Atmospheric Environment 43 (2009) 5193–5267

Contents lists available at ScienceDirect

Atmospheric Environment
journal homepage: www.elsevier.com/locate/atmosenv

Review

Atmospheric composition change: Ecosystems–Atmosphere interactions

D. Fowler a, *, K. Pilegaard b, M.A. Sutton a, P. Ambus b, M. Raivonen c, J. Duyzer d, D. Simpson e, f,
H. Fagerli f, S. Fuzzi g, J.K. Schjoerring h, C. Granier i, j, k, A. Neftel l, I.S.A. Isaksen m, n, P. Laj o, p,
M. Maione q, P.S. Monks r, J. Burkhardt s, U. Daemmgen t, J. Neirynck u, E. Personne v,
R. Wichink-Kruit w, K. Butterbach-Bahl x, C. Flechard y, J.P. Tuovinen z, M. Coyle a, G. Gerosa aa,
B. Loubet v, N. Altimir c, L. Gruenhage ab, C. Ammann l, S. Cieslik ac, E. Paoletti ad, T.N. Mikkelsen b,
H. Ro-Poulsen ae, P. Cellier v, J.N. Cape a, L. Horváth af, F. Loreto ag, Ü. Niinemets ah, P.I. Palmer ai,
J. Rinne aj, P. Misztal a, E. Nemitz a, D. Nilsson ak, S. Pryor al, M.W. Gallagher am, T. Vesala aj,
U. Skiba a, N. Brüggemann x, S. Zechmeister-Boltenstern an, J. Williams ao, C. O’Dowd ap,
M.C. Facchini g, G. de Leeuw aq, A. Flossman o, N. Chaumerliac o, J.W. Erisman ar
a
Centre for Ecology and Hydrology, EH26 0QB Penicuik Midlothian, UK
b
Risø National Laboratory, Technical University of Denmark, 4000 Roskilde, Denmark
c
Department of Forest Ecology, University of Helsinki, 00014 Helsinki, Finland
d
TNO Institute of Environmental Sciences, 3584 CB Utrecht, The Netherlands
e
Department Radio and Space Science, Chalmers University of Technology, 41296 Gothenburg, Sweden
f
Norwegian Meteorological Institute, 0313 Oslo, Norway
g
Istituto di Scienze dell’Atmosfera e del Clima – CNR, 40129 Bologna, Italy
h
Royal and Veterinary and Agricultural University, 1870 Frederiksberg C, Denmark
i
UPMC Univ. Paris 06, LATMOS-IPSL; CNRS/INSU, LATMOS-IPSL, 75005 Paris, France
j
NOAA Earth System Research Laboratory, 80305-3337 Boulder, USA
k
Cooperative Institute for Research in Environmental Sciences, University of Colorado, 80309-0216 Boulder, USA
l
Agroscope FAL Reckenholz, Swiss Federal Research Station for Agroecology and Agriculture, 8046 Zurich, Switzerland
m
Department of Geosciences, University of Oslo, Inst. For Geologibygningen, 0371 OSLO, Norway
n
Center for International Climate and Environmental Research – Oslo (CICERO), 0349 Oslo, Norway
o
Laboratoire de Météorologie Physique, Observatoire de Physique du Globe de Clermont-Ferrand, Université Blaise Pascal – CNRS, 63177 Aubière, France
p
Laboratoire de Glaciologie et Géophysique de l’Environnement, Observatoire des Sciences de l’Université de Grenoble, Université
J. Fourier – CNRS, 38400 Saint Martin d’Heres, France
q
Universita’ di Urbino, Istituto di Scienze Chimiche ‘‘F. Bruner’’, 61029 Urbino, Italy
r
Department of Chemistry, University of Leicester, Leicester LE1 7RH, UK
s
University of Bonn, Institute of Crop Science and Resource Conservation – Plant Nutrition, 53115 Bonn, Germany
t
Bundesforschungsanstalt für Landwirtschaft (FAL) Institut für Agrarökologie, 38116 Braunschweig, Germany
u
Research Institute for Nature and Forest, 9500 Geraardsbergen, Belgium
v
INRA, INA PG, UMR Environm & Grandes Cultures, F-78850 Thiverval Grignon, France
w
Department of Meteorology and Air Quality, Wageningen University and Research Centre, 6700 AA Wageningen, The Netherlands
x
Institute for Meteorology and Climate Research, Atmospheric Environmental Research (IMK-IFU), Forschungszentrum Karlsruhe GmbH,
82467 Garmisch-Partenkirchen, Germany
y
Soils, Agronomy and Spatialization (SAS) Unit INRA, 35042 Rennes, France
z
Finnish Meteorological Institute, 00560 Helsinki, Finland
aa
Dipartimento di Matematica e Fisica ‘‘Niccolò Tartaglia’’, Università Cattolica del Sacro Cuore, 25121 Brescia, Italy
ab
Institute for Plant Ecology, Justus-Liebig-University of Giessen, 35392 Giessen, Germany
ac
Institute for Environment and Sustainability, The European Commission, Joint Research Centre, 21020 Ispra, Italy
ad
Istituto per la Protezione delle Piante – CNR, 50019 Sesto Fiorentino, Italy
ae
Botanical Institute, University of Copenhagen, 1353 Copenhagen K, Denmark
af
Hungarian Meteorological Service, 1675 Budapest, Hungary
ag
Istituto di Biologia Agroambientale e Forestale – CNR, 00015 Monterotondo Scalo, Italy
ah
Institute of Agricultural and Environmental Sciences, Estonian University of Life Sciences, 51014 Tartu, Estonia
ai
School of GeoSciences, University of Edinburgh, EH9 3JN Edinburgh, UK
aj
Department of Physical Sciences, University of Helsinki, 00014 Helsinki, Finland
ak
Department of Applied Environmental Science, Atmospher Science Unit, Stockholm University, 10691 Stockholm, Sweden
al
Atmospheric Science Program, Department of Geography, Indiana University, 47405-7100 Bloomington, USA
am
School of Earth, Atmospheric and Environmental Sciences, The University of Manchester, M13 9PL Manchester, UK

* Corresponding author. Tel.: þ44 (0) 131 445 4343; fax: þ44 (0) 131 445 3943.
E-mail address: dfo@ceh.ac.uk (D. Fowler)

1352-2310/$ – see front matter Ó 2009 Published by Elsevier Ltd.

doi:10.1016/j.atmosenv.2009.07.068
5194 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267

an
Department of Forest Ecology, Federal Research and Training Centre for Forests, Natural Hazards and Landscape, 1131 Vienna, Austria
ao
Max-Planck-Institut für Chemie, 55128 Mainz, Germany
ap
Department of Experimental Physics and Environmental Change Institute, National University of Ireland, Galway, Ireland
aq
Climate and Global Change Unit, Research and Development, Finnish Meteorological Institute, 00560 Helsinki, Finland
ar
Energy Research Centre of The Netherlands, 1755 ZG Petten, The Netherlands

