JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 106,NO.

D19, PAGES 23,073-23,095,OCTOBER 16, 2001

Global modeling of tropospheric chemistry

with assimilatedmeteorology:
Model description and evaluation
IsabelleBey,• DanielJ. Jacob,
RobertM. Yantosca,
JenniferA. Logan,
BrendanD. Field, Afiene M. Fiore, Qinbin Li, Honguy Y. Liu,
LorettaJ. Mickley,andMartinG. Schultz
2
Divisionof EngineeringandAppliedSciences,andDepartmentof EarthandPlanetarySciences,
Harvard University,Massachusetts

Abstract. We presenta first descriptionand evaluationof GEOS-CHEM, a globalthree-

dimensional(3-D) model of troposphericchemistrydrivenby assimilatedmeteorological
observationsfrom the GoddardEarth ObservingSystem(GEOS) of the NASA Data
AssimilationOffice (DAO). The model is applied to a 1-year simulationof tropospheric
ozone-NO•-hydrocarbonchemistryfor 1994, and is evaluatedwith observations both for
1994 and for other years. It reproducesusually to within 10 ppb the concentrationsof
ozoneobservedfrom the worldwide ozonesondedata network. It simulatescorrectlythe
seasonalphasesand amplitudesof ozoneconcentrations for differentregionsand altitudes,
but tendsto underestimatethe seasonalamplitude at northernmidlatitudes. Observed
concentrationsof NO and peroxyacetylnitrate (PAN) observedin aircraftcampaignsare
generallyreproducedto within a factor of 2 and often much better. Concentrationsof
HNO3 in the remotetroposphereare overestimatedtypically by a factor of 2-3, a common
problemin global modelsthat may reflect a combinationof insufficientprecipitation
scavengingand gas-aerosolpartitioningnot resolvedby the model. The model yields
an atmosphericlifetime of methylchloroform(proxy for global OH) of 5.1 years, as
comparedto a best estimatefrom observationsof 5.5 +/- 0.8 years, and simulatesH202
concentrationsobservedfrom aircraftwith significantregionaldisagreements but no global
bias. The OH concentrationsare •20% higher than in our previousglobal 3-D model
whichincludedan UV-absorbingaerosol.Concentrations of CO tendto be underestimated
by the model, often by 10-30 ppb, which could reflect a combinationof excessiveOH (a
20% decreasein model OH couldbe accommodatedby the methylchloroformconstraint)
and an underestimateof CO sources(particularlybiogenic). The model underestimates
observedacetoneconcentrations over the SouthPacificin fall by a factor of 3; a missing
sourcefrom the oceanmay be implicated.

1. Introduction examineaerosol-chemistry-climate interactions[Roelofset

aL, 1997; Mickley et al., 1999; Adamset aL, 2001], and
Global three-dimensional(3-D) models of troposphe-
to guideinternational
environmental policyassessments [In-
ric chemistryarefastbecomingstandardtoolsfor improving tergovernmental Panel on Climate Change(IPCC), 1995,
our knowledge of chemical budgetsand processesin the 2001]. Severalcommunityintercomparisons of global tro-
troposphere. They are also beginning to be used in an
posphericchemistrymodelshavebeenconductedrecently,
exploratory way to provide chemical forecastsfor exper-
demonstrating the rapid growthof the field [Jacobet al.,
imental field programs [Flatoy et al., 2000], to provide 1997; Kanakidou et al., 1999; Rasch et al., 2000; IPCC,
a prioris for satellite retrievals [Palmer et al., 2001], to 2001].
A central theme in the developmentof global tropo-
sphericchemistrymodelsis the simulationof ozone-NO•-
hydrocarbonchemistry. Better understanding of the fac-
1NowatSwissFederal
Institute
of Technology,
Lausanne,
Switzerland. tors controlling troposphericozone is a major research
2NowatMax-Planck-Institut
forMeteorologie
Hamburg,
Germany. priority[WorldMeteorologicalOrganization(WMO), 1998].
More generally,ozone-NO•-hydrocarbon chemistrydeter-
Copyright2001 by the AmericanGeophysicalUnion. mines radical and oxidant processesin the troposphere
Papernumber2001JD000807. and lies therefore at the heart of most problems affect-
0148-0227/01/2001JD000807 $09.00 ing tropospheric
composition.Simulationof ozone-NO,-
23,073
 23,074 BEY ET AL.: GLOBAL MODELING OF TROPOSPHERIC CHEMISTRY

(o) GEOS-1 Sigma Levels (b) GEOS-STRAT

Sigma Levels
-lO 65

6O

55

5O

45

20
,-., 40 o
E
• 35
lOO .•
10
._

200 25 .
25 •'
20 50

100
400 15
2OO
10
6oo
400
.800
5
:'•oo
:1000 0 1 ooo

(c) GEOS-2 Sigma Levels (d) GEOS-TerroSigma Levels

80- - 0.01 8oi- - O.Ol

0.1 o.1

,.., 50
E -
• 45 _
45, .

• ,•o . ,•o .

..•_. 5
•. 35 55 -

10 •' lO
.

30 3O
. .

25 25 25 .25
_ .

20 50 2O .50
. .

100 lOO
15 15
.

lO
.
250 10' .
. 250

5 500 5 500
_

o 1000 0 1 ooo

Figure 1. Sigmaverticallevelsin successive

generations
of the GEOS assimilated
meteorological
data.
The GEOS-1 data (1985-1995) have20 levels from the surfaceto 10 hPa; the GEOS-STRAT data (1996-
1997) have46 levelsfrom the surfaceto 0.1 hPa;the GEOS-2 data (1998-1999) have70 levelsfrom the
surfaceto 0.01 hPa; the GEOS-Terra data (2000-) have 48 levels from the surfaceto 0.01 hPa.

hydrocarbonchemistryis difficult in a global model be-
cause of the large number of speciesinvolved (•100),
the nonlinearityof the chemistry,the numerical stiffness
of the system,and the couplingof chemistryto transport
over a wide range of scales. A numberof independently
developedmodelshave been reportedin the literatureover
the past few years [e.g., Collins et al., 1997; Brasseur
et al., 1998; Wang et al., 1998a; Lawrence et al., 1999;
Levy et al., 1999; Lelieveld and Dentenet, 2000]. They
sharesimilartheoreticalfoundationsbutdiffer in manyways
includingresolution,the drivingmeteorologicalfields,and
theapproaches anddetailfor simulatingemissions,chemical
processes,and deposition.
Our first-generationglobalmodelof tropospheric ozone-
NOx-hydrocarbonchemistrywas describedand evaluated
by Wanget al. [1998a,1998b] and subsequently refinedby
Horowitz and Jacob [ 1999] and Mickley et al. [ 1999]. It
usesmeteorological fieldsfrom a generalcirculationmodel
(GCM) developedat the GoddardInstituteof ScienceStud-
ies (GISS) [Hansen et al., 1983; Rind and Lerner, 1996].
We have sincedevelopedthe need for a model driven by
assimilatedmeteorologicalobservations in orderto provide
betterconstraints
on thesimulationof specificyears,to allow
investigations
of interannualvariability,and to set in place
a machineryto conductchemicalforecastsin supportof
aircraft missions.
We presenthere our second-generation global model us-
ing assimilatedmeteorologicaldatafrom the GoddardEarth
ObservingSystem(GEOS) of the NASA Data Assimilation
Office (DAO) [Schubertet al., 1993]. Developmentof this
second-generation modelinvolvedthe graftingof the Wang
et al. [1998a] modulesof photochemistry, emissionsand
depositionontotheoriginalGEOS chemicaltransportmodel
developedby Allen et al. [1996a,1996b] and Lin and Rood
[ 1996]. We give in the presentpapera generaldescription
andevaluationof the resultingmodel,whichwe call GEOS-
CHEM, focusingon tropospheric ozone-NOx-hydrocarbon
chemistry.This paperis intendedto providebackgroundfor
 BEY ET AL.: GLOBAL MODELING OF TROPOSPHERIC CHEMISTRY 23,075

severalrecentand ongoingstudiesusingthe GEOS-CHEM (Table 2). Advectionis computedevery 15 min (2øx2.5 ø

