝑔𝐶,𝐻𝐶𝑙 [HCl]g + 𝐾𝐿𝑎𝑛𝑔𝐶,𝐻𝑁𝑂3 [HNO3 ]g

R15 ClNO3 + HCl → Cl2 + HNO3 γ = γgs θ(HCl) ; γgs = 0.24

R16 ClNO3 + HBr → BrCl + HNO3 γ = γgs θ(HCl) ; γgs = 0.56

a
Formulations for the reactive uptake coefficient γ are from IUPAC (Cowley et al., 2010). [ ]g denotes gas-phase concentration in unit of
molecules per cm3 of air. γgs is the elementary reaction probability for a gas phase molecule colliding with the ice surface. θ is the fractional
695 coverage of a gas species on the ice surface. KLangC is a partition coefficient in units of cm3 molecule-1. KLinC is a partition coefficient in units of
molecule cm−2/molecule cm−3. T is air temperature in K. Nmax denotes the maximum number of available surface sites for a gas species per cm2
of ice surface. c is the average gas-phase thermal velocity for the reactant. θ, KLangC, KLinC, and Nmax for each species are calculated using the same
method throughout the table. R10 and R11 compete with each other; R14, R15, and R16 compete with each other; these competitions use
branching ratios determined by the relative rates.
700

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Table 4: Summary of aircraft measurements.

Campaign Location Time Instrument Species Detection limit Accuracy Reference f

CIMS a BrO 1.0 ppt c 23% (1)

CONTRAST W. tropical Pacific Jan-Feb 2014
DOAS b BrO 0.5 ppt d 30% (2)

CAST W. tropical Pacific Jan-Feb 2014 CIMS a BrO 0.1 ppt d 15% (3)

BrO 0.5 ppt d 30%

TORERO E. tropical Pacific Jan-Feb 2012 DOAS b (4)

IO 0.05 ppt d 20%

BrO 0.3 ppt e 25% + 0.2 ppt

e
Sep-Oct 2017 (ATom-3) BrCl 0.3 ppt 25% + 0.4 ppt
ATom Pacific and Atlantic CIMS a (5)
Apr-May 2018 (ATom-4) Cl2 0.4 ppt e 15% + 0.4 ppt

ClNO2 0.1 ppt e 15% + 0.05 ppt

HCl 100 ppt e 30%

ClNO2 2 ppt e 30%

WINTER E. US and offshore Feb-Mar 2015 CIMS a (6)
HOCl 2 ppt e 30%

Cl2 1 ppt e 30%

a CIMS: Chemical Ionization Mass Spectrometer

b
DOAS: Differential Optical Absorption Spectroscopy
c for 60 seconds data.

705 d for 30 seconds data.

e for 1 second data.
f References: (1) Chen et al. (2016); (2) Koenig et al. (2017); (3)Le Breton et al. (2017); (4)Dix et al. (2016); (5)Veres et al. (2019); (6) Lee et al.

(2018).

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Table 5: Global tropospheric ozone budget in GEOS-Chema

Version 12.9 b No halogen c

Ox
Sources (Tg a-1)
Chemistry 4359 4450
Stratosphere 554 543
Sinks (Tg a-1)
Chemistry 4077 4078
O(1D) + H2O 1960 2173
O3 + HO2 1020 1188
O3 + OH 468 543
Bromine 105 0
Iodine 310 0
Chlorine 13 0
Others 201 174
Deposition 836 915
Tropospheric burden (Tg) 314 353
Lifetime (days) 23.4 26
Oz
Sources (Tg a-1)
Ox → Oz 2042 2264
Carbonyl photolysis 931 912
Sinks (Tg a-1)
Oz → H2O 2361 2515
Deposition 611 661
Tropospheric burden (Tg) 7.1 7.4
Chain length N d 1.47 1.40
Effective ozone lifetime (days) e 60 71
710 a Annual mean budget for the odd oxygen family (Ox) and for the reservoirs (Oz) of the expanded odd oxygen family (Oy ≡ Ox + Oz). Here, Oz ≈
0.5 HOy accounts for the hydrogen oxide (HOx≡OH + peroxy radicals) and their reservoirs cycling with ozone. See the text in Section 5.2 and
Bates and Jacob (2020) for details. All values are given in ozone equivalent mass. For the halogen crossover reactions where two different
halogens are included (e.g. ClO + BrO), we split the ozone loss equally between the two halogens.
b as implemented in this work.
c version 12.9 with no tropospheric halogen reactions.
715
d O production efficiency per unit O , see equation (6) in the text for definition.
x z
e See equation (7) in the text for definition.

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720

Figure 1a. Global budget and cycling of tropospheric inorganic chlorine (Cly) in GEOS-Chem. Read 1.0(4) as 1.0x104. Reactions
producing Cl atoms are in red. Heterogeneous reactions are in green. The dotted box indicates the Cly family, and arrows into and out
of that box represent general sources and sinks of Cly. Reactions with rate <100 Gg Cl a-1 are not shown. ClO* stands for ClO + OClO +
725 ClO2 + 2Cl2O2; most is present as ClO. The superfast Cl-ClOO cycling is not included as it does not affect the Cl atom concentration.

Figure 1b. Same as Figure 1a but for tropospheric inorganic bromine (Bry).

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730 Figure 1c. Same as Figure 1a but for tropospheric inorganic iodine (Iy). IO* stands for IO + OIO + 2I2O2 + 2I2O3 + 2I2O4.

Figure 2. Global distribution of annual mean GEOS-Chem number densities of Cl atoms and mixing ratios of BrO and IO. Upper panels
show surface air values and lower panels show zonal means as a function of latitude and altitude. Dashed lines indicate the tropopause.