a r t i c l e i n f o a b s t r a c t

Article history: Ecosystems and the atmosphere: This review describes the state of understanding the processes involved in
Received 29 January 2009 the exchange of trace gases and aerosols between the earth’s surface and the atmosphere. The gases
Received in revised form covered include NO, NO2, HONO, HNO3, NH3, SO2, DMS, Biogenic VOC, O3, CH4, N2O and particles in the size
27 July 2009
range 1 nm–10 mm including organic and inorganic chemical species. The main focus of the review is on the
Accepted 29 July 2009
exchange between terrestrial ecosystems, both managed and natural and the atmosphere, although some
new developments in ocean–atmosphere exchange are included. The material presented is biased towards
Keywords:
the last decade, but includes earlier work, where more recent developments are limited or absent.
Dry deposition
Trace gas fluxes New methodologies and instrumentation have enabled, if not driven technical advances in measure-
Resuspension ment. These developments have advanced the process understanding and upscaling of fluxes, especially
Biogenic emissions for particles, VOC and NH3. Examples of these applications include mass spectrometric methods, such as
Compensation points Aerosol Mass Spectrometry (AMS) adapted for field measurement of atmosphere–surface fluxes using
micrometeorological methods for chemically resolved aerosols. Also briefly described are some advances
in theory and techniques in micrometeorology.
For some of the compounds there have been paradigm shifts in approach and application of both tech-
niques and assessment. These include flux measurements over marine surfaces and urban areas using
micrometeorological methods and the up-scaling of flux measurements using aircraft and satellite remote
sensing. The application of a flux-based approach in assessment of O3 effects on vegetation at regional scales
is an important policy linked development secured through improved quantification of fluxes. The coupling
of monitoring, modelling and intensive flux measurement at a continental scale within the NitroEurope
network represents a quantum development in the application of research teams to address the under-
pinning science of reactive nitrogen in the cycling between ecosystems and the atmosphere in Europe.
Some important developments of the science have been applied to assist in addressing policy questions,
which have been the main driver of the research agenda, while other developments in understanding have
not been applied to their wider field especially in chemistry-transport models through deficiencies in
obtaining appropriate data to enable application or inertia within the modelling community. The paper
identifies applications, gaps and research questions that have remained intractable at least since 2000
within the specialized sections of the paper, and where possible these have been focussed on research
questions for the coming decade.
Ó 2009 Published by Elsevier Ltd.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5196
1.1. Scale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5197
1.2. Reactivity of natural surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5197
1.3. Frameworks for analysis and interpretation of trace gas and aerosol exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5197
1.4. Bi-directional exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5198
1.5. Aerosols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5198
1.6. Ocean–atmosphere exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5198
1.7. Wet deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5199
2. Reactive gaseous nitrogen compounds – oxidized nitrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5199
2.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5199
2.2. Emissions from soils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5199
2.3. Emissions of NOy from plant surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5201
2.4. Canopy atmosphere interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5201
2.5. Models and measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5201
2.6. Exchange of HNO3, HONO, PAN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5202
2.7. NOx production and emission from snow surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5205
2.8. Up-scaling and regional and global trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5205
3. Biosphere atmosphere exchange of ammonia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5205
3.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5205
3.2. Advances in measurement methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5206
3.3. Key controls on biosphere atmosphere exchange of ammonia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5208
3.4. Effects of ecosystem type on ammonia biosphere–atmosphere exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5209
3.5. Modelling surface–atmosphere exchange of ammonia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5209
3.6. Dynamic simulation of ecosystem C–N cycling and ammonia fluxes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5210
3.7. Integrating ammonia exchange processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5211
3.8. Future challenges for ammonia exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5212
4. Sulphur dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5212
4.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5212
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267 5195

4.2. Worldwide advances in SO2 flux monitoring and modelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5213

4.2.1. Asia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5213
4.2.1.1. Sulphur dioxide deposition to soils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5213
4.2.1.2. Micrometeorological measurements over vegetated areas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5214
4.2.1.3. Long-term deposition studies and inferential modelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5214
4.2.2. North America . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5214
4.2.3. Europe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5215
4.2.3.1. Long-term flux monitoring in the UK . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5215
4.2.3.2. Other recent European datasets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5215
4.3. Control of surface uptake rates by leaf cuticular chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5216
4.4. Advances in deposition modelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5217
4.5. Future challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5217
5. Ozone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5218
5.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5218
5.2. Deposition rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5219
5.2.1. European forests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5219
5.2.2. Crops . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5220
5.2.3. Grasslands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5221
5.2.4. Other vegetated surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5221
5.2.5. Non-vegetated surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5221
5.2.5.1. Snow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5221
5.2.5.2. Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5221
5.3. Non-stomatal deposition processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5222
5.4. Model development and validation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5222
5.5. Risk assessment methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5223
5.6. Potential effects of climate change . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5224
6. Biogenic volatile organic compounds (BVOC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5225
6.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5225
6.1.1. Volatile isoprenoids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5225
6.1.2. Oxygenated volatile compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5225
6.2. Environmental controls on BVOC emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5225
6.2.1. Physiological and physico-chemical controls of emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5225
6.2.2. Physico-chemical controls of emission in species lacking specific storage structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5226
6.2.3. Uptake and release of volatile compounds by vegetation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5226
6.2.4. CO2-Dependence of emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5227
6.2.5. Induced emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5227
6.3. Contemporary difficulties in scaling BVOC emissions from leaf to ecosystem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5227
6.4. BVOC fluxes over Europe, by compound and in relation to the needs of photochemical oxidant models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5227
6.4.1. Flux measurement techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5227
6.4.2. Isoprene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5227
6.4.3. Monoterpenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5228
6.4.4. Sesquiterpenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5228
6.4.5. Methanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5228
6.4.6. Acetone and acetaldehyde . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5228
6.4.7. Other compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5228
6.5. The EU large field campaigns in the Mediterranean area: from BEMA to ACCENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5228
6.6. Remote sensing of BVOC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5229
7. Deposition and resuspension of aerosols onto and from terrestrial surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5230
7.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5230
7.2. Review of new measurement approaches and instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5231
7.2.1. Flux measurements of particle numbers (size-resolved or total), without information on chemical composition . . . . . . . . . . . . . . . . . 5231
7.2.2. Flux measurements of individual aerosol chemical species . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5232
7.3. Area sources of particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5232
7.3.1. Resuspension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5232
7.3.2. Urban emissions of aerosols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5232
7.4. Dry deposition of particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5233
7.4.1. Dry deposition rates to vegetation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5233
7.4.1.1. Friction velocity (u*) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5234
7.4.1.2. Surface roughness length (z0) and canopy morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5234
7.4.1.3. Particle diameter (Dp) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5235
7.4.1.4. Atmospheric stability (z ¼ 1/L) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5236
7.4.2. Parameterising and modelling deposition rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5236
7.4.3. Dry deposition rates to urban areas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5236
7.5. Uncertainties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5236
7.5.1. Uncertainties in the application of micrometeorological flux measurement techniques for deriving the local flux . . . . . . . . . . . . . . . 5236
7.5.2. Relating measured fluxes to surface exchange: flux divergence and the effect of chemical interactions . . . . . . . . . . . . . . . . . . . . . . . 5237
7.5.3. Interpretation of measurements for model verification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5238
7.6. Future research needs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5238
7.6.1. Deposition measurements and reporting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5238
7.6.1.1. Standardisation of eddy covariance approaches and data analysis procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5238
5196 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267

