7)

A EUREKA Environmental Project

Transport and Transformationof

Pollutants in the Troposphere

Proceedings of EUROTRAC Symposium '94

Garmisch-Partenkirchen, Federal Republic of Germany

11th-15th April 1994

EditorsPatricia M. Borrell, Peter Borrell,

Tomislav Cvitas and Wolfgang Seiler

EUROTRAC International Scientific Secretariat (ISS)Fraunhofer-Institut fiir Atmosphdrische Umweltforschung

I Garmisch-Partenkirchen

SPB Academic Publishing bv

Contents

Welcoming Addresses and Concluding Remarks

W. Seiler, Director of the ISS 3

T. Goppel, Minister for Environment and Development in the Government

of Bavaria 4

E. Eellenius, Chairman of the IEC 8

G. Hahn, German Federal Ministry for Research and Technology (BMFT) 10

A.R. Marsh, Chairman of the SSC 11

The Application Project

P. Borrell, An Introduction 15

0. Hov, R. van Aalst, N. Moussiopoulos and A. Volz-Thomas, Photo-oxidants 16

P. Grennfeld, D. Fowler and P. Warneck, Acidification and Depositionof Nutrients 17

P. Builtjes, G. Megie and R.P. Wayne, Contribution to the Development ofTools 18

General Discussion 18

A Future Project to follow EUROTRAC

W. Seiler, A Future Project to follow EUROTRAC 23

K.-H. Becker, Plea for Research on Photo-oxidants 27

J. Slanina, The Case for Eutrophication 29

P. Grennfeld, Needs for Future Research on Acidification 30

M. Schulz, An Environmental Issue: Heavy Metal Deposition - Trace Metalsin the Aerosol 32

j

General Discussion 33

Introductory Lectures

P. Warneck, Tropospheric Oxidation Chemistry 37A. Eliassen, Second Generation Abatement Strategies 47N. Moussiopoulos, Air Pollution Modelling in Southern Europe 48

xvi Contents

F. Fehsenfeld, Transport of O3 and O3 Precursors from Anthropogenic

Sources to the North Atlantic 56

Chemical Mechanisms and Atmospheric Processes

K.-H. Becker, The Atmospheric Oxidation of Aromatic Hydrocarbons and

its Impact on Photo-oxidant Chemistry 67

G.D. Hayman, The Oxidation of Biogenic Hydrocarbons 75

A. Lindskog, VOC Oxidations and Observations 83J. Beck, A. van Pul, D. De Muer, P. Van Haver, V. Bazhanov, C. Varotsos,A. Volz-Thomas, H.G.J. Smit, 0. Hov, F. Flatoy, P. Speth, H. Kunz,P. Simmonds, T. Trickl, M. Memmesheimer, M. Beekmann, G.'Ancelletand G.C. Grabbe, Exchange of Ozone between the Atmospheric BoundaryLayer and the Free Troposphere 89

H.E. Scheel, Interpretation of TOR Ozone Measurements 92

J. Bosenberg, Atmospheric Processes and Ozone Profiles 99

R. Neavyn, H. Sidebottom and J. Treacy, Reactions of Hydroxyl Radicalswith Polyfunctional Group Oxygen-Containing Organic Compounds 105J. Peeters, W. Boullart, J. Van Hoeymissen, Site-specific Partial RateConstants for OH Addition to Alkenes and Dienes 110

M. Siese, R. Koch, C. Fittschen and C. Zetzsch, Cycling of OH in theReaction Systems Toluene/O2/NO and Acetylene/O2 and the Addition ofOH to Isoprene 115

C. Vinckier, N. Van Hoof, F. Compernolle and S. Ashty, Product Distributionfor the Reaction of a-Pinene with Hydroxyl Radicals 120

J. Treacy, M. Curley and H. Sidebottom, Kinetics and Mechanism for theReactions of Ozone with Cycloalkenes 124

P. Neeb, O. Horie, S. Limbach and G.K. Moortgat, The Formation of FormicAcid and Organic Peroxides in the Ozonolysis of Ethene underAtmospheric Conditions 128

V. Dae'lej A. Mellouki, S. Teton, G. Laverdet, G. Poulet and G. Le Bras,Laboratory Studies of NO3 and OH Reactions involved in theAtmospheric Oxidation of VOCs 134

P. Biggs, C.E. Canosa-Mas, K.J. Hansen, P.S. Owen and R.P. Wayne,The Thermal Decomposition of Peroxyacetylnitrate in the Presence of NO3 139

P. Biggs, C.E. Canosa-Mas, J.-M. Fracheboud, D.E. Shallcross andR.P. Wayne, The Reactions of Alkyl, Alkoxy and Alkylperoxy Radicals withNO3 144

Contents xvii

M. Exner, H. Herrmann, G. Raabe and R. Zellner, A Kinetic Study ofNitrate (N03) Radical Reactions of Interest for Atmospheric AqueousPhase Chemistry within Continental Airmasses 149

L. Elmaimouni, C. Bourbon, C. Fittschen, J.P. Sawerysyn and P. Devolder,Reaction rates of the C2H5O (Ethoxy) Radical with O2 NO and NO2 153

/. Barnes, K.H. Becker, A. Bierbach, B. Klotz and E. Wiesen, AtmosphericChemistry of Unsaturated Dicarbonyl Compounds 158

K. Granby, O. Hertel, J. Holcmann, O.J. Nielsen, T. Nielsen, K. Sehested andA.H. Egelov, Organic Sulphur Compounds: Atmospheric Chemistry,Occurrence and Modelling 163

R. Hiiskes and K. Levsen, Photochemical Transformation of Pesticidesin the Atmosphere: Identification and Quantification of the Photoproducts 167

R. Zellner, A. Hoffmann, W. Malms and V. Mors, Time Resolved Studiesof NO2 and OH Formation in the Integrated Oxidation Chain of Benzene 171

A. Mayer-Figge, F. Kirchner, H.G. Libuda, F. Zabel and K.H. Becker,Thermal and Photochemical Stability of Peroxynitrates 175

J. Reuder, T. Gori, A. Ruggaber, L. Kins and R. Dlugi, PhotolysisFrequencies of Nitrogen Dioxide and Ozone: Measurements and ModelCalculations 180

