Tagged ozone mechanism for MOZART-4, CAM-chem and other ...

Geosci. Model Dev., 5, 1531–1542, 2012www.geosci-model-dev.net/5/1531/2012/doi:10.5194/gmd-5-1531-2012© Author(s) 2012. CC Attribution 3.0 License.

GeoscientificModel Development

Tagged ozone mechanism for MOZART-4, CAM-chem and otherchemical transport models

L. K. Emmons1, P. G. Hess2, J.-F. Lamarque1, and G. G. Pfister1

1Atmospheric Chemistry Division, National Center for Atmospheric Research, Boulder, CO, USA2Department of Biological and Environmental Engineering, Cornell University, Ithaca, NY, USA

Correspondence to:L. K. Emmons ([email protected])

Received: 5 July 2012 – Published in Geosci. Model Dev. Discuss.: 24 July 2012Revised: 31 October 2012 – Accepted: 2 November 2012 – Published: 6 December 2012

Abstract. A procedure for tagging ozone produced fromNO sources through updates to an existing chemical mecha-nism is described, and results from its implementation in theModel for Ozone and Related chemical Tracers (MOZART-4), a global chemical transport model, are presented. Artifi-cial tracers are added to the mechanism, thus, not affectingthe standard chemistry. The results are linear in the tropo-sphere, i.e., the sum of ozone from individual tagged sourcesequals the ozone from all sources to within 3 % in zonal meanmonthly averages. In addition, the tagged ozone is shownto equal the standard ozone, when all tropospheric sourcesare tagged and stratospheric input is turned off. The strato-spheric ozone contribution to the troposphere determinedfrom the difference between total ozone and ozone from alltagged sources is significantly less than estimates using atraditional stratospheric ozone tracer (8 vs. 20 ppbv at thesurface). The commonly used technique of perturbing NOemissions by 20 % in a region to determine its ozone con-tribution is compared to the tagging technique, showing thatthe tagged ozone is 2–4 times the ozone contribution thatwas deduced from perturbing emissions. The ozone taggingdescribed here is useful for identifying source contributionsbased on NO emissions in a given state of the atmosphere,such as for quantifying the ozone budget.

1 Introduction

The transport of pollution from one region (state, countryor continent) to another has been the goal of a great num-ber of studies due to its importance to local air quality, andconsequently human health and ecosystems (e.g.,Dentener

et al., 2010). Global chemical transport models have beenused in a variety of ways to determine source attributionsat given locations and source-receptor relationships. Pollu-tants such as carbon monoxide (CO), with relatively simplechemistry (i.e., directly emitted, lost through reaction withOH and dry deposition), can be easily “tagged” according toemission source types or regions for attribution studies (e.g.,Granier et al., 1999; Pfister et al., 2004, 2011) or inversemodelling (e.g.,Petron et al., 2004; Arellano et al., 2006).The contribution of isoprene emissions to formaldehyde, car-bon monoxide and other products was determined through atagging technique similar to that presented here for ozone,where duplicate “tagged” species were created for each car-bon compound derived from isoprene (Pfister et al., 2008a).The NOx budget was analysed in the study ofLamarque et al.(1996) by tagging each type of NOx source. For that study,the separate source tracers equaled the total NOx, and thenonlinearities of loss and production rates were taken intoaccount so that the sum of the tagged tracers equalled totalNOx.

Ozone, however, has quite complex chemical productionand loss processes, and is not directly emitted, so identify-ing its source contributions requires slightly different pro-cedures. One method of understanding source contributionsto tropospheric ozone has been to set the emissions of agiven region to zero and compare the results to a standardsimulation with no emission perturbation to determine theinfluence of that region on other regions (e.g.,Fiore et al.,2002; Guerova et al., 2006). Other studies have made a smallchange (5–20 %) in the emissions of a region, and then scaledthe resulting difference from a standard run to estimate thetotal impact of that region. This technique has been used

Published by Copernicus Publications on behalf of the European Geosciences Union.

1532 L. K. Emmons et al.: Tagged ozone mechanism

by the model comparisons performed for the Task Force onHemispheric Transport of Air Pollution (HTAP;http://www.htap.org). Analyses of these simulations have provided es-timates of foreign emissions on local ozone concentrations(e.g.,Fiore et al., 2009; Reidmiller et al., 2009; Wild et al.,2012). Wu et al.(2009) showed that estimates of ozone con-tributions are significantly different when estimated by re-moving all the emissions in a source region, in comparisonto making small perturbations in the emissions, due to thenonlinearity of ozone photochemistry.

A simplified NOx–ozone tagging scheme, suitable forlong chemistry climate simulations, has been presented byGrewe(2004). In that treatment, each NOx source producesa NOy (total reactive nitrogen) tracer in addition to the stan-dard chemical scheme. Each NOy tracer has a correspondingozone tracer that is produced at a fraction of the ozone pro-duction rate corresponding to the fraction of each NOy tracerto total NOy. This methodology was compared to the proce-dure of perturbing emissions as a means of estimating sourcecontributions byGrewe et al.(2010), with a specific applica-tion shown inGrewe et al.(2012). The contributions of NOxsources to ozone radiative forcing trends have also been esti-mated (Dahlmann et al., 2011).