7.6.1.2. Improved measurements in the accumulation mode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5238

7.6.1.3. Understanding the effect of stability and leaf properties on deposition velocities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5238
7.6.1.4. Filtering or accounting for chemical interactions and water uptake . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5239
7.6.2. Deposition models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5239
7.6.2.1. Migration to a probabilistic approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5239
7.6.2.2. Improvement of modelling approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5239
7.6.2.3. Impact of surface anisotropy on suspension & deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5239
7.7. Conclusions – aerosols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5239
8. Ecosystem–atmosphere exchange of the radiatively active gases – N2O and CH4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5240
8.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5240
8.2. Global budgets of N2O and CH4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5240
8.3. Biological sources of N2O and CH4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5240
8.3.1. The biology of production and consumption of N2O and CH4 in soils and sediments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5240
8.3.2. Distribution of active microbial populations in soils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5241
8.3.3. N2O and CH4 fluxes from the main global ecosystems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5241
8.3.4. Plant-mediated transport and production of N2O and CH4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5241
8.3.4.1. Methane from vegetation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5241
8.3.4.2. Nitrous oxide from vegetation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5241
8.4. New developments in measurements of N2O and CH4 and denitrification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5242
8.4.1. Flux chambers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5242
8.4.2. Micrometeorological methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5242
8.4.3. Comparison of eddy covariance with chamber methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5242
8.4.4. Recent methodological advances in measurements of total denitrification rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5243
8.5. Modelling of N2O and CH4 fluxes at site and regional scales: approaches, applications and uncertainties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5243
8.6. Validation of models by landscape and regional scale measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5244
8.7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5244
9. Exchange of trace gases and aerosols over the oceans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5245
9.1. New trace gas interactions at the air–sea interface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5245
9.1.1. Case studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5245
9.1.1.1. Acetone (ocean uptake) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5245
9.1.1.2. Methanol (ocean uptake) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5246
9.1.1.3. Isoprene (ocean emission) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5247
9.1.1.4. Halogenated organics (ocean emission and uptake) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5247
9.1.1.5. Monoterpenes (ocean emission) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5247
9.1.1.6. Alkyl nitrates (ocean emission) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5247
9.2. Aerosols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5247
9.2.1. Primary marine aerosol (PMA) source functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5247
9.2.2. Chemical composition of primary sea spray . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5248
9.2.3. Secondary aerosol production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5250
10. The processes of wet scavenging of aerosols and trace gases from the atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5251
10.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5251
10.2. Nucleation scavenging of drops and ice crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5251
10.3. Impaction scavenging of aerosol particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5251
10.4. Scavenging of gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5252
10.5. Clouds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5252
10.6. Orographic precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5252
10.7. Organic N in air and rain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5253
10.8. Conclusions and some priority areas of future research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5253
11. Ecosystem–atmosphere exchange – concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5254
11.1. Policy needs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5254
11.2. Current understanding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5254
11.3. Future developments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5254
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5255
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5255

1. Introduction exchange processes is a core activity in understanding the Earth

system. The subject of this review is much narrower than the
The composition of the earth’s atmosphere is unique in the scope of these opening lines, and is restricted to the trace gases
solar system in being largely determined by biological processes and aerosols exchanged between the atmosphere and the earth’s
in soils, vegetation and the oceans interacting with physical and surface. However, as is clear from much of the international
chemical processes within the atmosphere. The physical surface– assessment of changes in atmospheric composition since the
atmosphere exchange of most gases contributing major and trace industrial revolution, these trace atmospheric constituents are
constituents of the atmosphere is coupled to biological produc- changing the earth’s climate (IPCC, 2007), global biodiversity
tion processes and transferred through the surface–atmosphere (Millenium Ecosystem Assessment, 2005) and the biogeochemical
interface. Thus, developing a mechanistic understanding of the cycling of major nutrients including nitrogen, carbon, and
production and destruction processes and their interactions with sulphur.
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
The earth’s surface is a sink for some atmospheric trace gases
and aerosols, and a source for many others, and for most the
surface–atmosphere interface represents a zone within which most
of the overall control of fluxes occurs. An understanding of the rate
controlling processes at this interface is therefore vital in describing
the exchange process and understanding the global biogeochemical
cycles. Applications of science in this field are necessary to quantify
and model responses to human perturbation of many of the
biogeochemical cycles (C, N, S, halogens and metals to name but
a few). These perturbations include changes in land use or emis-
sions of trace gases to the atmosphere, through combustion and
industrial activities. Taking as an example the global nitrogen cycle,
human activity through combustion processes for oxidized nitrogen
and the Haber Bosch process for reduced nitrogen now dominates
the cycling of reactive nitrogen through the atmosphere and back to
terrestrial and marine ecosystems (Galloway et al., 2004). The total
emission of reactive nitrogen (Nr) from human activities at the end
of the 20th century exceeds that from natural processes by a factor
of 4 (20.7 Tg of oxidized and reduced reactive nitrogen Nr from
natural sources within a total of 104 Tg-N in 1993, Galloway et al.,
2004). As nitrogen is a limiting nutrient in many ecosystems,
these modifications of the natural cycling have profound effects on
ecosystem function, biodiversity and atmospheric composition
(Erisman et al., 2008). The human disturbance of the global carbon
cycle is also extensive, and the quantities involved are very large.
Global emissions of CO2 from fossil fuels since 1700 amount to
approximately 600 Gt-C, which have increased the atmospheric CO2
mixing ratio from 280 ppm to 380 ppm in 2006, an increase of about
30%, (IPCC, 2007).
These high level indicators of human influence provide essential
context for this review paper, but conceal the detailed changes
taking place and the range of chemical species and interactions
involved. The subject area includes many different chemical species,
and it is not possible to be comprehensive in this review for all gases.
In particular the subject of the global carbon cycle and CO2 in
particular are much too large to cover in this review. The focus of this
review is on the reactive trace gases and for the greenhouse gases,
CH4 and N2O. The gases are associated with a range of biological
sources and have varied chemical reactivity in the atmosphere and at
surfaces. These differences reveal the range of controls and temporal
and spatial variability in rates of exchange, which are the focus of the
review. The review moves through a range of chemical species,
identifying the current state of knowledge and, where possible
applications of the new developments in a policy context.
The gases emitted from terrestrial and ocean ecosystems
include all of the major greenhouse gases, H2O, CO2, CH4 and N2O,
the nitrogen gases (both in reduced and oxidized forms), sulphur
compounds, volatile organic compounds (VOC) and halogens.
Quantifying the fluxes of these trace atmospheric components is
a prerequisite within an assessmemnt process leading to the devel-
opment of policy on climate change, eutrophication, acidification
and photochemical oxidant formation. Many research groups have
become involved in the measurement and modelling of emission and
uptake (deposition) fluxes of trace gases and particles. The mecha-
nistic understanding has developed from two different fields of
study, the first was concerned with the sources of atmospheric trace
constitiuents, and the greenhouse gases were among the first
compounds for which surface fluxes were quantified directly by
field measurements. These included small scale (0.1 m–0.5 m2)
measurements of fluxes from soils and vegetation using chamber
methods for CO2, CO, CH4, N2O (Junge, 1963). The measurements
showed large spatial and temporal variability so that up-scaling to
regions generated very large uncertainties. The other development
was mainly associated with the atmospheric transport and deposi-
tion of pollutants, including nitrogen and sulphur compounds and
5197
the photochemical oxidants in the 1960s and 1970s (Husar et al.,
1978). These early studies were made to determine the importance of
surface removal which is better known as dry deposition (to distin-
guish the process from removal by precipitation) as a sink for reactive
trace gases (NO2, SO2, O3). Advances in understanding and computing
resources have allowed more sophisticated approaches to be adop-
ted, in which the processes at the surface recognised different sinks
and interactions with other trace gases, allowing rates of dry depo-
sition to change with time and with surface characteristics.
1.1. Scale
Emission or deposition schemes to quantify trace gas fluxes
operate at a range of scales depending on the applications, illustrated
in Fig. 1.1. For hourly integration the application is primarily
for research purposes and mechanistic study at the small scale
(<102 m2). For landscape scale measurements and for assessment of
the fate of pollutants at the regional scale (106 km2) the application
has both research and policy objectives. At this scale, spatial and
temporal integration provides robust parameterisation. The appli-
cation in global models to quantify sources and sinks is restricted in
spatial resolution, typically to 1  1, and likewise has research and
policy application Dentener et al., 2006. For the landscape scale, flux
measurements may be made directly, using micrometeorological
methods above canopies of vegetation, soil, or even ocean surfaces
and have become the method of choice for long-term flux
measurement. These techniques provide, in addition to the target
trace gas flux the turbulent exchange characteristics of the under-
lying surface and the partitioning of available radient energy which
enables the processes to be investigated at a sufficiently large scale to
integrate canopy scale fluxes over typically 105 m2 (Baldocchi et al.,
2001).
The sections focus mainly on individual trace gases or classes of
atmospheric particles, and each considers the surface–atmosphere
exchange over specific ecosystems. The exceptions are the ocean
surfaces and wet deposition, within which a range of relevant
compounds is considered.
1.2. Reactivity of natural surfaces
For many of the short lived gases (<2 days in the boundary
layer) there are multiple sinks at the surface and these include
foliar surfaces and soil whose properties as sinks for a range of
gases vary with humidity and the presence of surface water and
are influenced, sometimes strongly, by the presence of other gases
(Fig. 1.2). The chemical and physical complexity of terrestrial
surfaces, illustrated in Figs. 1.1 and 1.2 at the microscopic scale is
greatly simplified in the parameterisations used in models. The
simplification is necessary in part due to the nature of the flux
measuring systems, which integrate the net fluxes over large areas
of these surfaces, and fail to reveal the microscopic scale of
variability of the true exchange.
1.3. Frameworks for analysis and interpretation
of trace gas and aerosol exchange
The measurements of surface–atmosphere exchange provide at
the simplest level the mass exchange per unit area of surface, which
may be ground, water or leaf area, per unit time. To extract useful
information on the underlying processes it is necessary to quantify
the contributions each step in the transfer pathway makes to the
overall exchange between defined points, which in this scheme is
simplified to vertical levels between a source and a sink. The most
widely applied transfer scheme is a resistance analogue (Monteith
and Unsworth, 2007), in which the flux of trace gas or particle
5198 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267