M. van Weele, J. Vila-Guerau de Arellano and F. Kuik, Evaluation ofEmpirical Relations for the Photodissociation Rate of NO2 by Means ofRadiative Flux Measurements 185

A. Hofzumahaus, M. Mu'ller and A. Kraus, Experimental Determinationof J(O3—>O'D) in the Troposphere by Radiometric and ChemicalMeasurement Techniques 191

G. Seckmeyer, B. Mayer, G. Bernhard and R. Erb, Changes inUltraviolet Radiation 194

A. Lindskog and J. Mowrer, The 1993 Extended Measurement Period atRorvik 199

A.H. Egelov, K. Granby, T. Nielsen and N. Skov, Background OzoneContribution at a Non-remote TOR Site 203

R. Girgzdidne, D. Sopauskiene and A. Girgzdys, Formation and Changesof Atmospheric Ozone and Related Species Levels in Lithuania 207

H. Flentje, R. Dubois, F. Heintz and U. Platt, Long-path DOASMeasurements of Ozone and Other Species at Cape Arkona (Riigen Island) 212

F.M. McGovern, T.C. O'Connor and S.G. Jennings, Ozone Levels at MaceHead, Ireland 217

xviii Contents

B.J. Bandy, S.A. Penkett, P. Simmonds and G. Spain, Evidence of LongRange Transport Phenomena measured at Mace Head Research Station,Carna, Ireland 221

R.A. Burgess and S.A. Penkett, Non-methane Hydrocarbon Measurementsfrom the Weybourne Atmospheric Observatory during the TOR Campaign1993 224

G. Desmet, K. Van den Berghe, G. Dumont, D. Tielemans and E. Roekens,Study of the Photochemical Air Pollution in Belgium 228

A. Etienne, P.E. Perros, P. Colin, A.L. Dutot and G. Toupance, OzoneTime Variations at Porspoder TOR Station 235

A.L. Dutot, P. Colin, A. Etienne, P.E. Perros and G. Toupance, ChemicalMapping and Sector Analysis at the Porspolder TOR Station:Characterization of the Air Masses coming from the North Atlantic 239

F. Flocke, A. Volz-Thomas and D. Kley, The Use of Alkyl NitrateMeasurements for the Characterization of the Ozone Balance at TOR StationNo 11, Schauinsland 243

W.R. Stockwell, R. Sladkovic, HE. Scheel and W. Seiler, The Effect ofRegional Meteorology on Observed Ozone Concentrations in the GermanAlps 248

R. Sladkovic, H.E. Scheel and W. Seiler, Ozone Climatology at the MountainSites, Wank and Zugspitze 253

P. Filliger, B. Buchmann and B. Schwarzenbach, Air Pollution Measurementsat the High Alpine Station Jungfraujoch (3580 m a a.s.l.), Switzerland,1973 - 1993 259

G. Valli, R. Vecchi, E. Brambilla amd R. Barbiero, Ozone Measurements onPre-Alps in Lombardy (Italy) 263

B. Gomiscek and M. Pompe, The Variation of VOC and Ozone Concentrationat the Krvavec Site during the Summer 1993 266

V. Butkovid, T. Cvitas, L. Klasinc, S. Vidic and V. Duricid, Analysis of OzoneData from the TOR Station Puntijarka 271

N. Kezelef T. Cvitas and L. Klasinc, Analysis of Measurements with theCRANOX System in Zagreb 275

K. Labancz and Z. Ferenczi, Statistical Analysis of O3 Data measured atTOR Station 15 (K-puszta, Hungary) 279

V. Sdndor, L. Haszpra and G. Baranka, Early Spring Ozone Episodes inHungary 284

Contents xix

L. Bozo and G. Baranka, Model Simulation of Ozone Formation in an UrbanPlume over Hungary 290

B. Artinano, M. Pujadas, J. Plaza, S.N. Crespi, H. Cabal, B. Acena andJ. Teres, Air Pollution Episodes in the Madrid Airshed 294

E. Mantilla, J.F. Bea, R. Salvador and MM. Milldn, Meso-meteorologicalCycles and Transport of Photo-oxidants on the Eastern Coast of theIberian Peninsula: Field Measurements 298

C. Varotsos, G. Chronopoulos and P. Kalabokas, Seasonal Variation andCross-Tropopause Ozone Exchange at Athens, Greece 305

A. Baykal, S.G. Tuncel and U. Ozer, Measurement of Gas Phase Pollutants atUludag Mountain in Northwestern Turkey 310

R. Schmitt, Simultaneous Measurements of Carbon Monoxide, Ozone,PAN, NMHC and Aerosols in the Free Troposphere at Izana, Canary Islands. 313

V. Bazhanov, H. Rodhe, P. Oyola and R. Janson, High Elevated OzoneMeasurements at Areskutan: Connection with Nearby Ozone Soundings 317

G.C. Grabbe, J. Bosenberg and T. Schaberl, Ozone Distribution in the LowerTroposphere investigated with the MPI Ozone DIAL 322

V. Matthias, J. Bosenberg and V. Wulfmeyer, Improvement of OzoneMeasurements with DIAL by using an Additional Raman Channel 326

D. De Muer, H. De Backer and P. Van Haver, Trend Analysis of 25 Yearsof Regular Ozone Soundings at Uccle (Belgium) 330

P. Van Haver and D. De Muer, Seasonal and Long Term Variationof Stratospheric Ozone Intrusions into the Troposphere and PhotochemicalOzone Production in the Boundary Layer at Uccle (Belgium) 335

T. Trickl, Tropospheric Ozone Measurements: 1993 Results and the FutureofthelFULidar 341

R. Weller, R. Neuber, R. Lilischkis and O. Schrems, Vertical OzoneDistribution in the Marine Atmosphere over the Atlantic Ocean(46° S - 50° N) 344

H.G.J. Smit, W. Strdter, D. Kley and M.H. Proffitt, The Evaluation of ECCOzone Sondes under Quasi Flight Conditions in the EnvironmentalSimulation! Chamber at Jiilich 349