model [Singh et al., 2000a; Li et al., 2000; Palmer et al., horizontalresolution)or 30 min (4øx5 ø horizontalresolu-
2001; Liu et al., 2001; Bey et al., this issue]. tion) with a flux-form semi-Lagrangian methoddescribed
by Lin and Rood [1996]. Moist convectionis computed
2. Model Description usingthe GEOS convective, entrainment, anddetrainment
massfluxesas describedby Allen et al. [1996a,1996b].We
2.1. Model Framework
assume full mixingwithintheGEOS-diagnosed atmospheric
The GEOS assimilatedmeteorologicalobservationsused mixed layer generatedby surface
instability.
to drive the GEOS-CHEM model are available as a con-
2.2. Emissions
tinuous archive from 1985 to present,with 3- or 6- hour
temporalresolutiondependingon the variable. The GEOS We present in this paper a simulation for 1994, and
assimilationsystemhas gone through successivegenera- emissionsfor that year are given in Table 3. Simulations
tions: GEOS- i (1985-1995), GEOS-STRAT (i 996- i 997), for other years use adjustedanthropogenicemissions,as
GEOS-2 (1998-1999), and GEOS-Terra (2000-). The hor- described below.
izontal resolutionis 1ø latitudeby 1ø longitudein GEOS- 2.2.1. Anthropogenicemissions Simulationof specific
Terra and 2ø latitudeby 2.5ø longitudein earlier versions. yearswith a globaltroposphericchemistrymodel musttake
Meteorologicalfields are providedon a sigma coordinate into accountthe year-to-yearvariabilityof anthropogenic
with 20 vertical levels in GEOS-1, 26 in GEOS-STRAT, emissions. We use a base emission inventory for 1985
70 in GEOS-2, and 48 in GEOS-Terra ( Figure 1). The describedby Wanget al. [ 1998a] that includesNOx emis-
GEOS-CHEM model is presently used at Harvard with sionsfrom the Global EmissionInventory Activity (GEIA)
either GEOS-1, GEOS-STRAT, or GEOS-Terra products. [Benkovitzet al., 1996], nonmethanehydrocarbon(NMHC)
Table I liststhe GEOS variablesusedas input to the model. emissions from Piccot et al. [1992], and CO emissions
For computationalexpediencywe frequentlymerge levels developedat Harvard. We scaletheseemissionsfor specific
in the stratosphereand averagethe data horizontallyover years as follows. For unregulatedcountries (where no
a 4øx5 ø grid. The model transports24 chemicaltracers regulationshave been imposedto limit emissions),NOx
to describetroposphericO3-NOx-hydrocarbonchemistry emissionsare scaled using trends in CO2 emissionsfrom

Table 1. GEOS Fields Usedas Input to the GEOS-CHEM Model

Variable Resolutiona Application

Wind vector Inst 6 h advection

Surfacepressure Inst 6 h advection
Wetconvective
mass
flux,detrainment
b Avg6 h convection
Mixed layer depth Avg 3 h boundarylayer mixing
Temperature Inst 6 h chemistry
Specifichumidity lnst 6 h chemistry
Cloudoptical
depth
b Avg6 h photolysis
Surface albedo Inst 6 h photolysis,dry deposition(snowcover)
Land-Water indices Inst 6 h dry deposition,lightning
Sensibleheatflux Avg 3 h dry deposition
Solarradiationflux at surface Avg 3 h dry deposition
Surfaceair temperature Avg 3 h dry deposition,biogenicemissions
Surfacewind (10 m altitude) Avg 3 h dry deposition,NO.• soilemissions
Frictionvelocity Avg 3 h dry deposition
Roughness height Avg 3 h dry deposition
Watercondensation ratec Avg 6 h wet deposition
Totalprecipitationat the ground Avg 3 h wet deposition
Convectiveprecipitationat the ground Avg 3 h wet deposition
Column
cloudfraction
d Avg3 h biogenicemissions

aThe fields are given with three different temporal resolutions. "Inst 6 h" indicatesthat the quantity is an
instantaneous value given every 6 hours. "Avg 6 h" and "Avg 3 h" indicatethat the quantityis averagedover 6
and 3 hours,respectively.
bVerticallyresolved.
cActuallyprovidedasthechangein specifichumiditydueto moistprocesses. Interpretation
asa watercondensation
rateis approximate[Liu et at., 2001].
dUsedto separate
thedirectanddiffusephotosynthetically
activeradiation(PAR)in thecalculation
of isoprene
emissions.
 23,076 BEY ET AL.- GLOBAL MODELING OF TROPOSPHERICCHEMISTRY

Table2. Tracersfor GEOS-CHEMModelSimulation

of Tropospheric
Ozone-NO•-HydrocarbonChemistry

Tracer Composition

Ox 03 + O + NO2 + 2 x NO3
NO= NO + NO2 + NO3 + HNO2
HNO3
HN04
N205
PAN peroxyacetylnitrate
H202
co
C2H6
C3H8
ALK4 lumped_>C4 alkanes
PRPE lumped_>C3 alkenes
Isoprene
Acetone
CH3OOH
CH20
CH3CHO
RCHO lumped_>C3 aldehydes
MEK lumped_>C4 ketones
Methyl vinyl ketone
Methacrolein
MPAN peroxymethacryloyl nitrate
PPN
lumpedperoxyacylnitrates a
R4N2 lumpedalkyl nitrates

Otherthanperoxyacetyl
nitrate(PAN)andperoxymethacryloyl
nitrate(MPAN).

fossilfuel combustion,and CO and NMHC emissionsare 2.2.3. Biogenic emissions lsoprene emission rates
scaledusingtrendsin CO: emissionsfromliquidfuels. from vegetationin the Wanget al. [1998a]modelwere
YearlyCO: emissionsforindividual
countriesareprovided computedwith a modifiedversionof the GEIA inventory
byMarlandetal. [1999],whoprimarily
usedenergy statis- [Guenther
et al., 1995],theprincipal
modifications
beinga
ticspublished
bytheUnitedNations [1998].Forregulateddecreasein the leaf areaindex(LAI) fromtropicalforests
countrieswe use other emissioninventoriessuchas those andan improvedrepresentation
of light attenuation
within
providedbytheEnvironmental Protection
Agency (EPA)for the forest canopy. We have made here some additional
theUnited
States
[EPA,1997]andtheEuropean
Monitoringmodifications.
Onthebasisof recentestimates
of isoprene
andEvaluation
Program(EMEP) for European
countries fluxes
fortropical
vegetation
[Klinger
etal., 1998;Helmiget
[EMEP, 1997]. Table 4 shows the evolution of CO and al., 1998],andalsoto improveagreement
betweensimulated
NOxemissions
between geopo- and observedisopreneconcentrations,we have reduced
1985and1994fordifferent
litical regions. Global CO and NOx emissionsshowlittle emission ratesfor severalecosystems (tropicalrain forest,
changeover the years,but Europeanemissions decrease tropicalmontane, tropicalseasonal forest,dry taiga)by
while emissionsin Asia, Africa, and Oceaniaincrease.The a factorof 3. This leadsto a globalemissionrate for
largedecrease of emissions in Europeafter1991is dueto isoprene of 397Tg C yr-1. A biogenic source of acetone
regulatorycontrolbut alsoto the collapseof the former scaledto isoprene emissions waspreviously includedby
USSR. The largestincreaseof emissionsoccursin Asia. Wanget al. [1998a]. Becausemonoterpene oxidation
2.2.2.Biomass burningemissionsBiomass burning hassincebeenrecognized to representa majorsourceof
andwoodfuelemissions arefromaclimatologicalinventory acetone[Reisselet al., 1999],we nowdistributebiogenic
previously
described
byWang Thisinventoryemissions
etal. [1998a]. ofacetone
(15TgC yr-•) following
thepattern
of
includes differentcategoriesof burning(forestwildfires, monoterpeneemissions[Guentheret al., 1995] ratherthan
tropicaldeforestation,slash-and-bum savanna isoprene
agriculture, emissions.Monoterpeneemissions arenotdirectly
burning, andburning waste),andyieldsa included
of agriculture in themodelbecausetheireffectonglobalozone
globalCO emission of 520Tg CO yr-•. Emissionsof NO• chemistryis minimal.
andhydrocarbons
arederived
fromtheCOinventory
using
emission by Wangetal. [1998a].Wood 2.3. Chemistry
ratiosasdescribed
fuel emissionsof CO accountfor an additionaltotalof 133 The chemicalmechanism for the troposphere
includes
Tg CO yr-•. 80 speciesand over 300 reactionswith detailedpho-
 BEY ET AL.: GLOBAL MODELING OF TROPOSPHERIC CHEMISTRY 23,077

Table 3. Global Emissions for 1994 in the GEOS-CHEM Model

Species Emission Rate

NO•, TgN yr-•

Fossilfuel combustion 22.8
Biomass
burning 12
Soil 6.7
Lightning 3.4
Aircraft 0.5
Stratosphere 0.2
Total 45.6
CO,TgCOyr-1
Fossilfuelcombustion
andindustry 388
Wood fuel combustion 133
Biomass
burning 522
Total 1043
Isoprene,
TgC yr-•
Vegetation 397
Ethane,
Tg C yr-•
Industrial 6.6
Biomass
burning 3.0
Total 9.6
Propane,
TgC yr-•
Industrial 7.0
Biomass
burning 0.9
Total 7.9
• C4alkanes,
TgC yr-1
Industrial 31.2
>_Ca alkenes,
TgC yr- •
Industrial 11.8
Biogenic
sources 11.3
Biomass
burning 6.0
Total 29.1
Acetone,
TgC yr-•
Industrial 1.1
Biomass
burning 8.7
Biogenic
sources 15
Total 24.8

Table4. Evolutionof Anthropogenic

Emission
RatesBetween1985and1994

Species 1985 1991 1994

NO•, TgN yr-•

North America 6.2 6.4 6.5
SouthAmerica 1.3 1.4 1.5
Europe 7.6 7.5 7.0
Africa 1.3 1.5 1.6
Asia 4.1 5.1 5.5
Oceania 0.5 0.6 0.7
Total 21 22.5 22.8
CO,Tg COyr-•
North America 109.5 96.5 94.0
SouthAmerica 21.0 23.0 24.5
Europe 153.0 145.5 123.0
Africa 18.0 19.5 22.0
Asia 82.0 103.5 113.5
Oceania 9.0 10.0 11.0
Total 392.5 398.0 388.0