Fig. 1.1. A diagrammatic representation of the scales of measurement of trace gas fluxes for process studies (a transverse section through a Phaseolus vulgaris leaf, showing the
palisade and mesophyll cells bounded by epidermal cells and the airspaces for internal exchange between trace gases and intercellular fluid). The field scale at which most of the
micrometeorological flux measurements are made and the continental scale where models provide the emission and deposition fluxes. In this case the emission fluxes of oxides of
nitrogen over Europe are shown, revealing the importance of international shipping to emissions over continental scales.

is treated as an analogue of electrical current flowing through 1.4. Bi-directional exchange

a simple network of resistances, which may act in series if there is
just one sink at the surface, such as a pure water surface, or may
have several sinks at the surface, acting in parallel, each repre-
senting a distinct chemical component of the underlying surface.
A simple resistance network representing three different sinks
at the surface, and the two atmospheric resistances (Ra and
Rb, respectively the turbulent transfer resistance and the leaf
boundary-layer resistance) are illustrated in Fig. 1.3.
The atmospheric resistances may be separated from the total
resistance using independent measures of the turbulence above the
vegetation. The overall flux may be measured by a variety of micro-
meteorological methods (Monteith and Unsworth, 2007), and thus
the total of the surface or canopy resistances to transfer between the
source and sink may be quantified as the residual, as shown in Fig. 1.3.
For many of the trace gases, regardless of their reactivity, the
exchange fluxes may vary in sign as well as magnitude, with
emission and deposition being commonly observed. The most
widely known example of bi-directional exchange is CO2, which
exhibits both deposition and emission fluxes due to photosynthesis
and respiration respectively. In this case the concept of compen-
sation points as mixing ratios at which no net exchange takes place
is now widely recognised for a range of trace gases (NH3, NO, CO2)
but all controlled by very different processes.
The recognition of bi-directional exchange requires modelling
approaches to simulate the process for application in surface–
atmosphere exchange schemes, as illustrated for NH3 in Fig. 1.4.
1.5. Aerosols

The understanding of deposition and emissions of aerosols over

terrestrial surfaces has advanced considerably in the last decade,
after a long period in which application of a model developed by
Slinn (1982) has been a standard for many modelling approaches.
Likewise, the emission of aerosols by resuspension from terrestrial
surfaces has advanced following innovative new measurement
approaches described in this review.

1.6. Ocean–atmosphere exchange

For many years the ocean–atmosphere exchange of trace gases has

Fig. 1.2. Illustrating the importance of different sinks for reaction of trace gases at the
terrestrial surfaces, notably the external surfaces of vegetation often as in this case
covered by complex layers of epicuticular wax and illustrated in Fig. 1.1, the internal
structure of leaves, following uptake through the stomatal apertures and soils greatly
simplified in this illustration.
been treated in a simplistic way (Liss et al., 1981), in part due to the
relative simplicity of the ocean surface relative to terrestrial surfaces,
but also due to the limited knowledge base to support more complex
treatments. However there has been an accelerating interest in ocean–
atmosphere exchange as new techniques have become available
to make the flux measurements and as very new issues have been
identified. Current interest in ocean acidification and ocean eutro-
phication further raise the profile of ocean–atmosphere exchange, and
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
χO3 (z-d)
Ra
Rb O3
R = R a + Rb + R c
FO3 t
R c2 1
Rc3 cuticle R c1 Rc =
stomata 1 1
soil + +
R c1 R c2 R c3
χO3 (z 0' ) = 0
Fig. 1.3. A simple resistance analogy for a trace gas with sinks in stomata, on foliar
surfaces and in soil.
given that these surfaces cover 71% of the earth’s surface, the relatively
small section of this review paper on this topic belies its importance in
understanding atmospheric composition change.
1.7. Wet deposition
Process understanding in the scavenging of gases and particles
by precipitation has continued to advance, with important devel-
opments during the last decade. The applications of wet deposition
schemes are very important in the Long-Range Transport (LRT)
models and increasingly in global chemistry-transport models
(CTM) (Stevenson et al., 2006). These two applications make very
different demands on available knowledge and understanding. In
the case of LRT models in Europe (e.g. EMEP), the applications
form part of the integrated assessment process and within the user
community the pressure to provide ever finer spatial scale esti-
mates of inputs presents challenges in the capability of LRT models
and the meteorological models on which they depend. Current
demand for assessments of effects at the 1 km  1 km scale allows
the scale of the input estimate to approach the scale of an individual
nature reserve, for example.
The focus of this paper on surface–atmosphere exchange processes
spans a wide range of trace gases and particles. The motives for studies
of many of the specific gases were environmental policy related, for
example to determine the atmospheric lifetime, travel distance and
Fig. 1.4. A diagrammatic representation of bi-directional exchange, for NH3 exchange between the atmosphere and vegetation.
5199
deposition footprint of pollutants (e.g. with reference to acidification,
eutrophication, metal deposition or photochemical oxidants). These
applications require an understanding of the fate and transformations
of the emitted trace gases within the atmosphere. The developments
in understanding atmospheric chemistry of the trace gases discussed
in this paper are reviewed in the companion paper (Monks et al., this
issue) in this volume.
1 2. Reactive gaseous nitrogen compounds – oxidized nitrogen
2.1. Introduction
Developments in understanding surface–atmosphere exchanges
of NO and NO2 over the last decade have focussed on three specific
issues: the long-term emission of NO from soils; the interaction of
chemical processing of nitrogen oxides in and above plant canopies;
and the deposition of NO2 and HNO3 to foliar and soil surfaces. The
measurements have been made over different vegetation, but the
recent focus has been on forests, in part because the interactions
between these processes are greatest for forests, but also because
some of the measurements are simpler to make and interpret for
mature forests. This section outlines the developments in under-
standing NOy exchange between terrestrial ecosystems and the
atmosphere, concentrating on developments during the last decade.
2.2. Emissions from soils
Soil surface emissions of NO are the result of several biological
and abiotic processes in the soil producing and consuming NO.
Production and consumption of NO occurs predominantly via the
biological nitrification and denitrification processes. Nitrification is
the oxidation of soil NHþ 
4 to NO3 , and denitrification is the anaerobic