S. Blonsky, H Kunz and P. Speth, Tropopause Foldings over Central Europe 354

D. Brunner, W. Moser and J. Staehelin, NO, NO2 and O3 Measurementsfrom a Swissair Airliner 361

P. Jeannet, B. Hoegger, P. Viatte and D. Schneiter, Vertical Ozone Profilesover Payerne, Switzerland, during TRACT and POLLUMET 362

xx Contents

M. Beekmann, G. Ancellet and C. Mancier, Tropospheric Ozone Monitoringat the Observatoire de Haute Provence 367

F. Kramp, H.J. Buers, F. Flocke, D. Klemp, D. Kley, H. W. Pdtz, T. Schmitzand A. Volz-Thomas, Determination of OH Concentrations from the Decayof C5-C8 Hydrocarbons between Freiburg and Schauinsland: Implicationsfor the Budgets of Olefins 373

D. Mihelcic and A. Volz-Thomas, The Ratio of Organic Peroxy toHydroperoxy Radicals: Direct Measurements by Matrix Isolation /ESR Spectroscopy 379

P. Colin, P.E. Perros, A. Etienne, H. Boudries, A.L. Dutot, M. Maille andG. Toupance, Variation of PAN Concentration in Marine Troposphere:Relationships with Ozone 385

F. Heintz, U. Platt, H. Flentje, R. Dubois and H.J. Karbach, Long Term LP-DOAS Measurements of NO3 and Related Species at the New TOR StationKap Arkona 390

F. Heintz, J. Stutz, U. Platt, H. Flentje and R. Dubois, NO3 Lifetime andPossible Depletion Mechanisms measured at Kap Arkona 395

/. Hahn, Results of the Hydrocarbon Interlaboratory Comparison Experimentin TOR 399

Y. Andersson-Skold and A. Lindskog, A Preliminary Investigation ofPossible Chemical Contributors to the Observed Photochemical ReductionofVOCs 404

C.S. Christensen, C. Lohse, K. Granby, T. Nielsen and A.H. Egelov,Measurements of CJ-CJ Carbonyls at the Danish TOR Station and inCentral Copenhagen 410

T. Laurila, H. Hakola, H. Boij and S.M. Joffre, Concentrations of NMHCsand Ozone over the Baltic Sea and in an Urban Area 413

H. Boudries, G. Toupance and A.L. Dutot, Seasonal Variation ofAtmospheric Non-methane Hydrocarbons on the Western Coast ofBrittany, France 417

L. Hasznra, A. Gyuricza and I. Szildgyi, Preliminary Statistical Analysis ofNon-mejthane Hydrocarbon Measurements at TOR Station 15 (K-puszta,Hungary) 421

H.-P. Dorn, U. Brandenburger, T. Brauers and M. Hausmann, A NewIn-situ Laser Long-Path Absorption Instrument for the Measurementof Tropospheric OH 425

A. Hofzumahaus, U. Aschmutat, M. Hessling and F. Holland , In situMeasurement of Tropospheric OH and HO2 Radicals by Laser-InducedFluorescence 430

Contents xxi

The Contrast between Anthropogenic and Biogenic Emissions

M. Heymann, Y. Kasas and R. Friedrich, European Emission Datawith High Temporal and Spatial Resolution 437

J. Staehelin, D. Brunner and K. Schldpfer, VOC Emission Factorsfrom Traffic Tunnel Studies 444

R. Steinbrecher, Emission of VOCs from Selected European Ecosystems:The State of the Art 448

W.A.H. Asman, Problems with the Estimation of European AmmoniaEmissions 455

U. Hansen, D. Adolph and J.-G. Kim, Update and Temporal Resolution ofEmissions from Point Sources in GENEMIS 459

W. Winiwarter, J. Moravek, P. Faith, L. Kozakovic, K. Mareckova, J. Fiala,M. Schreuder, H. Kratka and J. Kutas, Temporal Disaggregation of TrafficEmissions in Central Europe 463

W. Maenhaut, G. Ducastel, K. Beyaert and J.E. Hanssen, ChemicalComposition of the Summer Aerosol at Ny Alesund, Spitsbergen, andRelative Contribution of Natural and Anthropogenic Sources to the Non-sea-salt Sulfate 467

F. Francois and W. Maenhaut, Chemical Composition and Sources of theSize-fractionated Atmospheric Aerosol collected at the Research PlatformNordsee 472

L. Horvdth, E. Fiihrer, A. Gyuricza, K. Lovas, Z. Nagy amd T. Weidinger,Gradient Flux Measurements of Gases above Short Vegetation and Forest 477

M. Zelger, J. Schween, B.T. Wichura, Th. Foken, T. Andersson, G. Roider,Th. Seiler, C. Frank, H. Losslein and R. Dlugi, MicrometeorologicalMeasurements for Flux Determination of Trace Substances 479

R.A. Street, S.C. Duckham, C. Boissard and C.N. Hewitt, Biogenic TerpeniodEmissions from Vegetation in Europe 480

K. Lovas and L. Horvdth, A Model Calculation on the Possible Effect ofMonoterpenes in the Ozone Formation above a Pine Forest 485

M. Kuhn And D. Poppe, Photo-oxidant Formation in the Presence of Isoprene:Comparison of Field Measurements and Model Calculations 489

H. Vogel, F. Fiedler and B. Vogel, The Sensitivity of Modelled OzoneDistributions in the State of Baden-Wurttemberg to Biogenic VOCEmissions 492

C.A. Pio, TV. Nunes and A.R. Valente, Measurement of VOC Emissionsfrom Pinus Pinaster Species by Bag Enclosure and Tracer Techniques 497

xxii Contents

R. Steinbrecher and R. Rabong, Emissions of Terpenoids and C2-C6

Hydrocarbons by Norway Spruce: Phytotron Experiments and Field Studies 502

R. Steinbrecher, W. Junkermann, J. Steinbrecher and J. Slemr, VOCs andPeroxides in Ambient Air above an Oak/Pine Forest in the MediterraneanRegion 506