Anthropogenic
emissions
include
fossilfuelcombustion
andindustrial
sources.
NorthAmerica
includesthe United Statesand Canada. South America includesalso Central America. Europe
includesthe formerUSSR. Africa includesthe Middle East. OceaniaincludesAustralia,Indonesia
and New Zealand.
 23,078 BEY ET AL.: GLOBAL MODELING OF TROPOSPHERIC CHEMISTRY

tooxidationschemesfor major anthropogenic

hydrocarbons modifications[Wang et al., 1998a]. The dry deposition
and isoprene, as describedby Horowitz et al. [1998]. velocitiesarecalculatedlocallyusingGEOS datafor surface
It has been updated with recent experimentaldata from valuesof momentum andsensibleheatfluxes,temperature,
DeMore et al. [1997], Atkinson [1997] and Brown et and solarradiation. Wet deposition(appliedto HNO3 and
al. [1999a,1999b]. We have also changedthe fate of H202 only) includesscavenging by convectiveupdraftsand
the hydroxy organic nitrates producedby isopreneoxi- anvilsand by large-scaleprecipitation;this algorithmwas
dation. Because these compoundsare now believed to developedby Liu et al. [2001], who evaluatedit in the
decomposequickly to HNO3 on surfaces[Chen et al., GEOS-CHEM bysimulation of theaerosoltracers2•0pband
1998], we assume direct formation of HNO3 instead of ?Be.
the organic nitrates. The effect of heterogeneous chem-
istry on troposphericozone has been reviewedby Jacob 2.5. Cross-TropopauseFlux of Ozone
[2000]. Followinghisrecommendations, we includefour re- Our initial approachto simulate the cross-tropopause
actions: NO2 --• 0.5 HNO3 + 0.5 HNO2, NO3 --. HNO3, ozoneflux was to specifyozoneconcentrations in the low-
N205 ---+2 HNO3, and HO2 ---+0.5 H202 + 0.5 02, using ermoststratosphere (70 hPa)and let the modeltransportthis
reaction probabilitiesof 10-4 for NO2, 10-3 forNO3,0.1 ozone as an inert tracer into the troposphere. We found
for N205, and 0.2 for HO2. Aerosol surface areas are that this approachoverestimates the flux by a factor of 3-
estimatedon the basisof global 3-D sulfateconcentration 4 with the GEOS-1 data, as diagnosedby the simulationof
fields with monthlyresolutionfrom Chin et al. [1996], as troposphericozoneconcentrations at high latitudesin winter
describedby Wanget al. [ 1998a]. wheretransportfrom the stratosphere is a major source.Liu
Photolysisfrequenciesin the troposphereare calculated et al. [2001] previouslyfound a similar overestimatein a
with the Fast-J algorithm of Wild et al. [2000], which 7Besimulation withtheGEOS-1fields;theyobserved that
uses a seven-wavelength quadratureschemeand accounts the overestimate is less with the GEOS-STRAT fields but
accuratelyfor Mie scatteringby clouds.Surfacealbedoand still of a factor2-3. We havenot yet tried this approachwith
vertically resolvedcloud optical depthsare taken from the the GEOS-2 or GEOS-Terra fields.
GEOS meteorologicalarchivewith 6-hour resolution.The To overcome the difficulty of excessivestratosphere-
model as describedhere usesclimatologicalozoneconcen- troposphereexchangein the GEOS-1 and GEOS-STRAT
trations as a function of latitude, altitude, and month to meteorologyfields, we have adoptedthe Synoz (synthetic
calculatethe absorptionof UV radiationby ozone. In more ozone)methodproposedby McLinden et al. [2000] to rep-
recent work, we have developedthe capacityto use ozone resentcross-tropopause transportof ozone. In this method,
columninformationfor the specificyear of simulation. stratosphericozone is representedby a passivetracer that
The chemicalmassbalanceequationsare integratedevery is releaseduniformly in the tropical lower stratosphere
hour using a Gear algorithm [Jacobsonand Turco, 1994] (between 30øS to 30øN and 70 to 10 hPa) at a rate con-
for all grid boxes below the tropopause. The tropopause strainedto matcha prescribedglobalmeancross-tropopause
is diagnosedin the model using the standardcriterion of ozoneflux• We adopted thetotalfluxof 475 Tg 03 yr-j
a 2 K km-• lapserate. Abovethe tropopause we usea recommendedby McLinden et al. [2000] and which results
simplifiedchemicalrepresentationwhich includesproduc- in a satisfactorysimulationof verticalozoneprofilesat mid
tionof reactivenitrogenoxides(NOv) fromN20 oxidation, andhigh latitudesin winter,asdemonstrated below.
productionof CO and formaldehydefrom CH4 oxidation,
and lossesof tracersby reaction with OH or photolysis. 3. Model Evaluation
Stratospheric
productionratesof NO u OH concentration
fields,andNO•:/HNO3 concentration
ratiosusedto partition We presenthere a generalevaluationof the model using
NOv are monthlymeansprovidedby the 2-D modelof a simulationconductedfor the year 1994. The simulation
Schneideret al. [2000]. Photolysisfrequenciesin the usesthe GEOS-1 fieldsdegradedfrom 2øx2.5 ø horizontal
are computedwith a standardradiativetransfer resolutionto 4øx 5ø for the sakeof computionalexpediency;
stratosphere
model [Loganet al., 1981]. The resultingcross-tropopause it includes20 sigmalevelsin thevertical,from thesurfaceup
NOv fluxis0.65Tg N yr-j (including
0.17Tg N yr-• as to 10 hPa with the lowest levels centered at about 50 m, 250
NOx and0.48 Tg N yr-• as HNO3). Themainpurpose m, 600 m and 1100 m above the surface for a column based
of this simplified stratospheficchemistryis to accountfor at sealevel. A 6-monthinitializationis conductedfrom July
decayof tropospherictracerstransportedin the stratosphere, 1, 1993, to January1, 1994, and we focusour analysison
andto providea sourceof NOv to thetroposphere. Cross- the 12-monthperiodfor 1994.
tropopausetransportof ozoneproducedin the stratosphere Simulatedozoneconcentrations are evaluatedby compar-
requiresa specialtreatment,as describedin section2.5. ison with 1994 and climatologicalozonesondeobservations
[Logan, 1999]. CO concentrationsare evaluatedwith air-
craft observations as well as surface data from Novelli et al.
2.4. Deposition
[ 1998]. Other speciessimulatedin the modelincludinghy-
Dry depositionof oxidantsand water solublespeciesis drocarbons,acetone,NO, PAN, HNO3, and H202 are eval-
computedusing a resistance-in-series
model basedon the uated throughcomparisonwith observationsfrom various
original formulation of Wesely[1989] with a number of aircraft missionsthat have been averagedover chemically
 BEY ET AL.: GLOBAL MODELING OF TROPOSPHERIC CHEMISTRY 23,079

60ø1,,

30%

30%

60ø5

80 ø '120øW 60øW 0':' 60øE '120øE '180':'

Figure 2. Regionsusedto aggregateaircraftobservationsfor the purposeof model evaluation.Results

arepresentedfor selectedregionsas listedbelow.The aircraftmissionandthe corresponding monthused
for samplingthe model are indicatedin paren.theses.1, easternCanada (July, ABLE 3B); 2, U.S. West
Coast (August,CITE 2); 3, Maine (October,SONEX); 4, Ireland (October,SONEX); 5, U.S. West Coast
(April, SUCCESS); 6, Kansas(April, SUCCESS); 7, Japancoast (February,PEM-West B); 8, Japan
(October, PEM-West A); 9, western Pacific (October, PEM-West A); 10, Hawaii (October, PEM-West
A); 11, easternBrazil (September,TRACE-A); 12, tropical South Atlantic (September,TRACE-A); 13.
Africa westcoast(September,TRACE-A); 14, Antarctic(September,PEM-Tropics A); 15, tropicalSouth
Pacific(September,PEM-TropicsA); 16, southEasterIsland(September,PEM-TropicsA); 17, Hawaii
(March, PEM-TropicsB); 18, Fiji (March, PEM-Tropics B); 19, EasterIsland (March, PEM-Tropics B).