reduction of soil NO3 to N2O and N2. In nitrification, NO is formed as
a by-product during the oxidation of NHþ 
4 to NO2 and possibly also as

a result of nitrifier reduction of NO2 leading to an NO production of
1–4% of the NHþ 4 being oxidized (Skiba et al., 1997). The NO produced
may be transformed within the soil profile by oxidation to NO 3 or it
may be released to the atmosphere following diffusion to the
soil surface. In denitrification, NO occurs as an intermediate in the
cascade of reductive processes, and in the soil profile NO reduction
may contribute to the formation of N2O. Abiotic production of
NO occurs from oxidation of nitrous acid (HONO) that has been
produced by protonation of biologically formed NO 2 (Venterea et al.,
5200 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267

2005). Under certain conditions e.g. after application of anhydrous

ammonia to agricultural soils or acidic forest soils, the coupled
biological-abiotic production of NO may constitute the dominant
process for soil NO emissions (Venterea and Rolston, 2000; Gödde
and Conrad, 1998). Factors that increase nitrification and denitrifi-
cation, e.g. substrate and O2 availability, temperature and pH are
thus predicted to influence NO formation. Likewise, factors affecting
transport processes in the soil are predicted to regulate emissions of
NO (and other gases). It has been hypothesized (Davidson, 1991) that
where WFPS (water-filled pore space) is less than 0.6, nitrification is
the dominant process and relatively high emissions of NO may
be observed. Under more reducing conditions, 0.6 < WFPS < 0.9,
denitrification dominates which has a higher potential for NO
production compared to nitrification (Skiba et al., 1997); however
under conditions where anoxic conditions are generated by high soil
water content or by compaction of fine textured soil the probability
of NO being re-consumed by the denitrifying community is greatly
enhanced. Soil water may also play a central role in mediating
chemical processes leading to NO formation (Venterea et al., 2005).
Under most soil conditions, both nitrification and denitrification
occur simultaneously and the net flux of NO between soil and atmo-
sphere is the result of both processes together. As current views of
controls over NO gas emissions are still incomplete and need revision
e.g. with emphasis on the role of abiotic formation (Venterea et al.,
2005) there is a continuous need to further develop and improve
methodologies to identify and characterise the NO formation
processes. Gödde and Conrad (1998) achieved this by a combined
modelling and experimental approach to determine the net NO flux in
relation to NO concentration to quantify production and consumption
rate constants and compensation concentration. Recent advances in
methodological approaches to deepen our understanding of soil based
NO emissions have included application of stable isotope techniques.
Stark et al. (2002) applied a 15N-isotope pool dilution method-
to obtain the simultaneous gross rates of NO forming processes
combined with soil emissions, and Russow et al. (2000) adopted
a kinetic isotope method (KIM) to study the complex N transformation
processes involved in soil NO emissions.
Fig. 2.1. Left: NO emission (mg N m2 h1) as a function of nitrogen deposition
NO and N2O emissions were measured continuously at 15 forest (g N m2 s1). Regression lines (solid ¼ significant, dashed ¼ non significant) for
sites in Europe (Pilegaard et al., 2006) including coniferous and coniferous and deciduous sites, respectively. Right: N2O emission (mg N m2 h1) as
deciduous forests in different European climates, ranging from a function of C/N ratio. The full line represents a linear regression and the dotted line
boreal to temperate continental forests and from Atlantic to Medi- a logarithmic regression.