P. Pistikopoulos, N. Moussiopoulos and G. Tsilingiridis, Biogenic NM-VOCEmissions from Greek Forests 511

M.L. Sanchez, M.J. Fernandez and J. Dominguez, VOC and CH4

Observations in a Forested Area and in a Flat Terrain in Castille and Leon 516

P. Boeckx and O. Van Cleemput, Methane Oxidation in a Landfill CoverSoil 521

R. Gabriel, G. Helas and J. Kesselmeier, Determination of the Concentrationof Organic Acids and Anorganic Ions in the Apoplastic Compartment ofBeech Leaves 525

P.M. Midgley and A. McCulloch, The Production and Global Distribution ofEmissions to the Atmosphere of 1,1,1 -Trichloroethane 529

J. Rudolph and R. Conrad, Vertical Distribution of Nitric Oxide Productionand Consumption in Soil Cores 533

E. Lorinczi and A. Ritivoiu, T. Camaroschi, First Emission Inventory ofAmmonia in Timis County 534

M. Maag, F. Eiland and A.-M. Lind, N2O Emission from Arable Soils:Contribution to an EU Database 541

P. Hummelsh0j, K. Pilegaard and N.O. Jensen, Flux Measurements of O3

and NO2 over a Regrown Wheat Field 544

W. Jaeschke, Th. Dietrich and U. Schickedanz, Determination of CO2-, NO-,NO2- and O3-Fluxes between the Atmosphere and a Strongly PollutedForest Ecosystem 549

H. Geifi, H. Hass, H. Jakobs and M. Memmesheimer, Flux Calculations ofOzone and its Precursors with the EURAD Model at the TORStation Schauinsland 550

R. Simo\ R. de Wit, J.O. Grimalt and J. Albaiges, Factors Controlling theEmissioh of Volatile Sulphur Compounds from a Monomictic, Sulphide-rich Karstic Lake to the Atmosphere 554

5. Blezinger, C. Wilhelm and J. Kesselmeier, Exchange of Reduced SulfurCompounds between Marine Phytoplankton and the Ocean 559

G. Uher and M.O. Andreae, The Diurnal Cycle of Carbonyl Sulfide inSeawater: A Simple Empirical Model 563

Contents xxiii

V.S. Ulshofer, O.R. Flock, G. Uher, S. Rapsomanikis and M.O. Andreae,Variability of Carbonyl Sulfide (COS) Concentrations in the MediterraneanSea and the Northeast Atlantic 568

D. Amouroux, O.F.X. Donard and S. Rapsomanikis, Sea-to-Air Selenium

Fluxes in the Eastern Mediterranean Sea 573

Deposition and Atmospheric Transport

R.M. Harrison, Chemical Transformations in the North Sea Atmosphere 581J.W. Erisman, C. Potma, G. Draaijers, E. van Leeuwen and A. van Pul,A Generalised Description of the Deposition of Acidifying Pollutants ona mall Scale in Europe 588H. Puxbaum and D. Wagenbach, High Alpine Precipitation Chemistry 597

S. Slanina, M. Plantaz and G.P. Wyers, Deposition: From LocalMeasurements to Conclusions on a European Scale 606

F. Fiedler, TRACT Field Measurements and Model Simulations: FirstResults 614

T. Spranger, E. Hollwurtel, F. Poetzsch-Heffter and A. Branding, DryDeposition Estimates from Two Different Inferential Models as compared toNet Throughfall Measurements 615

R. San Jose, L. Rodriguez and J. Moreno, An Application of the 'Big-LeafDeposition Approach to the Mesoscale Meteorological Transport andChemical Modelling in a Three Dimensional Context 620

A. Rebers, M. Schulz, L. Spokes, T. Jickells and M. Leermakers, A RegionalCase Study of Wet Deposition in the North Sea Area 621

L.L. Serensen, O. Hertel, J. Christensen, M. Schulz and R.M. Harrison,Fluxes of Nitrogen Gases to the North Sea 626

W.A.H. Asman, O. Hertel, R. Berkowicz, J. Christensen and E.H. Runge,Modelling the Atmospheric Nitrogen Input to the Danish Coastal Waters 632

W.A.H. Asman, R.M. Harrison and C.J. Ottley, The Net Air-Sea Flux ofAmmonia over the Southern Bight of the North Sea 635

H. Gu'sten, 'G. Heinrich, E. Mb'nnich and D. Sprung, Ozone Depletion withinthe Nocturnal Inversion Layer: Night-time Chemistry versus SurfaceDeposition 639

R. Dlugi, L. Kins, D. Miiller, G. Roider, H. Schoers, T. Seiler, M. Weber,M. Zelger, T. Foken, B. Wichura, H. Gilsten and G. Kramm, The Exchangeof Trace Gases and the Surface Energy Budget: An Intercomparison ofResults from Field Studies 643

xxiv Contents

G. Kramm, R. Dlugi, T. Foken, N. Molders, H. Muller andK.T. Pau U,On the Determination of the Sublayer Stanton Numbers of Heat and Matterfor Different Types of Surfaces 644

T.W. Choularton, H. Coe, S. Walton, M.W. Gallagher, KM. Beswick, C. Dore,J. Duyzer, H. Westrate, K. Pilegaard, N. O. Jensen and P. Hummelshoj,Photochemical Modification of Ozone and NOx Deposition to Forests:Results from the Speulderbos and Rivox Experiments 645

K. Granby, S.E. Gryning and O. Hertel, Hydrogen Peroxide Concentrationsin Relation to Mixing Heights at a Danish Sea Site and a Land Site:Comparison with a Trajectory Model 651

J. W. Erisman, M. Mennen, J. Hogenkamp, E. Kemkers, D. Goedhart,A. van Pul, G.P.J. Draaijers, J. Duyzer and G.P. Wyers, Dry DepositionMonitoring of SO2, NH3 and NO2 over a Coniferous Forest 655

R. Janson and L. Granat, Dry Deposition of Ammonium and NitrateCompounds to Coniferous Forest 660

M.A.H.G. Plantaz, A.T. Vermeulen and G.P. Wyers, Surface Exchange ofAmmonia over Grazed Pasture 661

J.R. Stedman and J.G. Irwin, Measurements of Acid Deposition at a Site inNorthern Britain 668