andgeographicallycoherentregions( Figure2). The regions July. The distributionof OH is in agreementwith current

in Figure 2 are thoseof Wanget al. [1998b] with updates knowledge,i.e. concentrations generallymaximum in the
from recentmissions(PEM-Tropics A [Hoell et al., 1999], tropicalmidtroposphere (reflectinghigh UV radiationand
SUCCESS [Toon and Miakelye, 1998], SONEX [Singh et water vapor) and in summer at 30øN (reflecting anthro-
al., 1999], and PEM-TropicsB [Raper et al., 2001]) and are pogenicenhancement of NOx and ozone). The maximum
similarto thosepresentedin thedatacompilationof Emmons values are higher by 10 to 20% than previous global 3-
et al. [2000]. The evaluationpresentedhere uses both D models [Hauglustaineet al., 1998; Wang et al., 1998b;
observations specificto 1994 and statisticsof observations Mickley et al., 1999]. The higher OH concentrationsrel-
for other years. Clearly, the ability to better constrainthe ative to our own previous models at Harvard appearsto
evaluationfor a specificyear is a major advantageof a result principallyfrom inclusionin the previousradiative
model driven by assimilatedmeteorologicalobservations, calculationsof an absorbingaerosolwith optical depth of
and the GEOS-CHEM model has been evaluated in other 0.1 at 310 nm varying inverselywith wavelength[Logan et
workswith suchtime-specificobservations[Liu et al., 2001; al., 1981]. The degreeof UV absorptionby tropospheric
Palmer et al., 2001; Bey et al., this issue]. However, aerosols,in particularorganicaerosols,is highly uncertain.
observations availablefor any givenyear are limited from a In the presentsimulationwe only include absorptionby
globalperspective,and interannualvariability is sufficiently sootparticleswith a wavelength-independent optical depth
small that evaluationwith observationsfor other years is of 0.001.
still usefulfor testingthe ability of the model to reproduce An evaluation of the global mean OH concentrations
generalfeaturesof globaldistributionsof troposphericozone simulatedby the modelcanbe madeusingthe methylchloro-
andrelatedspecies. form lifetime as a proxy [Spivakovslo,et al., 1990; Prinn et
al., 1995]. Spivakovskyet al. [2000] derivedfrom observa-
tionsan atmosphericlifetime of 4.6 yearsfor methylchloro-
form, in closeagreementwith Prinn et al. [ 1995]. Assuming
3.1. Hydroxyl Radical and Hydrogen Peroxide
stratosphericand ocean sinks for methylchloroformwith
Figure 3 showsthe zonally averaged24-hour mean OH correspondinglifetimes of 43 and 80 years, respectively,
concentrationssimulatedby the model for January and Spivakovskyet al. [2000] derivedan atmosphericlifetime
 23,080 BEY ET AL.: GLOBAL MODELING
Zonal Mean OH (10' moleculescm-•)
January
400
600
800
1000 ...... • ,
-90 -60 -50 0 50 60
Latitude(øN)
Figure3. ZonalmeanOH concentrations
(10s molecules
cm-3) simulated
July.
of methylchloroformagainstthe troposphericOH sink of
5.5 years. Wang et al. [1998b] and Mickley et al. [1999]
obtainedcorresponding lifetimesof 6.2 and7.3 yearsin their
respectivemodels(note that the methylchloroformlifetimes
of 5.1 and 6.2 yearsreportedby Wanget al. [1998b] and
Mickley et al. [ 1999] were calculatedconsideringonly the
column of methylchloroformup to 200 hPa and 150 hPa,
respectively).In our modelthe atmospheric lifetime against
the troposphericOH sink is 5.1 years. Our value is lower
than that of Spivakovskyet al. [2000] but is still within the
uncertaintyof the estimate.
Observations of H202 allow an additional evaluation of
HOx radicalconcentrations (HOx= OH + peroxyradicals)in
themodel. In mostof thetroposphere,
productionof H202 is
theprincipalsinkfor HOx. Figure4 showsobservedvertical
profiles of H202 obtainedduring severalaircraft missions
comparedto model valuesfor the same geographicalre-
gion and month. Observed and simulated concentrations
both peak at about 2 -km, reflecting combinedeffects of
decreasingproductionwith altitude(due to decreasingwater
vapor) and depositionto the surface. Comparisonsfor
specificregionsshow significantdisagreements, but there
is no consistentglobal bias. The unusuallyhigh values
observedover Brazil duringTRACE-A havebeenattributed
to rapid productionin biomassburningplumes[Lee et al.,
1997] and are not capturedby the model.
3.2. Carbon Monoxide
Simulated monthly mean CO concentrationsare com-
paredin Figure5 with climatologicalobservationsin surface
air (averagedover 5 to 10 years,dependingon the station)
as well as observationsfor 1994. Climatologicaland 1994
observedvaluesare similarwithin 10 to 20 ppbexceptat the
Tae-Ahn Peninsula(Korea) wherethe 1994 datapeak at 500
ppb in Novemberwhile the 6-yearmeanvaluepeaksonly at
300 ppb. The 1994 data for that monthconsistsof only one
measurement and can be discarded as anomalous. Observed
concentrationsare in generalhigher in the NorthernHemi-
OF TROPOSPHERIC CHEMISTRY
July
40O
• 600
800
, 1000
90 -90 -60 -30 0 50 60 90
Latitude(øN)
in themodelforJanuary
and
spherethanin the SouthHemisphere,reflectingthestronger
anthropogenicsources. The wintertimemaximum in the
NorthernHemispherereflectsin part low concentrations
of
OH (the main sink of CO) and in part reduced vertical
mixing. The spring maximum in the southerntropics
(AscensionIsland and Samoa) is due to seasonalbiomass
burning emissions. At most of the sites, simulatedCO
concentrations exhibit seasonal variations similar to those of
observations(with the exceptionof the peak at Ascension
Island, which occurs a month earlier in the model than
in the observations). However, at most of the sites the
model underestimates CO concentrationsby 10 to 20 pbb
(and up to 50 ppb). This is seenalso in Figure 6 which
showscomparison betweenverticalprofilesof observedand
simulated CO concentrations: the observed decrease of CO
concentrations
with altitudein the NorthernHemisphereand
the uniformverticalprofilesin the SouthernHemisphereare
capturedby the model,but the simulatedconcentrations are
systematicallytoo low by 10 to 30 ppb.
This problemof CO underestimate wasnot presentin our
previousglobal 3-D modelswhich usedsimilarinventories
[Wanget al., 1998b; Mickley et al., 1999]. It arisesfrom
higherconcentrations of OH in our model, as discussedin
section 3.1. In tests we have found that inclusion of an
absorbingaerosolin the radiativetransfercalculationcould
correctthe CO discrepancy, but thereare no goodobserva-
tional constraintsfor includingsuchan aerosol.In addition,
neither our simulationof methylchloroformlifetime nor
our calculatedH202 concentrationsshow any evident bias
relative to observations.
The direct CO emissionsusedin our model are in agree-
ment with the IPCC [ 1995] recommendationsbut are lower
than thoseusedin someotherglobal models:For example,
Hauglustaineet al [1998] and Granier et al. [2000] usea
globalsource
of 1218and1337Tg CO yr-•, respectively,
whilewe usea globalsource
of 1043Tg CO yr-1. The
differenceis mainly due to naturalsourcesfrom vegetation
and ocean which are poorly known and remain a matter
 BEY ET AL.: GLOBAL MODELING OF TROPOSPHERIC CHEMISTRY 23,081

of speculation.Anotheruncertainsourceterm for CO is and683Tg CO yr-1 [Holloway

etal., 2000].OurCOsource
oxidation of NMHC which is estimatedby IPCC [1995] fromNMHCoxidation of 355Tg CO yr-• maybetoolow
to bein therangeof 200to 600Tg CO yr-• butin recent becausethe model doesnot include oxidationof terpenesor
models as647Tg CO yr-• [Granieretal., 2000] higherbiogenic
isreported hydrocarbons, nordoesit includeNMHC

Maine (SONEX) Ireland (SONœX) JoponCoost(PEM West B) EosternBrozil(TRACE-A)

' ' 'Oct ' Oct
200 36 •oo
51
37
68
15
!oo 200
400 12 -00 e P00 400- -•E•-• 12
2

17 7
600
2
•oo 300 6007 '•,
13

800 •oo

:
,

1000 ! i i )00 ½. i i )00 , 1000 / ,

0 2 3 4 0 2 3 4 0 1 2 3 4 5 0 1 2 5 4 5

Tr•SAtlontic (TRACE-A) AfricoWCoost(TRACE-A) Japan (PEM West A) WPacific (PEM West A'
i

' ' 'Sep' 'Oct '

200

'Sep' •
39
.35
5
8
18
200 25
11o
2.3
'.oo

.00
2OO

4OO
1.3
10
50
10
400 12 400 ,-, _ 5 19

5 14-

6 11
600 ;oo 6OO

600
9

8OO 800 "•. too

c-lOOO
11
000
__• 1 )oo
66 800
•• .
ooo ½, '•'
25
i

o 5 4 5 0 1 2 5 4 5 0 1 2 5 4 5 o 1 4 5

D StPocific(PEMTropicsA) SEosterls(PEMTropicsA) Antarctic(PEMTropicsA) Hawaii (PEM TropicsB)

200 Sep 2 200 200 12
7

400¾_
'
76
69
400 12 400 40
600 72 14 16 2
t 2 12 ['-•• 4
800 52 • , • .3 800f •.3 800 .
1000
Z,,•0t lC• 1210000••33•18•000
•___• ;7'
Tropics)
Fiji
(PEM
Tropics
B) Eosterls
(PEM
'Mar
2oo•Mar•
t 2oo• 38
14