In this paper, we present a technique for quantifyingsource contributions to tropospheric ozone distributions by“tagging” emissions of NO and its resulting products andfollowing them to the production of ozone. This techniqueadds synthetic tracers to the chemical mechanism that do notmodify the original chemistry, but make use of the mixingratios and loss rates of the full, standard chemistry. The tag-ging scheme presented here has been used in several stud-ies (Lamarque et al., 2005; Pfister et al., 2006; Hess andLamarque, 2007; Pfister et al., 2008b; Emmons et al., 2010a;Brown-Steiner and Hess, 2011; Wespes et al., 2012), butnever fully documented. We present here the details of themechanism (in Sect. 2), and illustrate the additive qualitiesof the technique and comparisons to other attribution tech-niques (Sect. 3).

2 Tagged mechanism

The method we use to attribute the ozone concentration pro-duced by a given source type or region is through the “tag-ging” of nitrogen (i.e., NO and NO2) emissions. Essentiallya duplicate set of tracers for all compounds containing N areadded to the mechanism; these new tracers are affected bythe compounds of the full mechanism, but do not influencethem. The tagged NOx is traced through all of the odd nitro-gen species (e.g., PAN, HNO3, organic nitrates) to accountfor the recycling of NOx. The photolysis of tagged NO2 pro-duces tagged O, most of which goes on to produce taggedO3. Tagged O3 is then destroyed at the same rate as the to-tal ozone. While ozone production also requires the pres-ence of peroxy radicals (HO2 and RO2) resulting from the

Table 1. Tagged species in the MOZART-4 tagged ozone mecha-nism.

Symbolic name Atomic composition

XNO NOXNO2 NO2XNO3 NO3XHNO3 HNO3XHO2NO2 HNO4XNO2NO3 N2O5NO2XNO3 N2O5XPAN CH3CO3NO2XONIT CH3COCH2ONO2XMPAN CH2CCH3CO3NO2XISOPNO3 CH2CHCCH3OOCH2ONO2XONITR CH2CCH3CHONO2CH2OHXNH4NO3 NH4NO3OA OO1DA OO3A O3

oxidation of hydrocarbons, we have chosen to trace the ni-trogen species for determining ozone sources.

A procedure for tracing emissions of VOC (volatile or-ganic compounds) to peroxy radicals and then ozone hasbeen demonstrated byButler et al.(2011). It is similar to ourNO-tagging procedure in that it adds additional tracers forthe tagged compounds that do not change the original chem-istry. Since ozone formation requires both NO and peroxyradicals from VOCs, either pathway could be followed forsource attribution, depending on the goal of the study. Sincemost of the atmosphere is NOx-limited, and the focus of thiswork was large scale attribution in a global model, taggingNO is an appropriate choice. When tagging all troposphericcontributions to ozone, tracing nitrogen compounds shouldgive comparable results to tracing VOCs and peroxy radicals.However, if one wants to understand the impact of individ-ual VOCs, or source sectors that might have different VOCspeciation, then theButler et al.(2011) procedure would bevaluable.

Table 1 lists the additional, tagged species needed to de-termine the tagged ozone. The photolysis and kinetic re-actions for the tagged species are listed in Tables 2 and 3along with the corresponding reactions for the non-taggedspecies. The tagged N species are indicated by XN, whilethe tagged Ox species end in A (e.g., O3A). For the taggedreactions, any non-tagged species among the reactants areincluded as products in each reaction, so that their con-centration is not affected by the tagged species. Similarly,the non-tagged products are not included in the tagged re-action. For example, the standard reaction NO+ HO2 pro-duces NO2 + OH. In the tagged reaction, tagged NO goesto tagged NO2 using the current HO2 concentration, but theHO2 is unchanged by the reaction, and no additional OH is

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Table 2.Photolysis reactions of tagged species.

Original reaction Tagged reaction(s)

O3 +hν → O1D + O2 O3A +hν → O1DAO3 +hν → O + O2 O3A +hν → OANO2 +hν → NO + O XNO2 +hν → XNO + OAN2O5 +hν → NO2 + NO3 XNO2NO3 +hν → XNO2

NO2XNO3 +hν → XNO3HNO3 +hν → NO2 + OH XHNO3 +hν → XNO2NO3 +hν → 0.89*NO2 + 0.11*NO + 0.89*O3 XNO3 +hν → 0.89*XNO2 + 0.11*XNO + 0.89*O3AHO2NO2 +hν → 0.33*OH + 0.33*NO3 + 0.66*NO2 + 0.66*HO2 XHO2NO2 +hν → 0.33*XNO3 + 0.66*XNO2PAN + hν → 0.6*CH3CO3 + 0.06*NO2 + 0.4*CH3O2 + 0.4*NO3 XPAN +hν → 0.6*XNO2 + 0.4*XNO3MPAN + hν → MCO3 + NO2 XMPAN +hν → XNO2ONITR + hν → HO2 + CO + NO2 + CH2O XONITR +hν → XNO2

O3 without stratosphere

-100 -50 0 50 100Latitude

1000

100

Pres

sure

[hPa

]

0 5 10 15 20 25 30 35 40 45 ppbv

O3A-O3 difference

-100 -50 0 50 100Latitude

1000

100

Pres

sure

[hPa

]

-5 -4 -3 -2 -1 0 1 2 3 4 5 ppbv

Fig. 1. Simulation test with no stratospheric ozone, for June 2008.Left: Base ozone, without stratospheric input; Right: difference be-tween tagged ozone and base ozone.

produced (see Table 3). Therefore, oxidant levels and non-tagged species are unchanged and the photochemistry oc-curs just as if the tagging were not included. There are afew reactions that are nonlinear in nitrogen species, such asNO2+NO3, so the combination of tagged and non-tagged ni-trogen must be considered (as discussed inLamarque et al.,1996). As shown in Table 3, there are two tagged reactionsfor NO2 + NO3 + M → N2O5 + M:

XNO2 + NO3 + M → XNO2NO3 + NO3 + M

NO2 + XNO3 + M → NO2XNO3 + NO2 + M

The tagged species are operated on by wet and dry deposi-tion at the same rate as their non-tagged counterparts. Taggedozone, NO and NO2 are relaxed to zero in the stratosphere ona timescale of ten days. MOZART-4 does not include explicitstratospheric chemistry, but constrains the mixing ratios ofozone, NOx and NOy in the stratosphere to climatologies (seeEmmons et al., 2010bfor details).