W.A.J. van Pul, C.J.M. Potma, G.P.J. Draaijers, E. van Leeuwen andJ. W. Erisman, Small Scale Deposition Fluxes of Acidifying Componentsover Europe 673

A. Ibrom, C. Veithen, M. Marques and G. Gravenhorst, The Evidence ofCrown Rain Interactions in a Mountainous Spruce Forest 677

KM. Beswick, M.W. Gallagher, P. Hummelshoj, K. Pilegaard, N.O. Jensenand J. Duyzer, Aerosol Exchange to Speulder Forest 683

P. Seibert, H. Kromp-Kolb, U. Baltensperger, D.T. Jost, M. Schwikowski,A. Kasper and H. Puxbaum, Trajectory Analysis of Aerosol Measurementsat High Alpine Sites 689

F. Pichlmayer, K. Blochberger, W. Schoner and W. Stichler, Stable IsotopeAnalysis of Snow Profiles and Aerosol Samples collected at Sonnblick 694

jS.E. Larskn, J.B. Edson, P. Hummelshoj, N.O. Jensen, G. de Leeuw andP. G. Mes\ayer, Laboratory Study of the Particle Dry Deposition Velocityover Water 698

M. Schulz, T. Stahlschmidt, F. Frangois, W. Maenhaut and S.E. Larsen,The Change of Aerosol Size Distributions measured in a Lagrangian-typeExperiment to Study Deposition and Transport Processes in the MarineAtmosphere 702

Contents xxv

G. de Leeuw, A.M.J. van Eijk, P.G. Mestayer and S.E. Larsen, AerosolDynamics near the Air - Sea Interface 707

J. Injuk, R. van Grieken, L. Breitenbach and U. Wdtjen, Study of IndividualParticle Types and Heavy Metal Deposition for North Sea Aerosols 711

G.P. Wyers, M. Geusebroek, A. Wayers, J.J. Mols and A.C. Veltkamp,Dry Deposition of Submircon Aerosol on a Conifereous Forest 712

M. Schwikowski, U. Baltensperger, H.W. Gdggeler, A. Novo, G.C. Rossi,M. Kuhn, U. Nikus, R. Delmas, F. Maupetit, S. Preunkert, D. Wagenbach,A. Kasper, H. Puxbaum and W. Schoner, Snow Pit Sampling Intercomparisonat Weissfluhjoch, Switzerland 716

W. Schoner, H. Puxbaum, M. Staudinger and F. Maupetit, GeographicalPatterns in the Chemical Composition of Alpine Glacier Snow 721

U. Nickus, M. Kuhn and J. Haslhofer, Temporal Variation of Nitrate in anAlpine Snow Cover 725

U. Nickus, M. Kuhn, F. Maupetit, R.J. Delmas, D. Wagenbach, S. Preunkert,M. Schwikowski, U. Baltensperger, H.W. Gdggeler, A. Novo, G.C. Rossi,V. Trockner, W. Schoner, M. Staudinger, H. Puxbaum, F. Pichlmayer andW. Winiwarter, SNOSP Campaign 1991-1993: Spatial and TemporalVariability of the Chemical Composition of Snow in the Alps 728

W. Winiwarter, W. Schoner and H. Puxbaum, Ionic Contents of WintertimeDeposition at an Alpine Glacier: Results from a Decade of Sampling 731

R. Schajor, S. Preunkert, K. Hebestreit and D. Wagenbach, Deposition ofHeavy Metals onto High Elevation Alpine Snow Fields 735

T. Schaberl, M. Bauer, J. Bosenberg, G. Grabbe, G. Peters and C. SenffTransport Processes of Ozone in the Planetary Boundary Layer observedwith DIAL and Radar-RASS 736

A. Milukaite, B. Giedraitis, A. Nika, V. Yuozefaite and A. Galvonaite, TheInfluence of Long-range Transport on the Variation of Concentrations ofGaseous and Particulate Admixtures in the Atmosphere over Lithuania 741

A. Stingele, U. Corsmeier, K. Nodop, M. Kofimann and R. Vogtlin, TracerExperiment in the Nested Area of the TRACT Campaign 747

N. Kalthoff, H.-J. Binder, F. Fiedler, M. Kofimann, U. Corsmeier, R. Vogtlinand H. Schlager, The Boundary Layer Evolution during TRACT 748

M. Kofimann and B. Vogel, Comparison between Calculated and ObservedBoundary Layer Heights during the TRACT Campaign 753

H. Vogel, F. Fiedler, B. Vogel, J.S. Chang, A. Obermeier, C. John andR. Friedrich, Aggregation Factors and Rate Constants derived for theEmission Conditions in the TRACT Area 757

xxvi Contents

U. Corsmeier, M. Kofimann, R. Vogtlin and F. Fiedler, Water VapourTransport by Stationary Convective Cells over Hilly Terrain 761

A.M. Jochum, C.S. Strodl, H. Willeke and N. Entstrasser, The Transport ofHeat, Moisture and Ozone in the Atmospheric Boundary Layer in the UpperRhine Valley 766

R. Vogtlin, M. Loffler-Mang, M. Kossmann, U. Corsmeier, F. Fiedler,O. Klemm and H. Schlager, Spatial and Temporal Distribution of AirPollutants over Complex Terrain during TRACT 770

P. Lightman and A.R. Marsh, Pollutant Concentration Profiles over ComplexTerrain: Evidence for Flow between Valleys 776

B. Torok and Sz. Torok, 3-D Finite Element Modelling of Wind Flow overComplex Terrain 780

Modelling and Validation on Regional and Global Scales

H. Hass, H.J. Jakobs, M. Memmesheimer and A. Ebel, EURADSimulation of a TOR Episode 785

S.M. Joffre and M. Alberti, Modelling and Environmental InformationNeeds for Europe 790