terranean forests. Furthermore the sites differ in atmospheric N-

deposition ranging from low deposition (0.2 g N m2 yr1) to high
deposition (4 g N m2 yr1).
The relationships of the emissions of NO and N2O, with the
parameters, nitrogen deposition, forest type, age, C/N in the surface
horizon, pH, soil temperature and water-filled pore space (WFPS)
were investigated by means of stepwise multiple regression anal-
ysis. NO emission was dependent on forest type and positively
correlated with nitrogen deposition (Fig. 2.1). WFPS was tested for
curvature by including a quadratic term, but this was not signifi-
cant. Separately performed regression analyses for deciduous and
coniferous forests showed that the relationship between nitrogen
deposition and NO emission was only significant for the coniferous
forests: (NO (mg N m2 h1) ¼ 13.9 þ 25.5 [N deposition
(mg N m2 h1)], r2 ¼ 0.82). The N2O emission was significantly
negatively correlated with both the C/N ratio and the age of the
stands; a logarithmic transformation of N2O emission improved the
significance of the correlation.
Soil temperature is a key variable affecting the emission rates of
both gases (Fig. 2.2). Emissions of both NO (Slemr and Seiler, 1984)
and N2O (Skiba, 1998) increase with soil temperature due to the
positive effect of temperature on enzymic processes as long as
other factors (e.g. substrate or moisture) are not limiting. Soil water
acts as a transport medium for NO þ
3 and NH4 and influences the
rate of O2 supply and thereby controls whether aerobic processes
such as nitrification or anaerobic processes such as denitrification
dominate within the soil. While N2O emissions are known to
increase at higher water contents through larger losses from
denitrification the relationship between the NO flux and the soil
water is more complex. Due to limited substrate diffusion at very
low water content and limited gas diffusion at high water content,
nitric oxide emissions are suspected to have a maximum at low to
medium soil water content.
The effects of soil moisture and temperature on NO and N2O
emission were studied in laboratory experiment with soil cores
from a range of field sites (Schindlbacher et al., 2004). Soil moisture
and temperature explained most of the variability in NO emission
(up to 74%) and N2O (up to 86%) emissions for individual soils. NO
and N2O were emitted from all soils except from a boreal pine forest
soil in Finland, where the laboratory experiment showed net NO
consumption. NO emissions from a German spruce forest ranged
from 1.3 to over 600 mg NO–N m2 h1 and greatly exceeded
emissions from other soils. Average N2O emissions from this soil
tended also to be largest (170  40 mg N2O–N m2 h1), but did not
differ significantly from other soils. NO and N2O emissions showed
a positive exponential relationship with soil temperature.
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
400
NO emission [μg NO-N m-2 h-1]
300
200
100
0 Production of NOy on Scots pine branch surfaces by ultraviolet
-5 0 5 10
Forest floor temperature [°C]
Fig. 2.2. Relationship between daily mean forest floor temperature and daily mean NO
emissions at the Höglwald Forest (spruce, control) for the observation period January 1,
2004–December 31, 2006. For details on measurement and site characteristics see
Gasche and Papen (1999).
The results from the annual averages of field data did not show
significant relationships with soil temperature for either NO or for
N2O emission. Schindlbacher et al. (2004) showed that N2O emis-
sions increased with increasing WFPS or decreasing water tension,
respectively. Maximum N2O emissions were measured between 80
and 95% WFPS or 0 kPa water tension. The optimal moisture for
NO emission differed significantly between the soils, and ranged
between 15% WFPS in sandy Italian floodplain soil and 65% in loamy
Austrian beech forest soils. For the field data WFPS was not
a significant parameter for N2O emission, but had a positive signif-
icant effect on NO emission (Fig. 2.3). The annual average WFPS in
the field was higher than the optima found for NO in the laboratory
experiment, but since not all field sites were studied in the labora-
tory it is difficult to provide a general conclusion. The inter-annual
variation within single sites clearly showed relationships to both
temperature and soil moisture. An important factor for N2O emis-
sion is freeze-thaw events which can produce a significant outburst
of N2O (Kitzler et al., 2006).
100
NO emission (% of maximum)
80
60
40
20
0
0 20 40 60
WFPS(%)
Fig. 2.3. The relationship between NO emission and water-filled pore space at different
localities in the NOFRETE project (based on data in Schindlbacher et al., 2004).
5201
In general, relationships between nitrogen oxides emission and soil
moisture and soil temperature can be found within a single locality
when studying short-term variations. However, when comparing
annual values from different localities within a large region, parame-
terisations differ appreciably between locations and other factors such
as soil properties, stand age, and site hydrological conditions interfere.
This scale of variability has slowed the development of improved soil
NO emission inventories, and their application in global chemistry-
transport models. So while it is disappointing to observe current
generation CTMs using 1995 soil NO estimates, it is understandable
and identifies a need for better parameterisations and soil emission
databases for global application.
2.3. Emissions of NOy from plant surfaces
15 20 radiation has been observed in Hyytiälä, southern Finland (Hari
et al., 2003) (Fig. 2.4). Other studies have shown that irradiance-
dependent NOy emissions from snow and different chamber surfaces
have been observed to originate from HNO3 or nitrate photolysis. In
Hyytiälä forest, Raivonen et al. (2006) investigated whether the NOy
emitted from pine shoots could originate from photolysis of HNO3
attached to the needle surface. Field data of several years from
Hyytiälä were used to test this hypothesis. The HNO3 deposition,
estimated for the Hyytiälä site, has been high enough to account for
the NOy emission rates observed from the chambers. The particular
characteristics of the daily pattern of CO2 exchange or stomatal
control was not reflected in the NOy flux. When a pine branch
was rinsed, which reduced the amount of water-soluble nitrogen
compounds (e.g. HNO3, nitrates and HONO) from the needle surface,
NOy emissions from that branch decreased compared to another
non-rinsed branch. Therefore, it was concluded that the results
support the hypothesis and that HNO3 photolysis on plant surfaces
needs to be taken into account both from air chemistry and plant
sciences point of view.
2.4. Canopy atmosphere interactions
The interaction between chemical reactions of nitrogen oxides
taking place in the canopy and trunk space of a forest is a special
case because in this area chemical and turbulent timescales change
substantially leading to a very complex situation in which even the
direction of fluxes may change (Duyzer et al., 1995) (Fig. 2.5).
This makes it nearly impossible to interpret measurements of the
turbulent fluxes of some reactive trace species above the canopy from
single point eddy covariance measurements. Several models have been
Sandy loam developed to simulate the overall exchange and show the magnitudes
Silty loam of the different competing processes. These models describe the
Sandy clay loam
Loam(1) coupled processes of atmospheric transport and chemical processes
Loam(2) above and in canopies in detail. Over forests the situation is even more
complex. Flux measurements are usually carried out near the top of
rough canopies leading to potential inaccuracies in the K-theory
approximation. This theory is relatively easy to combine with vertical
atmospheric transport phenomena with fast chemical reactions.
2.5. Models and measurements
Measurements of small fluxes of NO and NO2 have shown spurious
results especially at low concentrations due to a lack of specificity of
monitors and a lack of instrument sensitivity, but other problems may
well have contributed, including violation of conditions under which
80 100
such fluxes may be measured above canopies and the complexity of
interactions; soils and sunlight driven reactions may both be sources
of NOy and these interact with the stomatal sinks and the chemical
processing within the canopy trunk space Duyzer et al., 1983.
5202 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Fig. 2.4. Effect of UV radiation on the NOy concentration in a small Teflon chamber that enclosed a clean pine branch or a branch that had been treated with NH4NO3 solution. The
branches were dead and dry, cut from the tree. UV wavelengths were filtered away using a Plexiglas plate (Raivonen et al., 2006).
As a result of these limitations there are only limited data
available for verification of models. Duyzer et al. (2004) described
the analyses of a dataset acquired in the framework of a European
project from an experiment carried out in a 20 m high coniferous
forest (Speulderbos, The Netherlands). A 1D multi-layer model of
a forest canopy was used to analyse the field data. In each layer
vertical transport was described using K-theory; canopy uptake
was described using a resistance layer model. Simple chemical
reactions between ozone and nitric oxide and photolysis of
nitrogen dioxide were described. The coupled differential equa-
tions were solved numerically. Input to the model calculations were
concentrations of nitrogen oxides and ozone at the highest level
above the forest, levels of radiation, temperature, humidity, wind
speed, turbulence parameters and an estimate of the emission of
nitric oxide. Output of the model is the concentration and fluxes of
the relevant components at the height of each level in and above
the canopy. These may be compared with measured fluxes of these
components at two levels above and one below the canopy. It is fair
to say that the comparison between measured and modelled fluxes
is not impressive. There are many possible explanations for this
observation but no clear single cause has been identified.
Depending on the magnitude of this soil flux the NO2 flux is
either downward or upward. In the case of the coniferous forest
described here and the conditions during the experiment the result
was that when the NO flux from the soil exceeded 10 ng m2 s1,
the NO2 emission was upward (i.e. away from the forest).
At high concentrations the NO2 flux is directed towards the
forest and at small concentrations the flux is more likely to be
directed towards the free atmosphere. This may be interpreted as
Fig. 2.5. A schematic of the various canopy interactions involved in the exchange of
nitrogen oxides between the free atmosphere and forests.
a compensation point above which the flux is directed towards the
surface and below which the flux is away from the surface.
In summary the flux of NO2 above a forest can be described with
the following function:
 