20
25

400 46 4001I 22

600 ' 17
600[• 9

800'•
1000
•9 10001
800[••&
•, , ,
42
,
0 1 2 5 4 5 0 1 2 3 4 5

H202 (ppb)
Figure4. Comparison of observed andsimulatedverticalprofilesof H202 concentrations.
Observations
areaveraged overtheregionsin Figure2. The opensquares aremeanobserved values(withhorizontal
barsfor standarddeviations),andthe opentrianglesand solidlinesare medianobservedvalues.Open
circlesanddashedlinesaresimulatedvaluesfor 1994,sampledoverthe sameregionandmonth.
23,082 BEY ET AL.' GLOBAL MODELING OF TROPOSPHERIC CHEMISTRY

Mould Bay (76N,1 19W) Heimaey (65N,20W)

25O 25

2OO 20

150 15

lOO 10

50 5

J F M A M J J A S 0 N D J F M A M J d A S 0 N D

Cape Meores (45N,123W) Niwot Ridge (40N,105W)

250 25

200 2O

150 15

100 10

50 5

J F M A M J J A S 0 N D J F M A M J J A S 0 N D

Harvard Forest (42N,72W) ,

Tenerife (28N, 16W)
300 5O

200 O0

100 5O

0
J F M A M J J A S 0 N D d F U A M J J A S 0 N D
Tae-ahn Peninsula(56N,126E) Mauna Loo, (19N,155W)
5O0

4OO

.500

200 '0- - .-- 0---0'"

50
100

i i i i 0
J F M A M J J A S 0 N D J F M A M J J A S 0 N D

Ragged Point (15N,59W)

,
AscensionIsland (7S,14W)
150 150

100 lO0

50 5o

• i i i ! i i , i i i i 0 i i i i i i i i i

J F M A M J d A S 0 N D A M J J A $ O N D

Samoa (14S, 170W) Cape Grim (40S, 144E)

IO0 lOO

8O 80

60 6o

40 40

20 2o

o
J F M A M J J A S 0 N D J F M A M J J A $ 0 N D

Figure 5. Comparisonof observedand simulatedmonthlymeanCO concentrations in surfaceair.

Trianglesand solidlinesare observed valuesfromNovelliet al. [1998]averagedover5 to 10 years
depending on the sites;verticalbarsarestandarddeviations
representinginterannual
variabilityof the
monthlymeans.Long-dashed linesaretheobserved
valuesfor 1994. Opencirclesanddashedlinesare
values from the model for 1994.
 BEY ET AL.' GLOBAL MODELING OF TROPOSPHERIC CHEMISTRY 23,083

emissions frombiofuelcombustion. Clearly,therearemajor ethaneconcentrations are usuallybelow 500 ppt at remote

uncertaintiesin the sourcesof CO thatcouldbe responsible sitesandin thefreetroposphereandincreasein theboundary
for our model underestimate of CO concentrations. layer of regionsinfluencedby anthropogenic pollution or
biomassburning. The model reproducesthe vertical struc-
3.3. Hydrocarbons and Acetone turesbut underestimatesobservedconcentrations,by up to a
Comparisonbetween simulatedconcentrationsand air- factor2 in someregionswith high anthropogenic emissions
craftobservations of ethaneareshownin Figure7. Observed (Maine and JapanCoast) and high biomassburningemis-

WestCoast(SUCCESS) Kansas (SUCCESS) Maine (SONEX) Ireland (SONEX)

Q •,pr ' c •Apr ' T--'Oct .... Oct ' 27
200 200 200 83

(• 447
•52
139
93
101
2O
52 221 96

215
52 66
400 1• 27
52
400 176
400 40 19
66 62 16 18

29 (• •,-• 69 80 15
600 600 600
4 •6 17 18

41 37 11

8OO 800 8O0

96 10 15

15 8 28
lOOO i I i ,,i 1000 1000 , i, i 1
o 60 120 180 240 3(10 0 60 120 180 240 300 0 60 120 180 240 300 0 60 120 180 240 300

Jo3onCoost(PEMWestB) EasternBrazil(TRACE-A) TrpSAtlontic

(TRACE-A) AfricoWCoost
(TRACE-A)

, !!!
,• • 642
| [ , .4•- 127 • 49
600 301600
• 4 T m 1Rq
I 600 264 •, • 613
1ooo ,
0 60 120 180 240 300 0 60 120 180 240 500 0 60 120 180 240 500 0 60 120 180 240 500

apan(PEMWestA) Wfac[fic(PEMWestA) SiPacCPac

(PEMTropics
A) SEasterls
(PEMTropics
A)

•oo ] 400
•oo•• oct [•
• •oo Sep
400 ' • •e • '

600 600 600 600

800 16 800 3 800 1 800

1000 ,•, , ,'• 1 1000

[ •• , ,49 t 1000 1000
•
0 60 120180240300 0 60 120180240300 0 60 120180240300 0 60 1201 80 240500
Antorctic ( PEMTropics A) Howell(PEMTropicsB) Fiji (PEMTropicsB) Eosterl
s (PEM TropicsB)

• 256 j

•2•j 'L 206

j
405
1 • 495
j]
447 [ 984
•2•

800 191 800 97 800 •97 800 234

ooo , , ooof ,1,, 1 ooo ooot

0 60 120 180 240 500 0 60 120 180 240 300 0 60 120 180 240 500 0 60 120 180 240 500

CO (ppb)
Figure 6. SameasFigure4, but for CO.
 23,084
BEYET AL.:GLOBALMODELINGOFTROPOSPHERIC
CHEMISTRY

Moine (SONEX) Irelond

,
(SONEX)U.S.
West
Coost
(CITE
2) JoponCoost (PEM
WestB)
2oo øe '=
•.-•L•-
'Oct;o
•o
]
• t
200[
[
L
•
' 'Oct',o
55 '
;
e
' Zug't •....}'
1 zuur
'qe
' 'Feb'
ß

, • e ' ½ 4 ß • s '
•uu , • 4 600

_ .;__• , •, • •3oo• , ,
U 400800120016002000
0 400800120016002000
0 400800120016002000
0 400800120016002000
EosternBrozil
(TRACE-A)
TrpSAtlontic
(TRACE-A)
AfdcoWCoost
(TRACE-A)
Jopon
(PEM
West
A)

0 ,
400800
120016002000
0 400800
120016002000
0 400800
120016002000
0 400800
120016002000
p
Wocific
.... (PEM
West
A) Pocific
(PEMWest
A) StPocific
(PEM Tropics
---• A) SEosterls
(PEMTro
Pics
A)
2oo•
• • Oct][
• 200

•oo•' •o •oo •o,,' •o,

89 •oo ' 10
:,
0 40........ 1000 "
• • 120016002000
0 400800120016002000
0 400800120016002000
0 400800120016002000
Antarctic
(PEMTropics
A) Hawaii
(PEMTropics
20oo Sep•• 20o Mar•,
] 20• Mar•.
• 200[
o_ Mar,,
• 12 5o , 1

•oo ;; ] ,oo

000 ,7 J 1)00 , J 10oot•....

0 4008001200160020000 400800120016002000
0 400800120016002000
0 400800120016002000
C•He (ppt)
Figure7. SameasFigure4, butfor ethane.

sions(SouthAfricaandBrazil). A similarunderestimate
bothanthropogenic
andbiomass
burning
emissions,
which
hadbeen
previously
reported
byWang
etal. [1998b],
thus pointsto a possible
underestimate
of bothcategories
of
indicating
that
this
problem
isprobably
notdue
toourhigheremissions.
OH concentrations
butmorelikelyto anunderestimate
of Globalethane
sources
of Wanget al. [1998b]aswellas
sources.
Model
results
aretoolowinregions
influenced
by in ourmodel
include
6.6Tg C yr-• fromanthropogenic
 BEY ET AL.: GLOBAL MODELING OF TROPOSPHERIC CHEMISTRY 23,085

activities (mainlynaturalgas)and3.0 Tg C yr-• frown Ireland)agreefairly well with the observations.