H.J. Jakobs, Use of Nested Models for Air Pollution Studies 799

H. Rodhe, Global Distributions of Atmospheric Sulfur Compounds and theirPotential Impact on Climate 807

H. Kelder, P. van Velthoven and M. Allaart, Exchange between theTroposphere and Stratosphere 808

G. Ancellet and M. Beekmann, Ozone Stratosphere Troposphere

Exchange: Climatology and Case Studies 812

M. C. Krol, Boundary Layer Parameterization for Global Chemistry Models 820

P.H. Zimmermann, F.J. Dentener, J. Lelieveld and P.J. Crutzen,Tropospheric Ozone: Its Sources and Sinks 824H.-J. Lotz-Iwen, A. Nolle and H. Wilhelms, On-line Access to RemoteSensing Pata and Ancillary Infirmation for Global EnvironmentalMonitoring 825

B. Langmann and H. Graf, Another Meteorological Driver (HIRHAM) forthe Chemistry Transport Model (CTM) of the EURAD-System: FirstSimulations with the Coupled System 830

D. Schmidt, U. Maas and J. Warnatz, Simplification of Chemical Kinetics forReactive Flow Calculations 834

Contents xxvii

N. Molders, M. Laube and G. Kramm, A Scheme for Parameterizing Ice andWater Clouds in Regional Models 839

N. Molders, H. Hass, H.J. Jakobs, M. Laube and A. Ebel, Consequences ofDifferent Cloud Parameterizations in MM4 and CTM 845

J.-M. Giovannoni, A. Clappier, F. Mueller, J. Kuebler, A. Duhamel,P. Grossi and A.G. Russell, Ozone Modelling, Control Strategy Analysisand Aqueous Phase Chemistry Developments 846

Y. Wang and M. Hantel, Convective Fluxes and Cumulus Parameterizationin the EURAD Model 850

M. Deliry and R. Ramaroson, Simulation of NOx Transformations in aCloud System: Potential Application to a Flash Lightning 856

H. Hass, E. Berge, P. Builtjes, A. Ebel, H.J. Jakobs, M. Memmesheimer,D. Simpson and R. Stern, A Comparison of Long-Range Transport Modelsapplied for a European Summer Episode 857

M. Memmesheimer, H. Hass, H.J. Jakobs, A. Ebel and J. Beck, Simulationof a Photo-Smog Episode in Summer 1990 858

J. Ching, R. Dennis, J. Novak and T. Clark, U.S. EPA Air and Water QualityModelling: A Visual Feast of Environmental Modelling Simulations 862

R. Lamprecht and D. Berlowitz, Performance Evaluation of a Lagrangian AirQuality Model for Passive Tracers by a Sensitivity Study with Field Data 863

M.A. Sofiev, Statistical Properties of the Model Verification Problem andSpecial Methods for Comparison of Measured and Calculated Data 869

M.V. Galperin, TV. Cheshukina, M.A. Sofiev and IS. Dedkova, MSC-EastExperience of Modelling of Sulphur and Nitrogen Compounds, Ozone andTrace Metal Long-Range Transport and their Depositions and Concentrations 874

J. Vyhnalikovd, Application of a Lagrangian Stochastic Model OLORIN toDispersion in NW Bohemia 879

D. Syrakov, M. Kolarova, D. Perkauskas, K. Senuta and A. Mikelinskene,Model of Long-Range Pollutant Transport and Acidity of Precipitation forthe Baltic Region 883

C. BorregojN. Barros and M. Coutinho, Application of TwoMesometeofological Models to the Lisbon Region: Preliminary Conclusions 885

L. Gantner and J. Egger, Nesting of Mesoscale Models in Complex Terrain 886

N. Moussiopoulos and P. Sahm, Illustrative Applications of the EUMACZooming Model 889

G. Ernst, Ch. Kessler, N. Moussiopoulos, Ch. Schneider and T. Vogele,Application of the EUMAC Zooming Model to a Small Scale Region 893

xxviii Contents

Instrumentation

H. Kern, E. Almasi and N. Kirshen, Measurement of Sub Part-per-billionLevels of Volatile Organic Compounds in Air by Pre-concentration andGC-MS 901G. Baldacchini, A. Ciucci and F. D 'Amato, Ammonia Lineshapes andLINEFIT 2.0 Program 906

R. Miicke, J. Dietrich, B. Scheumann, J. Slemr, F. Slemr and P. Werle,Application of Tunable Diode Laser Spectroscopy for QA/QC Studies:A Validation of Formaldehyde Measurement Techniques 910

R. Miicke, F. Slemr and P. Werle, Measurement of Atmospheric HO2

Radicals by Tunable Diode Laser Absorption Spectroscopy: A FeasibilityStudy 915

P. Werle, Signal Processing Strategies for Sub-ppb Trace Gas Analysis byTunable Diode Laser Spectroscopy 920

H. Mac Leod, I. Carrasco, H. Poncet, G. Megie, F. Huard and W. Riedel,Development of an Airborne Tunable Diode Laser Spectrometer for FluxMeasurements of CO, O3 and CH4 by the Eddy Correlation Technique 925

J. Stutz and U. Platt, Numerical Analysis of DOAS Spectra with Linear andNonlinear Least Square Fits 930

C. Camy-Peyret, M. Carleer, C. Clerbaux, R. Colin, A.C. Vandaele,C. Hermans, P.C. Simon, B. Bergquisk, B. Galle, C. Fayt, F. Goutail,M. Nunes-Pinharanda, J.P. Pommereau, M. Hausmann, F. Heintz, U. Platt,I. Pundt, T. Rudolph, J. Plane and N. Smith, Intercomparison of Instrumentsfor Tropospheric Measurements using Differential Optical AbsorptionSpectroscopy 935

M. Carleer, R. Colin, J.M. Guilmot, P.C. Simon and A.C. Vandaele, UV -Visible Absorption Cross-Sections of Relevant Atmospheric Trace Species 940

K. Schdfer, R. Haus and J. Heland, Remote Sensing of Emission Sourcesby Ground Based Fourier-Transform Infrared Spectrometry 944

A. Clappier, B. Calpini, E. Durieux, L. Fiorani, L. Jaquet andH. Van den Bergh, Numerical Simulation of a Pump-Probe LIDARExperiment 949

L. Fiorani, E. Durieux, B. Calpini, L. Jaquet and H. Van den Bergh,Intercomparison of the Analysis Procedures for Tropospheric OzoneLIDAR Measurements 950