1
FNO2 ¼ f FNO;soil  CNO2 
Rc;NO2
where all variables have their common meaning and CNO2 denotes
the concentration of nitrogen dioxide above the canopy. This
equation is rather qualitative but indicates the sensitivity of the flux
of NO2 above the canopy. More quantitative model runs are needed,
but these require a large amount of input data and the results are
still uncertain.
A simple resistance model (Duyzer et al., 2005a,b) was tested in
a deciduous forest (Sorø, Denmark) and is illustrated in Fig. 2.6.
Generally the understanding of the various processes and their
interaction is increasing. Nevertheless many uncertainties
remain and there is a need for further improvement of models,
especially for Lagrangian models incorporating chemical reac-
tions. On the other hand, the accuracy of the results of field
measurements has been rather low. It should be noted that
although the interaction between atmospheric chemical reac-
tions and exchange between the canopy and the atmosphere is
easy to understand its importance may be limited. In cases where
fluxes of nitrogen oxides are small the corrections could be large
in a relative sense but still rather small in an absolute sense. The
currently available models could very well be capable of making
estimates of the magnitude of these effects. In view of all the
uncertainties hindering improved estimates in testing of models
the limited quality of the description of atmospheric transport
processes within the canopy may not be a serious problem here.
2.6. Exchange of HNO3, HONO, PAN
The deposition of HNO3 to terrestrial surfaces has been shown to
be primarily controlled by the rates of turbulent exchange in the
atmospheric boundary layer and the leaf boundary layer (Huebert
and Robert, 1985). The highly reactive and soluble nature of gaseous
HNO3 leads to large rates of deposition, approaching the maximum
rates of deposition limited by turbulent exchange when each
molecule arriving at terrestrial surfaces is immediately absorbed at
the surface. In these conditions the surface is considered to be
acting as a perfect sink, canopy resistance is zero and the numerical
value for the deposition velocity becomes:
VgðNHO3 Þ ¼ Vmax ¼ 1=ra þ rb
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Fig. 2.6. Profiles of CO2, NO2, O3 and NO in a beech forest near Sorø, Denmark. The profiles clearly show the effects of stable conditions during night and daytime turbulence mixing
the full air column. CO2 is built up during night due to soil respiration; O3 is depleted during night due to deposition and chemical reactions. At the soil surface high concentrations
of NO are seen due to emission from the soil.
The values for deposition velocity in these conditions are very
sensitive to wind velocity values and approach several cm s1 even
over relatively short vegetation. The consequence of these large rates
of deposition are that even in areas with small HNO3 concentrations,
dry deposition contributes a substantial quantity if nitrogen. Taking an
ambient concentration of 0.1 ppb HNO3, the annual deposition of N for
a forest would be of the order 3 kg N ha1 annually from HNO3 alone.
The close coupling between rates of turbulent exchange and
dry deposition rates for HNO3 also generates substantial spatial
variability in N deposition in the landscape, with hotspots for N
deposition being forests and especially forest edges, hedgerows and
isolated, exposed hills, where wind speeds are larger.
Several studies have recently attempted to measure total
oxidized nitrogen (NOy) fluxes or even total reactive nitrogen
(Nr ¼ NOy þ NHx) to ecosystems (Turnipseed et al., 2006). These
approaches offer the prospect to apply eddy covariance techniques
for the robust and relatively cost effective determination of total
atmospheric N deposition, but they do not provide the chemical
speciation needed to further process understanding. There have,
however, also been advances in the understanding of individual N
compounds other than NH3, NO and NO2.
A recent lab study (Sparks et al., 2003) has confirmed that PAN
deposition through the stomata can make a significant contribution
to plant uptake of atmospheric N. In addition, recent instrument
developments in chemical ionisation mass spectroscopy (CIMS)
and thermal-dissociation laser induced fluorescence (TD-LIF) have
enabled the application of eddy covariance to the biosphere/
atmosphere exchange of preoxy acyl nitrates (PANs such as PAN,
PPN and MPAN). Measurements were made over two contrasting
5203
US pine forests at Duke Forest, North Carolina, (RH > 75%) and
Blodgett Forest, California, (RH < 30%) (Farmer et al., 2006; Turn-
ipseed et al., 2006; Wolfe et al., 2008).
At Duke Forest fluxes of PAN, PPN and MPAN were measured with
a CIMS technique (Turnipseed et al., 2006). There were no significant
differences in the Vd of the three different PAN compounds, but all
three species deposited about four times faster than predicted by the
model of Wesely (1989) during the day, and nearly an order of
magnitude faster during the night, indicating that aqueous solubility
considerations are insufficient to predict the behaviour of PAN on
surfaces. The average Vd was 2.5 mm s1 during day and 8 mm s1
during night. In contrast to the considerations of Wesely (1989), wet
surfaces showed a smaller non-stomatal resistance (Rns ¼ 125 s m1)
than dry surfaces (Rns ¼ 250 s m1).
At the much drier Blodgett forest site, the flux of the sum of all
PANs was measured by TD-LIF, based on thermal conversion and NO2
detection (Farmer et al., 2006). PAN was derived as the difference
between the ambient temperature and 180  C channel. They found
upward fluxes in summer and on average bi-directional exchange
with afternoon deposition in winter, when noon-time deposition
velocities averaged 8 mm s1. More recently, these measurements
have been repeated with the more selective CIMS technique (Wolfe
et al., 2008). Here measurements indicated larger average midday
values of Vd for PPN (12 mm s1) than for the PAN and MPAN
(4 mm s1), while both compounds deposited slowly at night
(Vd < 2 mm s1). The authors of this study attribute the difference in
the Vd between compounds to MPAN and PAN production inside the
canopy and suggest that the PPN fluxes are a better descriptor of the
surface deposition. They suggest that the non-stomatal uptake is
5204 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267

dominated, but not fully explained, by thermochemical decompo-
sition, and thus strongly linked to canopy temperature.
In summary, this recent measurement evidence suggests that
deposition rates of PANs in warm climates are at least a factor of 5
larger than predicted by commonly used models and non-stomatal
deposition is larger to wet and humid surfaces than to dry surfaces.
During the same TD-LIF study, Farmer et al. (2006) measured
fluxes of total alkyl nitrates (gas and aerosol phase), from the differ-
ence between the 180  C and 330  C channels. These compounds
showed large winter-time midday deposition velocities of 20 mm s1,
approaching those of HNO3 (25 mm s1). Even higher Vd of 30 mm s1
was derived by Horii et al. (2005) for what they interpret as isoprene-
derived hydroxyalkyl nitrates.
Nitric acid (HNO3) has traditionally been believed to deposit at
the maximum rate possible according to turbulence (Vmax) and its
flux measurement continues to be used to derive quasi-laminar
boundary-layer resistances for vegetation (e.g. Pryor and Klemm,
2004). This view has been challenged by recent measurements
that indicated non-negligible canopy resistances in the range of 50
to >200 s m1 during midday (Nemitz et al., 2004b, 2008). This
has been attributed to non-zero chemical compensation points
governed by the thermodynamic equilibrium with NH4NO3 on leaf
surfaces or fertilizer pellets. Fig. 2.7 shows an example of reduced
deposition of HNO3 and HCl over a Dutch heathland.
The view that HNO3 normally deposits with a near zero canopy
resistance still holds. There is an increasing measurement database
of HNO3 concentrations in national and regional networks suitable
for inferential modelling of HNO3 deposition (Tang et al., 2009),
which now provides independent confirmation from the model
results, that HNO3 deposition makes a very significant contribution
to nitrogen deposition across Europe. In addition, Europe-wide
monitoring activities have produced the first hourly monitoring
datasets of HNO3, which allows for a much more in-depth assess-
ment of the performance of oxidized nitrate chemistry in atmo-
spheric transport models (Tarrason and Nyiri, 2008).
Much development has occurred in measurement techniques
for nitrous acid (HONO), e.g. based on long path absorption
photometry (LOPAP) and differential optical absorption spectrom-
etry (DOAS). This has contributed to the improvement of process
understanding of sources of HONO in the atmosphere, e.g. revealing
larger daytime sources than previously thought and identifying
NO2 reactions with humic acid as a novel production mechanism

10

0
Fχ [ng m s ]
-2 -1

-10

-20 HNO3 HCl

-30

-40
15:00 18:00 21:00 00:00 03:00 06:00 09:00 12:00 15:00 18:00 21:00 00:00
30
25 Vmax(HNO3)
Vd [ mm s ]

Vmax(HCl)
-1

20
Vd(HNO3)
15
Vd(HCl)
10
5
0
15:00 18:00 21:00 00:00 03:00 06:00 09:00 12:00 15:00 18:00 21:00 00:00
500

400
Rc [s m ]
-1

300
HNO3
200
HCl
100

0
15:00 18:00 21:00 00:00 03:00 06:00 09:00 12:00 15:00 18:00 21:00 00:00
0.5 120