In eastern
biomass burning.As pointedoutby Wanget al. [1998b],this Canada,themodelunderestimates
observedvaluesby a fac-
globalinventoryis lowerthanpreviousestimates (12-13Tg tor2, a problem
previously
reported by Wangetal. [1998b].
C yr- t) fromRudolph[1995].Biogenic andoceanic sources Scalingacetoneemissions
to monoterpeneemissions (asis
of ethane are not included in our model. These sources done in the current version of the GEOS-CHEM model)
appearto be small[Rudolph,1995]but couldaccountfor ratherthan isopreneemissions(as was done in Wanget
1.6 Tg C yr-1 [Hauglustaineet al., 1998]whichwould al. [1998a,1998b])did not correctthisunderestimate.
The
a 15% increaseof ourcurrenttotalinventory.An modelunderestimates
represent by a factor of 2-3 observedacetone
underestimate of naturalgasesemissionsin the Piccotet al. concentrationsover the South Pacific in fall (PEM-Tropics
[1992] inventoryis a morelikely reasonfor the underesti- B aircraft mission). Matching theseobservations
would
mate, as found in simulationsof propaneand isobutane(D. requireeithera largedispersed
secondary source of acetone
J. Jacobet al., Atmospheric budgetof acetone,submittedto ora largeoceanic emission[Singhetal., 2000b].An inverse
Journalof Geophysical Reserach,2001,hereinafter referred analysisof acetonesourcesand sinksusingthe GEOS-
to as Jacobet al., submittedmanuscript,2001 ). CHEM modelis presented by D. J. Jacobet al. (submitted
Figure8 showsa comparison betweensimulated monthly manuscript,2001).
meansand aircraftobservations of isopreneconcentrations.
Observedvalues show a strong gradient in the boundary
3.4. Nitrogen Species
layer,decreasing from about1 ppb nearthe surfaceto less
than 0.05 ppb at 3 km at most of the sites. This vertical Comparison of observedandsimulated
NO andPAN con-
structureaswell asthe overallmagnitudesof concentrations centrations areshownin Figure10andFigure11. The model
are capturedby the model, lending some supportto our typicallyreproduces NO concentrations
withina factorof 2.
estimate
ofisoprene
emission
(397TgC yr- • globally).
The HighNO concentrations
oversouthern
AfricaandtheSouth
C-shapedprofilessimulatedover the southeastern United Atlanticare dueto biomassburningandlightning[Jacobet
Statesin summerreflectconvectivepumpingto the middle al., 1996;Pickeringet al., 1996]. Lowerconcentrations
are
troposphere,but no observations
are availableto test this obserYedelsewherein the tropics,and againtheseare well
model feature. captured
by the model.The mostseverediscrepancy
is an
Figure9 compares
observed
andmodeledverticalprofiles overestimateof NO concentrations
in the uppertroposphere
for acetone. Model results in midlatitudes (Maine and overHawaii andFiji duringPEM-TropicsB. As discussed

Peru
EasternCanada(ABLE5B) EasternBrazil (,•RACE-A) South Africa (1-RACE-A) ! T-- ! r '-r--• i [ i i ] , i -l--.-
500 5OO 500 ' '-' 5OO
Sep e.
ß
Jul
ß

60O 6O0 600 o 6OO

'e
ß

11÷ ß

700 7OO 700 6 7O0

.

8OO 78! 800 800 3 8OO

35 I
•-• 900 9OO 90O 9OO
¸
-- u

• 1ooo 000 i i i , i 11 000 , ....... 1000 ,

• O. 0.1 0.51 2 5 O.01 o.1 o.51 2 51o 0.01 0.1 0.51 2 510 0.01 0.1 0.51 2 510

Tennessee Southern U.S.

I'--T•I III 500 1 [ ! ,,q, i i 1
• 500
ß Aug .
ß

' Jul
ß

½'
• 600 ,
.
600 ,
ß

ß
ß
ß

700 700 ß

8OO 80O

..
9O0 900 ..

1 ooo i i i i i ! (• 1000 i i

O.Ol 0.1 0.51 2 510 0.01 0.51 2 5 10

Isoprene (ppb)
Figure8. SameasFigure4, butforisoprene.
Datafromthe"Peru"regionarefromHelmigetal. [1998];
datafromthe"Tennessee"regionarefromGuentheret al. [1996];datafromthe"Southern
U.S."region
are from Andronache et al. [ 1994].
 23,086
BEYETAL.:GLOBAL
MODELING
OFTROPOSPHERIC
CHEMISTRY

Eos_tern
Conodo
(ABLE
5B) Moine
(SONEX) Irelond
(SONEX)JoponCoost
(PEM
West
B)
200
ø'e•' Ju'l
t e' ' ' Oc•t
] •t 20c 'e •.
, .
•o 4 200•e...,,
•2
•
1 ,',,
1 •__I e F•b

% V ,, ,oo
,ooo
ø400
, 800•20016002000
;,: ,,oo 0 400800120016002000
0 400800120016002000
0 40080020016002000 1

EosternBroz[I
(TRACE-A)
TrpSAtlontic
(TRACE-A)
Afr;coWCoost
(TRACE-A)
Howoii
(PEM
Tropics
B)

400 ff ••
, ½ ,,
200
400
[
200
* %•P
200
% M•r
8oo ;•oo •oo a ? 8oo
0 400
800
320016002000
0 400
800
120036002000
0 400
800
120016002000
0 400
800
120016002000
Fij•(PEM
Tropics
B) Eosterls
(PEMTrop;cs
B)
' ' ' M'
200[• •iS-- ,•r
•o 20C ' ' ' M•r

600 • 500
800 3 •00

,ooog , , ', ,,oo ....

o oo,oo,oo=ooo o oo,oo,ooooo

Acetone (ppt)
Figure9. SameasFigure4, butforacetone.

byWang etal. [2001

], these
observations
weremadeunder
conditions
of particularly
intense
marineconvection
Nitricacid(HNO3)is produced
when reaction
in theatmosphere
by
of NO2withOH andby hydrolysis
of N205in
low-NOx
airfromthemarine
boundary
layerispumpedaerosols.
Majorsinks
aredryandwetdeposition.
Compari-
frequently
totheupper
troposphere. sonof modelresults
withobserved
HNO3concentrations
is
Peroxyacetylnitrate
(PAN) isareservoir
species
forNOx shown
inFigure12. Themodel
typically
overestimates
the
produced
by oxidation
of organic
compounds.
Observedobservations
bya factorof2-3.Thisproblem
iscommon
to
PANconcentrations
arehighoverthecontinental
regionsmostcurrentglobal
3-Dmodels of troposphericchemistry
(especially
whereinfluenced
bybiomassburning
orfossil [Wang
etal., 1998b;
Hauglustaineetal., 1998;Mickley
et
fuelemissions)
andlowinregions
remotefromdirect
NO• al.,1999;
Lawrence etal.,1999].
Thepartitioning ofHNO3
sources.The modelcaptures similartrends. Simulated intoaerosols
mightprovide
anexplanation
sincethemodel
concentrations
at northern
midlatitudes
areconsistent
with doesnotdifferentiate
betweengaseous
andaerosol
nitrate.
observed
valuesalthough the modeloverestimatesPAN Thereis alsostrongevidence
thatthemodelunderestimates
concentrations
over Japan inOctober,aproblem
previouslyprecipitation
scavenging
intheuppertroposphere,
asshown
notedby Wanget al. [1998b].Simulated
PANconcentra-by Liu et al. [2001]in a simulation
of 21øPb
and7Be
tions
fortheTRACE-A region,
which washeavily
impacted tracers.
Lawrence andCrutzen [1998]suggested
thatcirrus
bybiomassburning,arehighbutstillunderestimate
obser-
vations.
Suchunderestimate
waspreviously
notedforethaneprecipitation
could leadto a considerable
HNO3fromtheupper troposphere.
scavenging
Thisprocess
of
is not
andmayreflect
insufficient
NMHCemissionfrombiomassrepresented
in ourmodel.(Theyalsosuggested
thatcirrus
burningin themodel.
precipitation
wouldscavenge
H202; however,
thatseems
 BEY ET AL.: GLOBAL MODELING OF TROPOSPHERIC CHEMISTRY 23,087

dubioussinceH202 is onlyweaklypartitionedintothecirrus Figure 13 comparessimulatedand observedseasonalvari-

ice phase[Mari et al., 2000].) ations of ozone concentrations at 300, 500, and 800 hPa.
Where available,1994 seasonalvariationsare alsoreported.
3.5. Ozone The 1994 observationsare usually within 20 ppb of the
Evaluation of simulated ozone concentrations uses the climatology,with the exceptionof high latitudesat 300
multiyear climatology of ozonesondedata presentedby hPa where small shifts in tropopauseheight can introduce
Logan [1999] as well as 1994 ozonesondemeasurements. considerablevariability in ozone; model evaluationis not

Maine (SONEX) Ireland (SONEX) U.S. West Coast (CITE2) JapanCoast(PEM West B)

400m_.•,,/•m
''24'
•oor• •oo
400
/
[,,•..•._ 223
I 400'•' 2
600 ;/• 7 • •. 600 600

800
'e
e • 800
000__• ,"e','•-e • 1 ' -........... 1000 •e.._
-e ..... 119
"- I 1000 [ •• eß........... 11
"
0 40 80 120 160 200 0 40 80 120 160 200 0 40 80 120 160 200 0 40 80 120 160 200

EasternBrazil(TRACE-A) TrpSAtlontic(TRACE-A) AfricoWCoost(TRACE-A) Japan (PEM West A)

ß• 7 ,½' • ß 51

800 [ 4
ooo•, •---:-'-':....1 •ooo•....
lO, ooo•.... 1 'e t
800
• e-
1000 __
0 40 80 120 160 200 0 40 80 120 160 200 0 40 80 120 160 200 0 40 80 120 160 200

WPocific
(PEMWest
A) Pacific
(PEMWest
A) StPoc•f•c
(PEMTropics
A)SEosterls
(PEMTropics
A)
; [i2OO

400
:,t 2oo ½.- ego
•5 •
2o0
r •
½
,, ½•
9• •2
'' 80

•ooo•
I ,, •ooo'•
, •ooo• , , ,
,,
'• 1 ,c
o 4o so 12OlSO2OO o 4o •o 12o 16o 2oo o •o so •2OlSO2OO o 4o so 1•o•o2oo