E. Durieux, B. Calpini, L. Fiorani, L. Jaquet and H. Van den Bergh,Changing Atmosphere Study with a Shot per Shot LIDAR Instrument 957

Contents xxix

J. Slemr, J. Dietrich, B. Scheumann, P. Komp, M. Kern, W. Junkermann

and P. Werle, Intercomparisons of Formaldehyde Measuring Techniques 963

Clouds and Aerosols

T.W. Choularton, The Great Dun Fell Experiment 1993: First Results 969

U. Baltensperger, M. Schwikowski and H. W. Gdggeler, Scavenging ofAtmospheric Constituents by Snow 973G.V. Buxton, Mechanisms for Chemical Reactions in Cloud Droplets 978

H.-C. Hansson, B. Svenningsson, B. Martinsson, E. Swietlicki andA. Wiedensohler, Incorporation of Aerosols in Clouds 984

N. Chaumerliac, S. Cautenet, N. Huret and P.J. Gregoure, Influence of

Clouds in Tracer Fields 989

F. Raes, Aerosol Dynamics in the Atmospheric Multi-phase System 993

K. Sehested, T. Logager, J. Holcman and O.J. Nielsen, Formation andReactions of the NO3 Radical in Aqueous Solution 999S. Barlow, G. V. Buxton and G.A. Salmon, The Nature and Reactions ofNO3 in Aqueous Solution 1005

S. Wolff, K.J. Brockmann, W. V. Turner and S. Gab, Formation of Alkyland 1-Hydroxyalkyl Hydroperoxides on Ozonolysis in Water and in Air 1010

P. Lagrange, G. Wenger and J. Lagrange, Kinetic Study of the AqueousSO2 Oxidation by H2O2 at Low Concentration and without Buffer 1011

H. Herrmann, A. Reese and R. Zellner, Spectroscopy of SOx~ (x = 3, 4, 5)Radical Anions and their Kinetics in the Conversion of S(IV) in AqueousSolution 1017

J. Berglund and L.I. Elding, Kinetics and Mechanism for ManganeseCatalysed Oxidation of Sulfur(IV) by Oxygen in Aqueous Solution 1021

W. Pasiuk-Bronikowska and K.L. Rudzinski, Nonstationary Autoxidationof Metal Ions in Oxidation of Sulphite 1026

W. Pasiuk-Bronikowska, T. Bronikowski and M. Ulejczyk, ManganeseCatalysed Atitoxidation of Sulphite under Steady State Conditions 1030

Ch. Brandt and R. van Eldik, pH Dependence of the Fe(III) CatalysedAutoxidation of S(IV) Oxides 103 5

V. Lepentsiotis, F.F. Prinsloo and R. van Eldik, Kinetic and MechanisticStudy of the Influence of Mixed Sulfur-Nitrogen Oxides on the RedoxBehaviour of Manganese and Iron Ions in Aqueous Solution 1036

xxx Contents

I. Grgic, M. Poje, M. Novic, M. Bizjak and V. Hudnik, Catalytic Effects ofAtmospheric Aerosol Particles in Aqueous Solution: Iron(II, III) CatalysedOxidation of S(IV) 1037

P. Hoffmann, T. Sinner, A.N. Dedik, S. Weber, J. Ensling and H.M. Ortner,Iron in Atmospheric Aqueous and Particulate Samples 1041

G.V. Buxton, G.A. Salmon and J.E. Williams, The Reaction of SO5~-with Iron(II) 1044

P. Amels, H. Elias and K.J. Wannowius, Kinetics and Mechanism of theOxidation of DMS by Peroxo Compounds in the Aqueous Phase 1048

J. Hjorth, F. Cappellani, H. Falbe-Hansen, S. Sorensen and G. Restelli,Laboratory Studies on Products and Intermediates in the TroposphericOxidation of DMS 1049

J. W. Michel, H. Herrmann and R. Zellner, Rates of Liquid Phase HydrolysisReactions of Partially Oxidized Halogenated Compounds of AtmosphericInterest 1052

H. Herrmann, M. Exner, H.-W. Jacobi and R. Zellner, Influence of IonicStrengths on Reactions in the Tropospheric Aqueous Phase 1056

D. Amouroux, C. Pecheyran, G. Uher, V. Ulshofer, O.F.X. Donard andM.O. Andreae, Experimental Study of Photochemical Reactivity inSeawater: Impact on Selenium Speciation 1060

W. Behnke, Ch. George, V. Scheer and C. Zetzsch, Formation and Fateof C1NO2 from the Reaction between N2O5 and NaCl Solution and itsPossible Kinetic Mechanism 1064

F.F. Fentner, F. Caloz and M.J. Rossi, The Uptake Kinetics of HNO3

and N2O5 on Salt 1069

J. Lu'ttke and K. Levsen, Partitioning of Phenol and Nitrophenols in Gasand Liquid Phase of Clouds 1074

P. Foster, I. Denis and V. Jacob, Solid Aerosol Impact on the (3-PineneOH Radical Reaction Rate Constant 1079

S. Schweighoefer, B. Walter, T. Carstens, D. Hupperich and U. Schurath,Determination of Gas Phase Diffusion Coefficients for Application inMultiphase Atmospheric Chemistry 1080

K. Hesse, A. Schlemm, C. Wunderlich and U. Schurath, Flow Characteris-tics of Extremely Thin Jets: Mass Accommodation Coefficient of Ozoneon Water 1085

Ch. George, J.L. Ponche, Ph. Mirabel, W. Behnke, V. Scheer andC. Zetzsch, Mass Accommodation / Uptake Coefficients of N2O5 on PureWater and on NaCl Containing Droplets 1090

Contents xxxi

K. Acker, W. Wieprecht, D. Moller, S. Naumann, A. Oestreich and R. Auel,Evidence for Ozone Destruction in Clouds 1096

K. Bdchmann, P. Ebert, I. Haag, T Prokop, A. Roder and K. Steigerwald,Field Measurements for the Determination of the Main Cations, Anionsand Elements as well as Some Organic Species in Individual Raindropsas a Function of their Size 1101