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735
Figure 3. Global annual mean vertical speciation in GEOS-Chem of reactive chlorine (Cl* ≡ Cly – HCl), gaseous inorganic bromine (Bry),
and gaseous inorganic iodine (Iy, right).

740 Figure 4. Daytime surface air mixing ratios of BrO from island sites and ocean cruises, arranged from left to right in order of decreasing
latitude. Observed values (black) are means for the reporting period in different years. Open bars show the measurement detection limit
and indicate that the observation is below detection limit. Model values (red) are monthly mean values in 2016 taken for the same month
and location as the observations. References: (1) Saiz-Lopez et al., 2004; Saiz-Lopez et al., 2006; (2) Keene et al., 2007; (3, 5, 6) Sander
et al., 2003; (4, 11) Leser et al., 2003; Martin et al., 2009; (7) Read et al., 2008; Mahajan et al., 2010; (8, 9) Volkamer et al. (2010); (10)
745 Volkamer et al. (2015).

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Figure 5. Median vertical profiles of BrO mixing ratios from the CONTRAST (Jan-Feb 2014 over western tropical Pacific), CAST (Jan-
Feb 2014 over western tropical Pacific), TORERO (Jan-Feb 2012 over eastern tropical Pacific), ATom-3 (Sep-Oct 2017 over Pacific and
750 Atlantic), and ATom-4 (Apr-May 2018 over Pacific and Atlantic) campaigns. Observations are shown as medians in 1km vertical bins.
Model values are shown as medians sampled along the flight tracks. There are two independent CONTRAST BrO data sets. The black
solid line shows the CIMS data from Chen et al. (2016). The black dashed line shows the DOAS data from Koenig et al. (2017). The red
solid and dashed lines show model values sampled along the flight tracks at the time of the available CIMS and DOAS observations
respectively.
755

Figure 6. Surface air mixing ratios of HCl at coastal and island sites and from ocean cruises, arranged from left to right in order of
decreasing latitude. Observations (black) are means or medians depending on availability from the publications. Model values (red) are
760 monthly mean values in 2016 taken for the same month and location as the observations. References: (1, 5, 8, 9) Keene et al. (2009); (2)
Keene et al. (2007); (3) Crisp et al. (2014); (4) Dasgupta et al. (2007); (6) Sander et al. (2013); (7) Sanhueza and Garaboto (2002).

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765 Figure 7. Surface air mixing ratios of ClNO2 at coastal and island sites, arranged from left to right in order of decreasing latitude.
Observed (black) and modeled (red) values are maxima for the reporting period. Model maxima are based on hourly values sampled at
the same location and time period as the observations. References: (1) Priestley et al. (2018); (2,4,6) Sommariva et al. (2018); (3,5) Bannan
et al. (2017); (7) Phillips et al. (2012); (58) Kercher et al. (2009); (9,10) Jeong et al. (2018); (11) Mielke et al. (2013); (12) Riedel et al.
(2013); (13) Kim et al. (2014) (14) Osthoff et al. (2008) (15) Faxon et al. (2015).

770

Figure 8. Vertical profiles of HCl, HOCl, Cl2, and nighttime ClNO2 mixing ratios during the WINTER campaign over the eastern US
and offshore in February–March 2015. Observations are shown as individual 1 min data points, with medians and 25th–75th percentiles
in 500m vertical bins. ClNO2 data exclude daytime (10:00–16:00 local) when mixing ratios are near zero in both the observations and
775 the model. Model values are shown as medians sampled along the flight tracks.

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Figure 9a. Vertical profiles of BrCl, Cl2, and ClNO2 mixing ratios from the ATom-3 campaign over the Pacific and Atlantic in September-
October 2017. Observations are medians and 25th–75th percentiles in 1km vertical bins. Model values are medians sampled along the
780 flight tracks.

Figure 9b. Same as Figure 9a but for the Atom-4 campaign in April-May 2018.

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785

Figure 10. Daytime surface air mixing ratios of IO from island sites and ocean cruises, arranged from left to right in order of decreasing
latitude. Observed values (black) are means for the reporting period in different years. Model values (red) are monthly mean values in
2016 taken for the same month and location as the observations. References: (1,4,9,12) Mahajan et al. (2012); (2,7,10) Großmann et al.
790 (2013); (3) Mahajan et al. (2010); (5) Volkamer et al. (2015); (6) Prados-Roman et al. (2015); (8) Gómez Martín et al. (2013).

Figure 11. Median vertical profile of IO mixing ratios from the TORERO (Jan-Feb 2012 over the eastern tropical Pacific) campaign.
Observations are shown as individual 1 min data points, with medians and 25th–75th percentiles in 1km vertical bins. Model values are
795 shown as medians sampled along the flight tracks.

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Figure 12. Effects of halogen chemistry on tropospheric OH, NOx, and ozone concentrations. The Figure shows differences in annual
mean concentrations between the standard simulation and a sensitivity simulation removing all tropospheric halogen reactions. The top
800 panels are for surface air and the bottom panels are for zonal means as a function of latitude and latitude. Only tropospheric grid boxes
are shown.

805 Figure 13. Contributions of different pathways to the global annual loss of tropospheric ozone as a function of altitude. The “Other”
pathway includes sinks from reactions with alkenes and HNO3 deposition.

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Figure 14. Annual average vertical profile of ozone mixing ratios from ozonesonde observations and the model for six zonal bands.

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810 Figure 15. Seasonal variation of surface ozone at a range of Global Atmospheric Watch (GAW) sites. Observational data are from the
World Data Centre for Reactive Gases (WDCRG) and are 3-years monthly averages (2015–2017). Modeled values are monthly averages
for 2016.

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