3 Results

The results presented here are from simulations ofMOZART-4 (Emmons et al., 2010b) for 2008, after a 6-month spin-up for each tagging simulation. The meteorologi-cal fields used to drive MOZART-4 for this study are from the

NASA Global Modelling and Assimilation Office (GMAO)GEOS-5 assimilation products (http://gmao.gsfc.nasa.gov/products/). The emissions are the same as used inWespeset al.(2012), with anthropogenic emissions from D. Streets’ARCTAS inventory (seehttp://www.cgrer.uiowa.edu/arctas/emission.html), which is based onZhang et al.(2009), andfire emissions from the Fire Inventory from NCAR (FINN,Wiedinmyer et al., 2011).

NO emissions are included for surface anthropogenicsources (including fossil fuel and biofuel combustion), openfire burning, from soil, lightning and aircraft. Soil emissionsinclude a contribution from fertiliser, with the natural sourcecalculated online based on soil moisture (cf.,Emmons et al.,2010b). Lightning emissions are also calculated online in themodel, using thePrice et al.(1997) parameterisation depen-dent on cloud height (seeEmmons et al., 2010b, for details).Aircraft emissions are emitted as a 3-D field with monthlyvariation (Emmons et al., 2010b). Table4 gives the monthlyglobal NO emissions for each sector. The majority of theemissions, by far, are from anthropogenic surface sources.However, away from urban areas, and in the free troposphere,the other sources can be locally very important for ozone pro-duction.

3.1 Test of method

To illustrate that the tagging method is sound, and has beenimplemented without any errors, a simulation without anystratospheric ozone transport into the troposphere has beenperformed. In a standard simulation, above the tropopauseO3, NO, NO2 and HNO3 are relaxed to a stratospheric cli-matology with a 10-day relaxation time constant. For thistest simulation, both the tagged and untagged versions ofO3, NO, NO2 and HNO3 are relaxed to zero above thetropopause. The results of this simulation, where all tropo-spheric NOx sources have been tagged, are shown in Fig.1.Without any influx of stratospheric ozone to the troposphere,we expect the tagged ozone and base ozone to be nearlyidentical. The difference between the base and tagged ozonedistributions in this test case is less than about 1 ppbv in

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Table 3.Gas-phase reactions of tagged species.


O + O2 + M → O3 + M OA + O2 + M → O3A + MO + O3 → 2*O2 OA + O3 → O3

O + O3A → OO1D + N2 → O + N2 O1DA + N2 → OA + N2O1D + O2 → O + O2 O1DA + O2 → OA + O2O1D + H2O → 2*OH O1DA + H2O → H2OH2 + O1D → HO2 + OH H2 + O1DA → H2O + OH → HO2 + O2 OA + OH → OHHO2 + O → OH + O2 HO2 + OA → HO2OH + O3 → HO2 + O2 OH + O3A → OHHO2 + O3 → OH + 2*O2 HO2 + O3A → HO2N2O + O1D → N2 + O2 N2O + O1DA → N2ON2O + O1D → 2*NO N2O + O1DA → N2ONO + HO2 → NO2 + OH XNO + HO2 → XNO2 + HO2NO + O3 → NO2 + O2 XNO + O3 → XNO2 + O3

NO + O3A → NONO2 + O → NO + O2 XNO2 + O → XNO + O

NO2 + OA → NO2NO2 + O3 → NO3 + O2 XNO2 + O3 → XNO3 + O3

NO2 + O3A → NO2NO3 + HO2 → OH + NO2 XNO3 + HO2 → HO2 + XNO2NO2 + NO3 + M → N2O5 + M XNO2 + NO3 + M → XNO2NO3 + NO3 + M

NO2 + XNO3 + M → NO2XNO3 + NO2 + MN2O5 + M → NO2 + NO3 + M XNO2NO3 + M → XNO2 + M

NO2XNO3 + M → XNO3 + MNO2 + OH + M → HNO3 + M XNO2 + OH + M → XHNO3 + OH + MHNO3 + OH → NO3 + H2O XHNO3 + OH → XNO3 + OHNO3 + NO → 2*NO2 XNO3 + NO → XNO2 + NO

NO3 + XNO → XNO2 + NO3NO2 + HO2 + M → HO2NO2 + M XNO2 + HO2 + M → XHO2NO2 + HO2 + MHO2NO2 + OH → H2O + NO2 + O2 XHO2NO2 + OH → XNO2 + OHHO2NO2 + M → HO2 + NO2 + M XHO2NO2 + M → XNO2 + MCH4 + O1D → 0.75*CH3O2 + 0.75*OH + 0.25*CH2O + 0.4*HO2 + 0.05*H2 CH4 + O1DA → CH4CH3O2 + NO → CH2O + NO2 + HO2 CH3O2 + XNO → CH3O2 + XNO2CH2O + NO3 → CO + HO2 + HNO3 CH2O + XNO3 → CH2O + XHNO3C2H4 + O3 → CH2O + 0.12*HO2 + 0.5*CO + 0.12*OH + 0.25*CH3COOH C2H4 + O3A → C2H4EO2 + NO → EO + NO2 EO2 + XNO → EO2 + XNO2C2H5O2 + NO → CH3CHO + HO2 + NO2 C2H5O2 + XNO → C2H5O2+ XNO2CH3CHO + NO3 → CH3CO3 + HNO3 CH3CHO + XNO3 → CH3CHO + XHNO3CH3CO3 + NO → CH3O2 + NO2 CH3CO3 + XNO → CH3CO3 + XNO2CH3CO3 + NO2 + M → PAN + M CH3CO3 + XNO2 + M → XPAN + CH3CO3 + MPAN + OH → CH2O + NO3 XPAN + OH → XNO3 + OHPAN + M → CH3CO3 + NO2 + M XPAN + M → XNO2 + MC3H6 + O3 → 0.54*CH2O + 0.19*HO2 + 0.33*OH + 0.5*CH3CHO + 0.56*CO C3H6 + O3A → C3H6

