Disposal of Dangerous Chemicals in Urban Areas and Mega Cities: Role of Oxides and Acids of Nitrogen in Atmospheric Chemistry

354 Pages·2013·8.23 MB·English

by  Jochen Stutz

Disposal of Dangerous Chemicals in Urban
Areas and Mega Cities
NATO Science for Peace and Security Series
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SeriesC:EnvironmentalSecurity
Disposal of Dangerous Chemicals
in Urban Areas and Mega Cities
Role of Oxides and Acids of Nitrogen
in Atmospheric Chemistry
editedby
Ian Barnes
University of Wuppertal
FB C–Department of PhysicalChemistry
Wuppertal, Germany
and
ń
Krzysztof J. Rudzi ski
Institute ofPhysicalChemistry of thePAS
Warsaw, Poland
Published inCooperation withNATO EmergingSecurity ChallengesDivision
Proceedings of theNATOAdvancedResearch Workshopon
Disposal ofDangerous Chemicalsin UrbanAreas and MegaCities
Gdansk,Poland
9–13October2011
Libraryof Congress Control Number: 2012943344
ISBN 978-94-007-5036-4 (PB)
ISBN 978-94-007-5033-3 (HB)
ISBN 978-94-007-5034-0 (e-book)
DOI 10.1007/978-94-007-5034-0
Published bySpringer,
P.O.Box17, 3300AA Dordrecht,TheNetherlands.
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Preface
TheNATOAdvancedResearchWork“DisposalofDangerousChemicalsinUrban
AreasandMegaCities”tookplaceinGdan´sk,Poland,9–13October2011andwas
attendedby39participantsfromtencountries.Themajoraimoftheworkshopwas
tolookatthepresentstateofknowledgeontheroleofoxidesandacidsofnitrogen
inoxidantradicalformationandcyclingandconsequentlytheoxidationcapacityof
theatmosphereingeneralandurbanareasandmegacitiesinparticular.
Oxidesandacidsofnitrogenplayanimportantroleinregulatingtheatmospheric
levelsoftheOHradicalwhichisthemainimitatorofthedegradationofchemicalsin
theatmosphere.Theworkshopgaveacomprehensiveoverviewonthemethodsused
tomeasurenitrogen(NO )andnitrousacid(HONO)inthetroposphereanddifficul-
2
ties associated with certain techniques were highlighted. Reports from recent field
measurements usingverysensitiveHONOinstrumentsservedtoshowthe growing
recognitionamongthescientificcommunitythatphotolysisofHONOisamuchmore
importantdaytimeOHradicalthanpreviouslythought.Presentationsonthestateof
theartinOHandHO radicalatmosphericmeasurementmethodswereanimportant
2
topic of the workshop and recently recognised difficulties, in particular with HO
2
radicals,werehighlighted.
Our present understanding of the gas, aqueous and particulate/aerosol phase
atmosphericdegradationchemistryofchemicalsunderdifferentNO environments
x
was presented and discussed in great detail. The potential importance of photo-
enhancedreactionsonsurfacesandparticleswashighlightedatthemeetingthrough
the presentation of recent research. This is an area that is currently finding many
applications for the removal of chemicals from the atmosphere, e.g. through
photocatalyticremediationprocesses.
Examples of measurements of NO and chemicals in the atmosphere were
x
presented for rural and urban environments and also megacities such as Cairo in
conjunctionwithmodellingstudieswhichattempttosimulatethefieldobservations
usingstate-of-theartknowledgeonthechemistryandradicallevels.Theseexam-
pleshelpedtohighlightsomeofthemoreimportantgapsinourknowledgeonthe
degradation of chemicals in the atmosphere, e.g. large uncertainties in different
steps of the degradation routes, missing sources for the important OH radical
v
vi Preface
precursor HONO, and very importantly an inadequate knowledge of OH/HO
2
radical recycling in the degradation of chemicals. Modelling the impact of mega-
citiesonairqualityandclimateisassociatedwithmanydifficultiesandunknowns.
Thesewereconciselypresentedattheworkshopalongwithnewapproachestothis
immenseproblemwhicharebeingappliedwithin,forexample,theEUFP7project
MEGAPOLI.
Theworkshophasplayedanimportant roleincollectingtogethermostaspects
of the current state of knowledge on the role of oxides and acids of nitrogen in
the atmospheric degradation of chemicals from the viewpoint of measurement,
chemistryandmodelling.Themanuscriptspresentedhereintheproceedingsreflect
the presentations given at the workshop. PDFs of the presentations are available
[email protected]
Ian Barnes, Ali Shakour and Krzysztof Rudzinski (worship organisers),
April2012.
Group photograph showing most of the participants at the NATO ARW held in the Novotel,
Gdan´sk,Poland,9–13October2011
Acknowledgements
The ARW was kindly financed by the following organizations for the workshop
convenersareextremelygrateful:
NATOScientificandEnvironmentalAffairsDivision,Brussels
http://www.nato.int/science/index.html
The EC 6th Framework Programme, EUROCHAMP project “support for Infra-
structures–IntegratedInfrastructureInitiative”
http://www.eurochamp.org/
vii