R. Forkel, W. Seidl, A. Ruggaber and R. Dlugi, Fog Modelling based onRoutinely Measured Data 1105

W.A.H. Asman, Below Cloud Scavenging Coefficients for Highly SolubleGases 1111

R.N. Colvile, T.W. Choularton, K.N. Bower, M.W. Gallagher, J.N. Cape,D. Fowler, K.J. Hargreaves, G.J. Dollard, T.J. Davies, S.A. Penkett,R.A. Burgess and BJ. Bandy, Field Studies of the Interaction of OxidisedNitrogen Compounds with Clouds 1114

M. Wells, K.N. Bower, T. W. Choularton, M. Sutton, J.N. Cape, D. Fowler,K.J. Hargreaves, G.J. Dollard and T.J. Davies, A Study of the AmmoniaBudget through a Hill Cap Cloud 1119

E. Seyffer and G. Helas, Formic and Acetic Acid Determinations in the Gasand Liquid Phase of Hydrometeors at the Summit of Great Dun Fell, U.K. 1123

M. Preifi, R. Maser, D. Schell, W. Jaeschke, K. Acker, W. Wieprecht andD. Moller, Measurements of S(IV) and H2O2 in the Gas and Liquid Phaseat Great Dun Fell 1129

D. Schell, R. Maser, M. Preifi, W. Wobrock, K. Acker, W. Wieprecht,S. Pahl, H.-W. Georgii and W. Jaeschke, The Dependence of Cloud WaterChemical Concentrations on Drop Size and Height above Cloud Base atGreat Dun Fell: Instrumentation and First Results 1133

M. Bizjak, B. Divjak, S. Kozak-Legisa, M. Poje and V. Hudnik, GDF '93:Aerosol Black Carbon (Soot) and Cloud Water Transition MetalConcentration 1138

B.G. Arends and G.P.A. Kos, The Measurement of Cloud DropletMicrophysics at Great Dun Fell 1143

M.A. Sutton\ E. Perthue, J.N. Cape, R.L. Storeton-West, D. Fowler,B.G. Arendi H. Muls, T.W. Choularton, M. Wells and K.N. Bower,Measurements of the NHx Budget over Great Dun Fell: SurfaceAtmosphere Exchange and Cloud Chemistry 1148

S. Fuzzi, L. Ricci, M.C. Facchini, G. Orsi, L. Tarozzi and J.A. Lind, Low,Molecular Weight Carbonyl Compounds and HMSA in Cloud Water atGreat Dun Fell 1153

xxxii Contents

W. Junkermann, J. Dietrich, P. Wolf, W. Wieprecht, J. Slemr, G. Kolthoffand R. Niessner, Investigations of the Vertical Distribution of TraceComponents in the Lower Troposphere using a Cable Car 1156

K.N. Bower, M. Wells, M. W. Gallagher and T. W. Choularton, TheModification of Aerosol by Clouds 1162

T. Engelhardt, R. Gieray and P. Wieser, Chemical Characterisation of Pre-,In- and After-Cloud Aerosols by Laser Microprobe Mass Spectrometry 1170

C. Ziegenbein, I.J. Ackermann, H. Feldmann, H. Hass, M. Memmesheimerand A. Ebel, Aerosol Treatment in the EURAD Model: RecentDevelopments and First Results 1176

H. Bunz, M. Koyro, W. Lindner, O. Mohler, K.-H. Naumann, H. Saathoffand W. Schock, Aerosol Chamber and Modelling Studies of AtmosphericHeterogeneous Processes 1180

A.N. Skouloudis and W. Eifler, Description of the Size Spectrum Evolutioncharacterising Aero-Disperse Particles with the Algorithm FIA2PES2 1186

C.E.L. Myhre, O. W. Saastad, C.J. Nielsen, I. Floisand, F. Stordal andG.O. Braathen, On the Uptake of HC1 and HBr on Stratospheric AerosolMimics 1191

A. Wiedensohler, M. Wendisch, H.-C. Hansson and D. Orsini, Change ofthe Submicrometer Particle Size Distribution during Cap Cloud Formation 1197

A. Virkkula, R.E. Hillamo, M. Mdkinen, T. Mdkeld and T.A. Pakkanen, AirPollution Episodes associated with Low Visibility in the Finnish Arctic 1199

T. Nielsen, A.H. Egelov, K. Granby and H. Skov, Atmospheric Occurrenceof Particulate Organic Nitrates 1201

T.C. O'Connor, F.M. McGovern, S.G. Jennings and C. Philipp, AitkenNuclei Measurements and Evidence of Gas-to-Particle ConversionProcesses at Mace Head, Ireland 1206

M. Bianchi, E. Brambilla, R. Dell 'Era and A. Testa, Atmospheric Aerosolsin Lombardy 1210

S. Despiau and S. Cougnenc, Physico-Chemical Characteristics of Aerosolstransported over the French Mediterranean Coast 1214

i

M. Schwikowski, O. Poulida, U. Baltensperger and H. W. Gdggeler,In-cloud Scavenging of Aerosol Particles by Cloud Droplets and IceCrystals during Precipitation at the High Alpine Site Jungfraujoch 1221

O. Poulida, M. Schwikowski, U. Baltensperger, J. Staehelin and W. Henrich,Physical Processes affecting the Chemical Composition of Precipitation atthe High Alpine Site Jungfraujoch, Switzerland 1225

Contents xxxiii

M.F. Kalina and H. Puxbaum, Two Characteristic Types of Snow CrystalSize Distribution observed in Clouds at Mount Sonnblick (3106 m a.s.l.),Austria 1231

M.F. Kalina and H. Puxbaum, Riming - an Explanation for the StrongSeasonality of Major Ions in Wet Precipitation at a High Alpine Site(Sonnblick Observatory, Austria)? 1235

A. Kasper and H. Puxbaum, Examination of the Equilibrium State ofHNO3, NH3, NH4+, NO3- and SO4

2 at a High Alpine Site (SonnblickObservatory, Austria) 1240

A. Kasper, A. Leopold, H. Puxbaum and M. Legrand, Determination ofFormic Acid in the Gas Phase at a High Alpine Site (Sonnblick Observatory,Austria) 1244

List of Participants 1249

Index of authors 1277