+ 0.31*CH3O2 + .25*CH3COOH + 0.08*CH4C3H6 + NO3 → ONIT C3H6 + XNO3 → C3H6 + XONITPO2 + NO → CH3CHO + CH2O + HO2 + NO2 PO2 + XNO → PO2 + XNO2C3H7O2 + NO → 0.82*CH3COCH3 + NO2 + 0.27*CH3CHO + HO2 C3H7O2 + XNO → C3H7O2 + XNO2RO2 + NO → CH3CO3 + CH2O + NO2 RO2 + XNO → RO2 + XNO2ONIT + OH → NO2 + CH3COCHO XONIT + OH → XNO2 + OHCH3COCHO + NO3 → HNO3 + CO + CH3CO3 CH3COCHO + XNO3 → XHNO3 + CH3COCHOENEO2 + NO → CH3CHO + 0.5*CH2O + 0.5*CH3COCH3 + HO2 + NO2 ENEO2 + XNO → ENEO2 + XNO2MEKO2 + NO → CH3CO3 + CH3CHO + NO2 MEKO2 + XNO → MEKO2 + XNO2MPAN + OH + M → .5*HYAC + 0.5*NO3 + 0.5*CH2O + 0.5*HO2 + M XMPAN + OH + M → 0.5*XNO3 + OH + MALKO2 + NO → 0.4*CH3CHO + 0.1*CH2O + 0.25*CH3COCH3 + 0.9*HO2 ALKO2 + XNO → ALKO2 + 0.9*XNO2

+0 .75*MEK + 0.9*NO2 + 0.1*ONIT + 0.1*XONITISOP + O3 → 0.4*MACR + 0.2*MVK + 0.07*C3H6 + 0.27*OH + 0.06*HO2 ISOP + O3A → ISOP + 0.1*O3A

+ 0.6*CH2O + 0.3*CO + 0.1*O3 + 0.2*MCO3 + 0.2*CH3COOHISOPO2 + NO → 0.08*ONITR + 0.92*NO2 + HO2 + 0.55*CH2O + 0.23*MACR ISOPO2 + XNO → ISOPO2 + 0.08*XONITR

+ .32*MVK + .37*HYDRALD + 0.92*XNO2ISOPO2 + NO3 → HO2 + NO2 + 0.6*CH2O + 0.25*MACR + 0.35*MVK ISOPO2 + XNO3 → ISOPO2 + XNO2

+ 0.4*HYDRALD



Table 3.Continued.


ISOP + NO3 → ISOPNO3 ISOP + XNO3 → ISOP + XISOPNO3ISOPNO3 + NO → 1.206*NO2 + 0.072*CH2O + 0.167*MACR XISOPNO3 + NO → 0.206*XNO2 + 0.794*XONITR + NO

+ 0.039*MVK + 0.794*ONITR + 0.794*HO2 ISOPNO3 + XNO → 1.000*XNO2 + ISOPNO3ISOPNO3 + NO3 → 1.206*NO2 + 0.072*CH2O + .167*MACR XISOPNO3 + NO3 → 0.206*XNO2 + 0.794*XONITR + NO3

+ 0.039*MVK + 0.794*ONITR + 0.794*HO2 ISOPNO3 + XNO3 → 1.000*XNO2 + ISOPNO3ISOPNO3 + HO2 → 0.206*NO2 + 0.008*CH2O + 0.167*MACR + ISOPNO3 + HO2 → 0.206*XNO2 + ISOPNO3

0.039*MVK + 0.794*ONITR + 0.794*HO2MVK + O3 → 0.8*CH2O + 0.95*CH3COCHO + 0.08*OH MVK + O3A → MVK + 0.2*O3A

+ 0.2*O3 + 0.06*HO2 + 0.05*CO + 0.04*CH3CHOMACR + O3 → 0.8*CH3COCHO + 0.275*HO2 + 0.2*CO MACR + O3A → MACR + 0.2*O3A

+ 0.2*O3 + 0.7*CH2O + 0.215*OHMACRO2 + NO → NO2 + 0.47*HO2 + 0.25*CH2O + 0.25*CH3COCHO MACRO2 + XNO → XNO2 + MACRO2

+ 0.53*CH3CO3 + 0.53*GLYALD + 0.22*HYAC+ 0.22*CO

MACRO2 + NO → 0.8*ONITR MACRO2 + XNO → 0.8*XONITR + MACRO2MACRO2 + NO3 → NO2 + 0.53*GLYALD + 0.22*HYAC + 0.53*CH3CO3 MACRO2 + XNO3 → XNO2 + MACRO2