Contents
1 FieldObservationsofDaytimeHONOChemistryandItsImpact
ontheOHRadicalBudget.............................................. 1
JochenStutz,KamWengWong,andCatalinaTsai
2 NO MeasurementTechniques:PitfallsandNewDevelopments.... 15
2
Jo¨rgKleffmann,GuillermoVillenaTapia,IustinianBejan,
RalfKurtenbach,andPeterWiesen
3 AnOverviewofMeasurementTechniquesforAtmospheric
NitrousAcid.............................................................. 29
XianliangZhou
4 AssessmentofHONOMeasurements:TheFIONACampaign
atEUPHORE............................................................ 45
MilaRo´denas,AmaliaMun˜oz,FranciscoAlacreu,TheoBrauers,
Hans-PeterDorn,Jo¨rgKleffmann,andWilliamBloss
5 StateoftheArtOHandHO RadicalMeasurementTechniques:
2
AnUpdate................................................................ 59
DwayneHeard
6 HO andRO RadicalsinAtmosphericChemistry................... 77
x x
DamienAmedro,AlexanderE.Parker,CoralieSchoemaecker,
ChaithanyaJain,PranayMorajkar,PaulS.Monks,KojiMiyazaki,
YoshizumiKajii,andChristaFittschen
7 TheExchangeofSoilNitriteandAtmosphericHONO:
AMissingProcessintheNitrogenCycleandAtmospheric
Chemistry................................................................ 93
HangSu,YafangCheng,andUlrichPo¨schl
8 NitrogenOxides:VehicleEmissionsandAtmospheric
Chemistry................................................................ 101
TimothyJ.Wallington,JohnR.Barker,andLamNguyen
ix
x Contents
9 ModelingAtmosphericHONOConcentrations
ontheRegionalScale.................................................... 115
BernhardVogelandHeikeVogel
10 HeterogeneousAtmosphericChemistryofNitrogenOxides:
NewInsightsfromRecentFieldMeasurements ...................... 125
StevenS.Brown,NicholasL.Wagner,WilliamP.Dube´,
andJamesM.Roberts
11 VOCDegradationintheAtmospherebyNanophotocatalysts....... 139
RashidA.Khaydarov,RenatR.Khaydarov,OlgaGapurova,
andN.K.Nasirova
12 ProductionoftheAtmosphericOxidantRadicalsOH
andHO fromtheOzonolysisofAlkenes.............................. 151
2
WilliamJ.Bloss,M.S.Alam,A.R.Rickard,M.Camredon,
K.P.Wyche,T.Carr,andP.S.Monks
13 TheoreticalInvestigationoftheNO InitiatedReactionofVOCs... 163
3
SolvejgJørgensen
14 MeasurementsofTraceGasesatSaint-PetersburgState
University(SPbSU)intheVicinityofSaint-Petersburg,Russia..... 173
YuryTimofeyev,DmitryIonov,MariaMakarova,YanaVirolainen,
AnatolyPoberovsky,AlexanderPolyakov,HamudImhasin,
SergeyOsipov,AntonRakitin,andMarinaKshevetskaya
15 Nitro-andNitro-Oxy-CompoundsinMultiphaseParticle
Chemistry:FieldandAnalyticalStudies.............................. 185
YoshiteruIinumaandHartmutHerrmann
16 HeterogeneousandLiquid-PhaseReactionsofBVOCs
withInorganicPollutantsintheUrbanAtmosphere................. 195
KrzysztofJ.Rudzin´ski
17 ChemistryofOrganicSulfatesandNitrates
intheUrbanAtmosphere............................................... 211
RafalSzmigielski
18 TracersforBiogenicSecondaryOrganicAerosolfroma-Pinene
andRelatedMonoterpenes:AnOverview............................. 227
MagdaClaeys,RafalSzmigielski,ReinhildeVermeylen,WuWang,
MohammadSafiShalamzari,andWillyMaenhaut
19 AnIonizationMethodBasedonPhotoelectronInduced
ThermalElectronGeneration:capillaryAtmospheric
PressureElectronCaptureIonization(cAPECI)..................... 239
ValerieDerpmann,IustinianBejan,HendrikKersten,
KlausJ.Brockmann,IanBarnes,Jo¨rgKleffmann,ThorstenBenter,
HannahSonderfeld,andRalfKoppmann