Antarctic (PEM TropicsA) Hawaii (PEM Tropics B) Fiji (PEM Tropics B) EasterIs (PEM Tropics B)
' ep' ' ' 'Mar• 106 2OO 542 2OO
200 •
7
200 •--" 9O
88
97
572
357
298
E).•
=•F':' 99
166
/, 182
241 384 "' 205
400 21 400 40O 4O0
55 268 •
.
113
20 144

22 19 247
600 600 6OO 6O0
• 243
15 26 170
6 143
105 87 110

8OO 8O0
800 16 800 29 98 115

236 176
1000 i • , 1000F• , , , I 1 ooo • i , I , i 000 I I i I

0 40 80 120 160 200 0 40 80 120 160 200 o 40 80 120 160 200 0 40 80 120 160 2(

NO (ppt)
Figure 10. Sameas Figure4, butfor NO.
 23,088 BEYETAL.:GLOBAL
MODELING
OFTROPOSPHERIC
CHEMISTRY

Moine
(SONEX) Irelond
(SONEX) U.S.
West
Coost
() JoponCoost
(PEM
West
B)

•, ] 200 t 200 '

•oo • •oot..• ::1•oo• ••_•
800 BOO BOO

•ooo' ' ½', •

0 100200500400500
•'
0 100200500400500
•oo• •oo', , ,
0 100200500400500 0 100200300400500
Eos(ernBroz[I
(TRACE-A)
TrpSAtlont[c
(TRACE-A)
Afr[coWCoost
(TRACE-A)
Jepon
(PEM
West
A)

•oo[
• ,e•.
• ,• ,• ,e•;
e½T
• •oo[
•.-,e•,,
J •.•
• • • 400 •• 2 •0o

•,oo * ,•
•ooo• • . •,oo
,oo.,•
= •. ,oo• ::•
• 0 100200500400500 0 100200500400500 0 100200500400500 0 100200•00400500
L p
• Wocific
(PEM
Wes(A) Poc[fic
(PEMWes(A)StPocific
(PEM Tropics
A)SEos(erl
(PEMTropics
A) s

200 20 • • 200 Sep•g 200o

, .oo
' 2• 600 •7 600
: ,.
6 ,,
24 2

800
[
1000 •6
• 100(
801 2 1300
•00 24 1•00
•00
, ,•o 34 '• ,
0 100200300400500 0 100200300400500 0 100200300400500 0 100200300400500
Howoii
(PEMTropics
) Fiji(PEM
Tropics
B) Eosterls
(PEMTropics
B)

•oo• ' 17 •oo• • • •oo

.oo
•oo••
800
• t ,oo
]00
•oo ,:
lOOO '- 1:oo,• •:oo• , , , • 1 •:oo•
0 100200300400500 0 100200300400500 0 100200300400500 0 100200300400500
PAN (ppt)
Figure11.SameasFigure4, butforPAN.

wellconstrained
at300hPabecause
ofthishighvariability.ppb of the observedvaluesandhavethe correctseasonal
Thedistribution
andseasonalvariation
of troposphericphase.At highnorthern latitudes
themodelcaptures the
ozonein theclimatology
is described
in detailbyLogan spring maximum inthelowertroposphere
andthemaximum
[1999].Witha fewexceptions,
modelresults
arewithin10 fromMaytoAugust in themiddletroposphere.
Seasonal
 BEY ET AL.: GLOBAL MODELING OF TROPOSPHERIC CHEMISTRY 23,089

ation of cross-tropopause
variationsat northernmidlatitudesare relatively well repre- transport(lessthan that shown
sented.However,the model tendsto underestimateslightly by Wanget al. [1998a]). Elevatedconcentrations at 800
the amplitude
of the seasonal variationin the extratropicshPa at Boulderin summerare likely due to pollutionfrom
(Hohenpeissenbergand Saporrofor example),a problem Denver,which we do not capturewell in the model. Good
which we ascribetentativelyto insufficientseasonalvail- simulationis usuallyachievedin the tropicsandsubtropics

Mc•ir,e(SONEX) Irelond(SONEX) U.S. West Coost (CITE2) Ja,onCoost (PEM West B)

200 ' •..o.....

-al•--- 'o•t' t 200I
[ __••
'•45--'1 ' .o......
'o•t' t 200 ....
27•-'1 e..o AugI 200 .... e
400 s 400 400 'e 400

aoo • .... 1 søøt •- I

8oo[•• • ,o] 8oo
•
1000/• ,•-e, , , / 1000 • ,R , ,
0 200 400 600 800 1000 0 200 400 600 800 000 0 200 400 600 800 1000 0 200 400 600 800 1000

Easterngrozil(TRACE-A) TrpSAtlontic(TRACE-A) AfricoWCoost

(TRACE-A) Jopon (PEM WestA)
• 'o ' •ep'
2o0 % Sep
•1 200 • Se•
• 200
[• • f•5It 200•
[ "'•'
• •- bct'
ß
400 • ,2 400 • • 4oo• • s 1 4oo•
& 16 5

800 • 4o 800 800

• 1000•
0 200 400 600 800 1000
•000
"'•0 200 400 600 800 1000
1000/
0 200
,•--, .... h'"
400 600
,
800 1000
• 800[
/ 10001•
0 200 400 600 800 1000

WPo•ific
•PE•W•st
A) •oci•ic
(,PEM,
We•t
A) StPoc[f[c
(PEM
Tropics
A)SEosterls
(PEM
Tropics
A)
••ook o•, ] •oo
[ •.• o• ] •ook,..o
•e• t •ook
• 23 4

•oo• • I •oo• • I •oo • •oo

•oo• , ] •oo•
• ,•t •oo•• ,,• •oo•;
•oo• • ] •oor• • •oo •oo
ooo• .... • ,ooom .... • •ooo• ..... I •ooo• ......
0 200 400 600 800 1000 0 200 400 600 800 1000 0 200 400 600 800 1000 0 200 400 600 800 1000

Antorctic(PEMTropicsA) Howoil(PEM TropicsB) Fij• (PEM TropicsB) Eosterls(PEM TropicsB)

' ' g•p' t [ '• ' 'Mor' t t•' ' 'Mo•' t t •' ' 'M•'
•oo .•.............
• •oo[½, •• •oo• •,• ,oo..
600• 600 • • •• 2• • ••

8o0 8o0 •
, 800• ,2] 800[•
•ooo, , , , ; t lOOO
•½• lOOO• •ooo•
0 200 400 600 800 1000 0 200 400 600 800 1000 0 200 400 600 800 1000 0 200 400 600 800 1000

HNO; (ppt)
Figure 12. SameasFigure4, but for HNO3.
 23,090 BEYETAL.:GLOBAL
MODELING
OFTROPOSPHERIC
CHEMISTRY

Resolute
(74N,95W)- 800mbor Resolute
(74N,95W)- 500mbor Res(•lute
(74N,95W)- 50Orebar
200 ' ß I .....

•
•

o
,oo ........ ,oo
80
60

40
80
60

40
150
i I

'' --
ii 1
j F M A M J J A $ 0 N D J F M A M J J A $ 0 N D J F bl A bl J J A $ 0 N D

Edmonton
(55N,114W)- 800mbar Edmonton
(55N,114W)- 500mbar Edmonton
(53N,114W)- 50Orebar

J F M A M J J A S 0 N D J F M A M J J A $ 0 N D J F M A M J J A S 0 N D

Hohenpe[ssenberg
(47N,11E)- 800mbarHohenpe[ssenberg
(47N,11E)- 500mbarHohenpeissenberg
(47N,11E)- 500mbar
100[ ........ 100•
............. I 200
150
• 100
o 40 40 '

J F M A M J J A S 0 N D J F M A M J J A S 0 N D J F M A M J J A $ 0 N D

Sapporo
(45N,141E)- BOOmbar Sapporo
(45N,141E)- 50Orebar Sapporo
(45N,141E)- 50Orebar
,oo
80 ,oo............
80 f ..... ,
•
• •o •o
-• •øI
o 40 40

2• 2• • • 50
0 •
J F M A M J J A S 0 N D J F M A M J J A S 0 N D J F M A M J J A S 0 N D

Boulder
(40N,105W)- 80Orebar Boulder
(40N,105W)- 50Orebar Boulder
(40N,105W)- 500mbor
,oo[
80
,oo[•
80
............ .•oo............
• O0
o 40 40

2• , , , ,
20
0
50
0
J F M A M J J A S 0 N D J F M A M J J A S 0 N D J F M A M J J A $ 0 N D

Kogoshimo
(32N,131E)- 800mbor Kogoshimo
(32N,151E)- 500mbor Kagoshimo
(32N,131E)- 50Orebar
,oo
80 ,oo
80 ............
/ \ ,oo
f ............
•
o 40 40
100• .-e ....