+ 0.25*CH2O + 0.22*CO + .25*CH3COCHO+ 0.47*HO2

MCO3 + NO → NO2 + CH2O + CH3CO3 MCO3 + XNO → XNO2 + MCO3MCO3 + NO3 → NO2 + CH2O + CH3CO3 MCO3 + NO3 → XNO2 + MCO3MCO3 + NO2 + M → MPAN + M MCO3 + XNO2 + M → XMPAN + MCO3 + MMPAN + M → MCO3 + NO2 + M XMPAN + M → XNO2 + MONITR + OH → HYDRALD + 0.4*NO2 + HO2 XONITR + OH → 0.4*XNO2 + OHONITR + NO3 → HYDRALD + NO2 + HO2 XONITR + NO3 → 0.5*XNO2 + NO3

ONITR + XNO3 → 0.5*XNO2 + ONITRXO2 + NO → NO2 + 1.5*HO2 + CO + 0.25*CH3COCHO + 0.25*HYAC + 0.25*GLYALD XO2 + XNO → XNO2 + XO2XO2 + NO3 → NO2 + 1.5*HO2 + CO + 0.25*CH3COCHO + 0.25*HYAC + 0.25*GLYALD XO2 + XNO3 → XNO2 + XO2XOH + NO2 → 0.7*NO2 + 0.7*BIGALD + 0.7*HO2 XOH + XNO2 → XOH + 0.7*XNO2TOLO2 + NO → 0.45*GLYOXAL + 0.45*CH3COCHO + 0.9*BIGALD + 0.9*NO2 + 0.9*HO2 TOLO2 + XNO → TOLO2 + 0.9*NO2C10H16 + O3 → 0.7*OH + MVK + MACR + HO2 C10H16 + O3A → C10H16C10H16 + NO3 → TERPO2 + NO2 C10H16 + XNO3 → C10H16 + XNO2TERPO2 + NO → 0.1*CH3COCH3 + HO2 + MVK + MACR + NO2 TERPO2 + XNO → TERPO2 + XNO2DMS + NO3 → SO2 + HNO3 DMS + XNO3 → DMS + XHNO3N2O5 → HNO3 (het) XNO2NO3 → XHNO3 (het)

NO2XNO3 → XHNO3 (het)NO3 → HNO3 (het) XNO3 → XHNO3 (het)NO2 → 0.5*NO + 0.5*HNO3 (het) XNO2 → 0.5*XNO + 0.5*XHNO3 (het)

Table 4.NO emissions used in this study (global totals in Tg yr−1).

Sector Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Annual Avg

Anthropogenic 69.9 69.9 69.9 69.9 69.9 69.9 69.9 69.9 69.9 69.9 69.9 69.9 69.9Fires 3.4 4.4 6.4 9.0 3.5 4.5 6.1 7.8 7.9 4.1 2.9 2.6 5.2Soil 7.3 6.9 8.4 10.5 13.1 14.2 15.5 14.6 11.6 9.6 7.9 7.3 10.6Lightning 6.2 5.8 5.8 6.4 6.6 7.0 7.3 7.8 7.0 6.4 6.0 5.8 6.5Aircraft 1.3 1.3 1.3 1.3 1.3 1.4 1.4 1.4 1.4 1.4 1.3 1.3 1.3Total 88.1 88.3 91.8 97.1 94.4 97 100.2 101.5 97.8 91.4 88 86.9 93.5

the zonal average. The slight difference is due to the smallamount of ozone formed directly without NOx catalysis inthe oxidation of hydrocarbons (Emmons et al., 2010b).

3.2 Tropospheric sources

Figures 2 and 3 show maps of the tropospheric columnof each tagged ozone contribution (anthropogenic surfacesources, fires, soil, lightning, aircraft and the stratosphere)for January and July 2008. For this analysis, we use achemical tropopause defined as the altitude where ozonereaches 150 ppbv (e.g.,Stevenson et al., 2006). The sur-face anthropogenic emissions are the largest contribution inthe Northern Hemisphere in both seasons, while lightning

is the dominant source in the Tropics. The location of fireemissions changes with season, with the savanna region ofnorthern Tropical Africa having the strongest contributionin January. In July, the tropical regions of South Americaand Africa have notable ozone contributions from agricul-tural fires, with the large wildfires in Siberia and Canada alsoevident. The contribution from soil NO emissions are mostapparent in the summer season of each hemisphere, whilethe stratospheric contribution is largest in winter.

Figures4 and 5 show the vertical distribution of ozoneand the tagged contributions in zonal averages for Januaryand July, respectively. Each panel shows the location ofthe 150 ppbv contour of ozone (used for determining the



Surface Anthropogenic Fires

Soil Lightning

Aircraft Stratosphere

Tagged O3 Column (O3 < 150 ppbv) - Jan

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 DU

Fig. 2. Tropospheric columns of each tagged ozone source for Jan-uary 2008. Stratospheric contribution is determined as the differ-ence between total ozone and tagged ozone from all troposphericsources. The chemical tropopause of O3 at 150 ppbv is used.

tropospheric columns in the previous figures). In January, an-thropogenic surface sources are maximum in the lower andmiddle troposphere of the Northern Hemisphere (NH), whilein July strong summertime convection distributes its ozonecontribution throughout the troposphere at mid-latitudes.A similar summer-winter pattern is seen in the SouthernHemisphere (SH), but the anthropogenic sources are so muchsmaller there, the anthropogenic ozone contribution is muchless. The vertical distribution of the ozone contributions fromfires and soil emissions shows the seasonal variation in boththe sources and convection and transport patterns. Lightningand aircraft emissions originate in the upper troposphere,with aircraft activity largest in the NH and lightning peakingin the tropics and in summer at mid-latitudes. While light-ning produces only NO (at least in the model), sufficientconcentrations of CO and VOCs are transported within theconvective systems to lead to large amounts of ozone pro-duction (e.g.,Hauglustaine et al., 2001). Aircraft have verylow CO and hydrocarbon emissions coincident with NO,but background levels of CO and VOCs are sufficient forozone production in the upper troposphere, resulting in up to30 ppbv ozone contribution in the zonal average in July. Thestratospheric ozone contribution clearly shows the level ofthe tropopause approximately at the 100 ppbv contour, withhighest values in the troposphere in the winter hemisphere.