0 .... i • • i i • i 0 i i i • , , •
J F M A M J J A • O N D J F M A M J J A S O N D J F M A M J J A S 0 N D

Figure
13.Comparison
ofobserved
andsimulated
monthly
meanconcentrations
ofozone at800,500,
and300hPa.
Observations
(open
triangles
andsolid
lines)
arefrom
theozonesonde
climatology
ofLogan
[1999];
vertical
bars
arestandard
deviations
corresponding
tointerannual
variability.
Long-dashed
lines
aretheobserved
values
for1994(there
arenoobservations
in1994atSamoa
andNatal).
Model
values
(opencirclesanddashedlines)arefor 1994.
 BEY ET AL.: GLOBAL MODELING OF TROPOSPHERIC CHEMISTRY 23,091

to within the constraintsofferedby the observations.The maximumdue to biomassburningemissionsthat the model

observedminima in easternAsia (Kagoshimaand Naha) captureswell. The longitudinalgradientobservedin the
due to the summermonsoonare capturedby the model. southerntropicsbetween Natal and Samoa is also well
The springmaximumandsummerminimumobserved in the captured.
northernsubtropics (Hilo, for example)arewell represented Table 5 givesthe global budgetof tropospheric
ozone
by the model throughoutthe troposphere. Observations in the model. The global photochemicalproductionand
in thesouthern
tropics(Natal)showa largeaustralspring destruction
ratesof ozoneare4900Tg yr-t and4300Tg

Naha (26 N, 127 E) - 80Orebar Nahe (26 N, 127 2) - 50Orebar Naha (26 N, 127 E) - 300mbar
,00 -- 100 - 200

8O
80 150
• $0
0-- '-©'../ •--. •--@-
• 60 40
100
o

2O 20 50
0 0
J F M A M J J A $ 0 N D J F M A M J J A S 0 N D J F M A M J J A $ 0 N D

Hilo (20 N, 155 W) - 800mbar Hilo (20 N, 155 W) - 50Orebar Hilo (20 N, 1.55 W) - 300mbor
100 100 200

80
80 150
60

40

20
40

20
'--

' • • ' 100

50

d F M A M J J A S 0 N D J .• M A M J J A S 0 N D J F M A M J J A S 0 N D

Natal (6 S, 35 W) - 800mbar Natal (6 S, 35 W) - 50Orebar Natal (6 S, 35 W) - 300mbar

lOO lOO : 2OO

80 80 150
60 60
100
40 4o

20 20
5o
o o o
j F M A M J J A S 0 N D J F M A M J J A $ 0 N D J F M A M J J A $ 0 N D

Samoa (14 S, 170 W) - 80Orebar Samoa (14 S, 170 W) - 500mbar Samoa (14 S, 170 W) - 30Orebar
200

lOO
80
lOO•
80
150

1 O0

60
•o

20

J F M A M
.e .....

J J A S
e.

0 N D
60
•'-.. _•
4o

20

J F M A M J J A $ 0 N
,

D
50

0
J F M A M J J A S 0 N D

Lauder(45 S, 169 E) - BOOmbar Lauder(45 S, 169 E) - 500mbor Lauder(45 S, 169 E) - 30Orebar

100 100•1 200.............
80 80 150
60 60
•oo
20 50
0 , , , A, , , , • , • A ,•, 0 • • , , • , i , , • ,

J F bl A M J J A S 0 N D O F M A M J J A S 0 N D d F M a M J O A S 0 n D

Syowa(69 S, 39 E) - 80Orebar Syowo(69 S, 39 E) - 500mbor Syowa (69 S, 39 E) - 30Orebar

100 1 O0 ......... 200 ....... "' ....

BO 80
150

,, 60 6O

1oo
'''t.a-'
-(•
....
0'• 40.. ._
_o
.•
o 40
o
50
20

, , , • , , • i , , • , 0 _ , , • • , , , , , , , o , • , , • , , . , , , , •...
d F M A M d d A S 0 N D d F M A M d d A $ 0 N O d F M A bt J d A S 0 N D

Figure 13. (continued)

 23,092 BEY ET AL.: GLOBAL MODELING OF TROPOSPHERIC CHEMISTRY

Table 5. Global Budgetfor TroposphericOzonein the GEOS-CHEM Model

Global NorthernHemisphere SouthernHemisphere

Sources,
TgOayr- •
Chemicalproduction 4900 3100 1800
Stratospheric
influx 470 280 190
Total 5370 3380 1990
Sinks,
TgOayr- •
Chemical loss 4300 2600 1700
Deposition 1070 740 330
Total 5370 3340 2030
Burden,Tg Oa 315 175 140

The budgetis for the extendedodd oxygenfamily definedas Oa + NO2 +2 x NO3 + PAN + PPN + MPAN + HNO4 + HNO3 +
3 x N9.O5 andappliesto thecolumnup to themodeltropopause.Valuesareannualmeansfor 1994.

yr-•, respectively,
with a stratospheric
inputof 470 Tg The model systematicallyunderestimates observedCO
yr-•. Previousglobal3-D modelsindicatephotochemicalconcentrationsby 10-30 ppb, which couldreflecta problem
productionrangingfrom3314to 4550Tg yr-• andphoto- with current source inventories as well as an overestimate
chemicallossrangingfrom2511to 4065Tg yr-• [WMO, of OH. Simulation of ethane indicates an underestimate of
1998; Lelieveldand Dentener, 2000]. Stratosphericinputs sources.The largeunderestimate
of acetoneconcentrations
inthesemodels
varyfrom390to768Tg yr- 1 [WMO,1998]. over the South Pacific suggestsa large oceanic source.
Our calculatedvaluesfor the photochemicaltermsare at the Simulated concentrationsof NO and PAN are generally
high end of previousmodels.They are in particularhigher within a factor of 2 of observed values (often much bet-
than in our previousglobal 3-D modelsat Harvard;Mickley ter) and show the correct vertical structure. The model
et al. [ 1999] and Wanget al. [ 1998b] reportproductionrates overestimates
HNO3 concentrations by factorsof 2-3 in the
of 4330and4100Tg yr-• andlossratesof 3960and3680 remotetroposphere, a problemwhichwe attributein partto
Tg yr-•, respectively.
Thedifference
appears
to reflectthe insufficientscavenging.
strongerUV actinicfluxesin thepresentmodel,asdiscussed The model reproduceswell the global distributionof
previously. troposphericozone concentrationsas determinedfrom
ozonesondeobservations. It simulatesusually to within
4. Conclusion 10 ppb the 1994 observations as well as the multiyear
climatology(whichare similarexceptnearthe tropopause).
This paperprovideda first descriptionof GEOS-CHEM, it capturesthe observedseasonalphasesand amplitudes
a global 3-D model of troposphericchemistrydriven by in differentregionsof the troposphere.There is a slight
GEOS assimilatedmeteorologicalfields from the NASA underestimate in the amplitudeof the seasonalvariationin
Data Assimilation Office (DAO). A 1-year simulationis the extratropicalNorthernHemispherewhich we attribute
presentedfor 1994, and results are evaluatedwith obser- to insufficientseasonalvariationin the parameterizedcross-
vationsboth for 1994 and for other years. We show that tropopause ozoneflux.
the modelis capableof representingthe generalfeaturesof In a companionpaper [Be),et al., this issue], we use
the global distributionsof troposphericozone and related the GEOS-CHEM model to examine the Asian outflow of
speciesalthoughthereare somesignificantdiscrepancies. ozone,CO, and NOu species overthe westernPacificby
Global chemicalproductionandlossratesof tropospheric simulation of observations from the PEM-West B aircraft
ozone,as well as global OH concentrations,are at the high missionin February-March1994.
end of values previouslyreportedin global 3-D models
includingearlier generationsof our 3-D model at Harvard. Acknowledgments. This researchwas supportedby the
This differenceappearslargely due to our suppression of NASA AtmosphericChemistryModelingand AnalysisProgram
an UV-absorbingbackgroundaerosol(with an opticaldepth (ACMAP) andby the NASA EarthObservingSystem(EOS). We
wish to thankClarissaSpivakovskyfor very helpfuldiscussions.
of 0.1 at 310 nm) that was presentin the earlier models.
We aregratefulto AndrewFuscofor processing isopreneobserva-
Althoughorganicaerosolsin the troposphereare expected tions.
to absorb UV radiation, there are no observationsavailable
to usefullyconstrainthe correspondingopticaldepthat the References
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OH for possiblybeingtoo high by •20%. dimensional
9'9'9'Rn
calculations
usingassimilated
dataanda
 BEY ET AL.: GLOBAL MODELING OF TROPOSPHERIC CHEMISTRY 23,093

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 BEY ET AL.: GLOBAL MODELING OF TROPOSPHERIC CHEMISTRY 23,095

I. Bey, SwissFederalInstituteof Technology

(EPFL), DGR- M. G. Schultz,Max-Planck-Institutffir Meteorologie,Bundesstr.
LPAS, CH-1015 Lausanne.,Switzerland.(e-mail: 55, D-20146 Hamburg,Germany.(e-mail:
isabelle.bey
@epfl.ch) martin.schultz@dkrz. de)
B. D. Field, A.M. Fiore, D. J. Jacob,Q. Li, H. Y. Liu, J. A.
Logan,L. J. Mickley,R. M. Yantosca, Divisionof Engineering
and
AppliedSciences andDepartment of EarthandPlanetarySciences,
HarvardUniversity,29 Oxford St., Cambridge,MA 02138. re- (ReceivedDecember20, 2000; revise(iA?fil • 6, 201)1;
mail: bdf;amf; djj; qli; hyl;jal; ljm; bmy@io.harvard.edu) ,,':•cccpied
April 27, 200?.',