Figure 6 (top row) shows zonal averages for Januaryand July of the contributions of ozone at the surface fromeach NO source type. As seen in the previous figures,

Surface Anthropogenic Fires

Soil Lightning

Aircraft Stratosphere

Tagged O3 Column (O3 < 150 ppbv) - Jul

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 DU

Fig. 3.As Fig.2, for July 2008.

the anthropogenic contribution is dominant in the NorthernHemisphere for both summer and winter. In the SouthernHemisphere, lightning and stratospheric air are a larger frac-tion of the total ozone. Biomass burning has a large seasonalvariation, however, with a relatively small contribution tothe total. Soil emissions peak in the summer mid-latitudesof both hemispheres. The bottom row of Fig.6 shows theozone amounts for different sources at 400 hPa, with verydifferent relative contributions than at the surface. Lightningis the largest contribution in the Tropics and sub-Tropics.The stratospheric contribution is most significant in NH win-ter and spring. Anthropogenic emissions are the source fortwice as much ozone in the NH than the SH, but contribute asmaller fraction than at the surface. The small white area be-tween the contributions from lightning and the stratosphereindicates the difference between the sum of the individu-ally tagged sources and the result from tagging all sources atonce. This shows the level of nonlinearity in the method andcorresponds to 3 % or less in the zonal average at 400 hPa,and less than 1 % at the surface.

The same source contributions to NOx, PAN, HNO3 andtotal NOy at 400 hPa are shown in Fig.7 for July. As forozone, the most important contributions are from anthro-pogenic and lightning emissions for all three of these species.The stratospheric source for these compounds is determinedin the same manner as for ozone (the difference between sim-ulated total of the species and the contribution from all tro-pospheric sources tagged). For NOx, the stratospheric con-tribution is barely noticeable in these plots, but for HNO3it is important, and for the SH winter is essentially the onlysource south of 50◦ S.



Total O3

-100 -50 0 50 100Latitude

1000

100

Pres

sure

[hPa

]

All Trop Sources

-100 -50 0 50 100Latitude

1000

100

Pres

sure

[hPa

]

Surface Anthro

-100 -50 0 50 100Latitude

1000

100

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sure

[hPa

]

Fires

-100 -50 0 50 100Latitude

1000

100

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sure

[hPa

]

Soil

-100 -50 0 50 100Latitude

1000

100

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sure

[hPa

]

Lightning

-100 -50 0 50 100Latitude

1000

100

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sure

[hPa

]

Aircraft

-100 -50 0 50 100Latitude

1000

100

Pres

sure

[hPa

]

Stratosphere

-100 -50 0 50 100Latitude

1000

100

Pres

sure

[hPa

]

Tagged O3 Zonal Average - Jan

0 1 2 5 10 15 20 25 30 35 40 45 50 75 100 150 ppbv

Fig. 4.Zonal average of each tagged ozone source for January 2008.Stratospheric contribution is determined as the difference betweentotal ozone and tagged ozone from all tropospheric sources.

HNO3 shows the largest missing contribution between thesum of individual source tags and all sources (the white areain the plot between the lightning and stratosphere contribu-tions). This is due to the nonlinearity of wet deposition andHNO3 is much more soluble than the other reactive nitro-gen compounds. The washout rate for the tagged HNO3 isthe same as for total HNO3, but the amount of tagged HNO3will be limited by the available mass of that tag. So, at times(and places) all of the mass of a HNO3 tag may be removedfrom the atmosphere, eliminating any possibility of recyclingto NO2 (through photolysis) and reformation of HNO3.

3.3 Stratospheric ozone

One commonly studied source of ozone is the stratosphericcontribution to the troposphere. Many modelling studies haveused a tracer (“O3S”) that is set to the ozone mixing ratio inthe stratosphere and is destroyed below the tropopause at thesame rate as ozone (e.g.,Roelofs and Lelieveld, 1997; Wanget al., 1998; Emmons et al., 2003). This technique, however,gives an upper limit to the stratospheric ozone contribution,as tropospheric air that is transported into the stratosphereis reset to the stratospheric value. By tagging all of the tro-pospheric sources (surface anthropogenic, biomass burning,

Total O3

-100 -50 0 50 100Latitude

1000

100

Pres

sure

[hPa

]

All Trop Sources

-100 -50 0 50 100Latitude

1000

100

Pres

sure

[hPa

]

Surface Anthro

-100 -50 0 50 100Latitude

1000

100

Pres

sure

[hPa

]

Fires

-100 -50 0 50 100Latitude

1000

100

Pres

sure

[hPa

]

Soil

-100 -50 0 50 100Latitude

1000

100

Pres

sure

[hPa

]

Lightning

-100 -50 0 50 100Latitude

1000

100

Pres

sure

[hPa

]

Aircraft

-100 -50 0 50 100Latitude

1000

100

Pres

sure

[hPa

]

Stratosphere

-100 -50 0 50 100Latitude

1000

100

Pres

sure

[hPa

]

Tagged O3 Zonal Average - Jul

0 1 2 5 10 15 20 25 30 35 40 45 50 75 100 150 ppbv

Fig. 5.As previous figure, for July 2008.

soil, lightning and aircraft emissions), we can determine theamount of ozone produced from tropospheric sources and,thus, the stratospheric contribution from the difference of thetagged amount and the total ozone.

Figure8 shows the stratospheric contribution determinedfrom the tagged tropospheric sources, as well as from the tra-ditional “O3S” tracer. The O3S tracer gives a much greaterestimate of stratospheric ozone than the tagged ozone does,both in the mid-troposphere and at the surface. At the surface,where O3S shows over 20 ppbv, the tagged ozone gives nomore than 8 ppbv.Hess and Lamarque(2007) showed simi-lar differences in zonal averages of surface O3S and taggedozone. The vertical distributions of tagged ozone shown inFigs. 4 and 5 illustrate that a significant amount of tropo-spheric air gets into the stratosphere (i.e., above the 150 ppbvozone contour). With the O3S tracer, those contributionswould get reset to stratospheric air, but the tagging methodpreserves those as tropospheric sources. When consideringthe whole troposphere (ozone less than 150 ppbv), the frac-tion of the tropospheric ozone burden that is from the strato-sphere is 58 % based on O3S, and 17 % based on the taggedozone. These differences are comparable to those found us-ing different measures byEmmons et al.(2003) in an analysisof the Northern Hemisphere springtime ozone increase.



Surface - Jan

-50 0 50Latitude

0

10

20

30

40

50

O3

[ppb

v]

AnthroSoilFiresAircraftLightningStrat

Surface - Jul

-50 0 50Latitude

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ZA O3 Sources

400hPa - Jan

-50 0 50Latitude

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[ppb

v]


400hPa - Jul

-50 0 50Latitude

0

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ZA O3 Sources

Fig. 6. Zonal average of tagged ozone source contributions at thesurface and at 400 hPa, for January and July of 2008. Stratosphericcontribution is determined as the difference between total ozone andtagged ozone from all tropospheric sources combined.

3.4 Comparison to perturbed source attribution

Simulations with perturbed emissions are primarily used toquantify the impacts of changes in emissions scenarios, buthave also been used to approximate total source contribu-tions. As mentioned above, many previous studies have de-termined ozone contributions from source regions by de-creasing the NO emissions of that region and scaling the dif-ference between the perturbed run and a standard run (e.g.,Fiore et al., 2009; Reidmiller et al., 2009). The differencesbetween attributing source contributions through perturba-tion or tagging procedures have been presented byGreweet al. (2010, 2012), illustrating the nonlinearity of ozonechemistry and its effect on attributing ozone sources. Wehave performed a similar analysis of our tagging scheme incomparison to perturbation results and show here that thenonlinearity of ozone chemistry has a significant impact onthe conclusions drawn from perturbation simulations.

We have performed two simulations in this manner withNO emissions in Asia reduced by 5 and 20 %, so as to com-pare it with our method of tagging NO. Figure9 showsthe original NO surface emissions (shipping, anthropogenic,fires and soil) for July 2008, also indicating the Asian re-gion that has been either tagged or perturbed. This region isroughly the combination of the South Asia and East Asia re-gions used in the HTAP simulations (e.g.,Fiore et al., 2009).Figure 10 shows a comparison of surface ozone attributedto emissions in Asia using these two techniques for severalreceptor regions (the N. America and Europe regions aresimilar to, but not exactly the same as, the HTAP regions).The two methods give notably different results. However,the two perturbation cases give essentially the same resultswhen scaled to correspond to 100 % attribution. Comparable

NOx sources - Jul

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y [p

ptv]

400hPa

Fig. 7. As Fig. 6, for tagged NOx, PAN, HNO3 and NOy sourcecontributions at 400 hPa in July.

results were seen in other models with different chemicalschemes (Wu et al., 2009; Wild et al., 2012). Over Asia, theaverage surface ozone produced from sources in Asia is 20–25 ppbv in the Tagged method, but 1–6 ppbv in either Per-turbed method. The seasonal cycle is also different, with theTagged method peaking in April and having a minimum inAugust, while the Perturbed method shows a broad summermaximum. In the downwind regions, the seasonal cycle ismore similar in the two methods, with the magnitude of thedifferences decreasing while progressing from the northeastPacific to North America to Europe.

The results from the simulations with perturbed emissionsagree well with the results of the HTAP simulations pre-sented in Fig. 11 ofFiore et al.(2009). In the HTAP results,the estimated contribution of East Asia in North America isabout 1.5 ppbv in spring and less than 1 ppbv in summer. Thismatches our results for the Perturbed case in the N. Amer-ica panel of Fig.10. Brown-Steiner and Hess(2011) found asimilar difference between the HTAP results and their simu-lations with CAM-chem using the same tagged ozone proce-dure as presented here. That study found tagged ozone fromAsia at the surface in North America to be 2–2.5 times thatdetermined by the HTAP perturbed attribution procedure.

Since these two procedures for determining ozone sourcecontributions give such different results, it is important tounderstand the causes, as well as which questions each pro-cedure can address. If one wants to determine the effect ofa change in emissions (due to policy controls or climatechange), then the perturbed method is appropriate. However,the tagged ozone mechanism quantifies the contribution for agiven source for a given state of the atmosphere, without anychange in the chemical composition, and is useful in deter-mining the ozone chemical budget.

Although a perturbation of 5 or 20 % in the emissions mayseem small, it can have a significant impact on the local



(O3-O3A) January O3S January

(O3-O3A) July O3S July

500hPa

(O3-O3A) January O3S January

(O3-O3A) July O3S July

Surface

0 2 4 6 8 10 15 20 25 30 35 40 50 ppbv

Fig. 8. Stratospheric ozone contribution from the tagged NOmethod (left) and from the stratospheric ozone tracer, O3S (right),at 500 hPa (top) and the surface (bottom).

chemistry. In particular, the OH and HO2 distributions arevery sensitive to changes in NO, which will lead to changesin the ozone production and loss rates. These effects werediscussed inPfister et al.(2006), in the analysis of ozonefrom biomass burning plumes using the tagged and perturbedmethods, and are further illustrated here.

The rate-limiting reactions for ozone production and losscan be written as:

P(O3) = [NO]∗K ′

P where K ′

P = (kHO2[HO2]+kRO2[RO2])

L(O3) = [O3] ∗K ′

L where K ′

L = (kOH[OH] + kHO2[HO2])

For the tagged ozone,P (O3A) = [XNO] * K ′

P andL(O3A) = [O3A] * K ′

L where theK ′s are the same for the to-tal ozone and tagged ozone rates because the OH and peroxyradicals are identical (because the tagged ozone is simulta-neously calculated with the full chemistry). In the perturbedcase, however, the change in NO emissions causes a changein OH, HO2, RO2, etc., so theK ′s are not the same betweenthe base run and perturbed run. Figure11illustrates these dif-ferences inK ′

P andK ′

L. Hourly output for the Base, Tagged

NO Emissions July

0.e+00 1.e-14 1.e-12 2.e-12 5.e-12 1.e-11 2.e-11 5.e-11 1.e-10 2.e-10 kg-m2/s

Fig. 9. NO surface emissions for July. Black dashed line shows re-gion of tagged or perturbed emissions.

Asia

0 2 4 6 8 10 12Month

05

10

15

20

2530

Asia

n O

zone

[ppb

v] Tagged

20% Pert. 5% Pert.

NEPacific

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0

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4

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0.00.5

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1.5

2.0

2.53.0

Asia

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[ppb

v]

Surface O3

Fig. 10. Surface ozone attributed to Asian emissions based ontagged and perturbed NOx emissions, averaged over four receptorregions, as a function of month. The 20 % perturbed contribution is5 times (and the 5 % perturbation case is 20 times) the differencebetween the standard simulation and a simulation with 80 % NOxemissions in Asia. The receptor regions are Asia (0◦ –60◦ N, 60◦ –180◦ E, same as emissions), NE Pacific (30◦ –55◦ N, 190◦ –235◦ E),N. America (15◦ –55◦ N, 235◦ –300◦ E) and Europe (30◦ –70◦ N,0◦ –45◦ E).

and Perturbed results are used to calculateP(O3)/[NO] andL(O3)/[O3] to representK ′

P and K ′

L. The results shownare averages of the hourly calculations over 20–29 July, andthen differenced with the Base calculation. For the taggedcase,K ′

P andK ′

L are within a few percent of the Base case,whereas the perturbedK ′

P is up to 15 % higher than the Basecase andK ′

L is as much as 40 % lower. These images alsoshow that the nonlinearity effects vary significantly spatially,depending on the magnitude of NOx concentrations and therelative abundances of NOx and VOCs. Changes in NOx will



6 P(O3)/[NO] (Tagged-Base) 6 P(O3)/[NO] (Pert-Base)

6 L(O3)/[O3] (Tagged-Base) 6 L(O3)/[O3] (Pert-Base)

-45

-20

-15

-10

-5

-2

0

2

5

10

15

%

Fig. 11.Differences (%) inK ′P

andK ′L

(see text) between Taggedand Base runs (left panels) and between Perturbed and Base runs(right). Average of hourly output for 20–29 July 2008.

affect ozone production and loss differently depending onthe NOx and VOC levels. The greatest changes inK ′

P andK ′

L in the perturbed case are over the major urban areas ofeastern Asia (Bejing, Shanghai, Pearl River Delta, Tokyo).Since these are the largest source regions they will signifi-cantly drive the regional averages shown in Fig.10.

4 Conclusions

A technique of tagging ozone from various source regionsby using artificial tracers of NO and its oxidation productshas been described. This method shows a high degree oflinearity: the sum of tagged ozone from individual sourcesis equal to the tagged ozone of all sources, within 3 % inzonal averages in the troposphere. We have also shown, ina test simulation where the stratospheric input has been setto zero, that the tagged ozone from all tropospheric NOxsources is equal to the total ozone. This tagging procedure al-lows source contributions to NOx products, such as PAN andHNO3, to be quantified as well. Comparisons to other stan-dard attribution methods show significant differences. Thecontribution of stratospheric ozone to the troposphere usingthis tagging method is significantly lower than estimates us-ing a stratospheric ozone tracer. In comparison to determin-ing source contributions by perturbing NO emissions, thetagging method gives significantly higher contributions, atleast for an example for Asia emissions. These differencesare due to the nonlinearity of ozone chemistry, where bothozone production and loss rates are affected by a change inNO concentrations.

The mechanism file and source code modifications forMOZART-4 and CAM-chem are available from the authors.

Acknowledgements.This article has been greatly improved asa result of the thoughtful reviews by M. Evans and T. Butler,helpful discussions with S. Arnold, and comments on earlierdrafts by D. Kinnison and A. Boynard. The GEOS-5 data usedin this study have been provided by the Global Modelling andAssimilation Office (GMAO) at NASA Goddard Space FlightCenter. The National Center for Atmospheric Research is fundedby the National Science Foundation.

Edited by: V. Grewe

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