0.4 RH u* 100
RH (z0') [%]
u* [m s ]

80
-1

0.3
60
0.2
40
0.1 20
0.0 0
15:00 18:00 21:00 00:00 03:00 06:00 09:00 12:00 15:00 18:00 21:00 00:00
GMT

Fig. 2.7. A time series of HNO3 and HCl exchange measured above a Dutch heathland with a denuder gradient system with online analysis by ion chromatography. The panels show:
(a) fluxes, (b) deposition velocities of HNO3 and HCl in comparison with their maximum values and (c) Rc for HNO3 and HCl, (d) friction velocity (u*) and relative humidity (h). Data
represent 2.5 h running means of 30 min. Vd(HNO3) and Vd(HCl) are reduced compared with their maximum values, presumably due to non-zero chemical compensation points
originating from deposited NHþ 4 salts. From Nemitz et al. (2004a).
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
(Kleffmann et al., 2005; Stemmler et al., 2006). By contrast, appli-
cations of these approaches to flux gradient measurements are still
rare, which nevertheless confirm surface sources of HONO (Vitel
et al., 2002; Kleffmann et al., 2003).
2.7. NOx production and emission from snow surfaces
Snow lying on the Earth’s surface has traditionally been viewed
as a chemically inert medium, whose influence on the overlying
atmosphere was exerted through its albedo effect, and by
restricting exchange of gases between the air and land/sea surfaces.
The a priori view was that the boundary layer and troposphere over
Antarctica would be somewhat uninteresting, with low concen-
trations of reactive radicals such as OH, HO2, NO and NO2, and
a composition dominated by longer-lived chemical species. The
equivalent regions of the Arctic atmosphere were assumed domi-
nated by long-range transport of anthropogenic emissions from
lower latitudes. However, recent research has shown that this
picture is far from the truth, and that snow is a highly photo-
chemically active medium. Snow-pack impurities, of which there
are many, can be photolysed to release reactive trace gases to the
atmosphere. These processes are likely to be active anywhere that
sunlight irradiates snow. The importance of these processes to
boundary layer composition varies with geographical location; in
regions with a high background of radicals, for example arising
from anthropogenic pollution, emissions from snow are of lesser
importance. But in the remote polar regions, emissions from snow
can be the dominant source of reactive trace gases and have a major
influence on boundary layer chemical composition. This conclusion
was first reached for NOx (NO þ NO2), which was measured in
the boundary layer at Summit, Greenland at surprisingly high
concentrations, and with a ratio to NOy that suggested a local
source. Measurements of NOx within the snow-pack interstitial air
revealed concentrations that were higher still, suggesting that the
snow-pack itself was the source, with a gradient to the atmosphere.
Subsequent measurements made in Antarctica confirmed that
NOx production within the snow-pack was a feature of both
polar regions (Jones et al., 2000). Additional measurements
confirmed that NOx generated within the snow-pack was released
to the overlying boundary layer (Jones et al., 2001), contributing
to the higher than expected NOx concentrations that were
encountered.
The air chemistry of polar regions is a rapidly developing field
and extends substantially beyond interest in oxidized nitrogen, in
which surface processes clearly provide the major source of reac-
tive oxidized nitrogen in Antarctic regions. Discussion of other trace
gases, including halogen and mercury compounds are beyond the
scope of this review, however a valuable review of polar halogen
chemistry and links to oxidized nitrogen chemistry is provided by
Simpson et al. (2007).
2.8. Up-scaling and regional and global trends
The complexity of processes involved in NO emissions from soils
has resulted in a significant uncertainty in the regional and global
source strength of soils for NO. However, different methodologies
have been developed, e.g. relatively simple statistical models as
well as process-based model approaches, to cope with the problem
of regionalisation of soil NO fluxes. The most widely used approach
to calculate regional NO emissions from soils is based on the work
of Yienger and Levy (1995). These authors consider land use and
respective background emission strengths, nitrogen fertilization
rate (2.5% loss of applied nitrogen), temperature effects (three
classes: cold-linear, exponential and optima) as well as the pulsing
of NO emissions following prolonged dry periods (four classes,
5205
based on intensity of rainfall) to estimate soil NO emissions.
Yienger and Levy also provide a canopy reduction factor to include
estimates of the chemical conversion and re-deposition of NO as
NO2 within the canopy. Compared to the methodology by Yienger
and Levy, the Skiba-EMEP/CORINAIR approach is more simplistic.
Based on a literature review by Skiba et al. (1997) this approach
postulates that 0.3% of any form of nitrogen is volatilized as NO, i.e.
regardless whether it originates from inorganic or organic fertil-
ization or atmospheric N deposition. Furthermore, a background
emission of 0.1 ng NO–N m2 s1 (z0.032 kg NO–N ha1 a1) was
assumed (Simpson et al., 1999). In addition, EMEP/CORINAIR also
use a more detailed methodology (BEIS-2), which originates from
the work of Novak and Pierce (1993) and considers soil temperature
as well as different land use classes. A statistical summary model
was developed by Stehfest and Bouwman (2006), which is based
on the most extensive literature review currently available.
This methodology for calculating soil NO emissions on global and
regional scales considers land-use, N fertilization rate [Fertilizer],
soil N content (three different classes, estimated as 1:10 of soil
organic carbon content) [SON] and climatic regions. The method-
ology was recently adapted to calculate a European wide inventory
of NO emissions from forest soils (Kesik et al., 2006). Kesik et al.
used the process-oriented ecosystem model Forest-DNDC. The
model was extensively tested for its performance to predict NO
emissions at the various NOFRETETE field sites, which were located
across Europe and, thus, were covering different climatic condi-
tions (Pilegaard et al., 2006). Regionalisation was finally achieved
by linking the model to a detailed GIS database holding all relevant
information for initializing and driving the model such as data on
vegetation (e.g. forest type) and soil properties (e.g. texture, soil pH,
organic C content) and climate (either present day conditions or
projected future climate predictions). This approach demonstrated
for the first time the huge regional differences in NO emissions
from forest soils across Europe as shown in Fig. 2.8, to estimate its
significance on a regional scale and to unravel the importance of
atmospheric N deposition for the magnitude of forest soil NO
emissions.
3. Biosphere atmosphere exchange of ammonia
3.1. Introduction
Substantial progress has been made during the last five years in
understanding ammonia biosphere–atmosphere exchange. Experi-
mental studies have included controlled laboratory analysis, while
a series of micrometeorological studies have assessed net fluxes
occurring under field conditions. In particular, major advances have
been made in modelling the different aspects of ammonia exchange.
This has included not just analysis of the drivers of the vertical flux
densities, but also a consideration of non-stationarities, such as
advection effects and chemical interactions. Traditionally, micro-
meteorological experiments were designed to avoid these effects,
focusing as far as possible on ‘ideal’ micrometeorological conditions,
so as to better quantify the vertical exchange processes, and develop
parametrisations for ‘dry deposition schemes’ in regional models
(Fowler and Duyzer, 1989; Fowler et al., 1998; Sutton et al., 1994;
Simpson et al., 2006). However, for ammonia, it has become
increasingly clear that these non-stationarities represent important
effects that are widespread in the real environment and need to be
quantified (Sutton et al., 2007, 2008c).
The developments in the last decade have arisen from a wide range
of national and international projects. National studies have particu-
larly addressed exchange with key ecosystems of regional importance,
such as ammonia losses from agricultural systems (e.g. Milford et al.,
2001a; Walker et al., 2006; Wichink Kruit et al., 2007) and the
5206 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Fig. 2.8. Importance of atmospheric N deposition for NO emissions from forests soils. The
map shows the difference in NO emissions between a scenario with zero atmospheric
N deposition and present day atmospheric N deposition. In large parts of central Europe
but also Scandinavia forest NO emissions are likely to decrease significantly if atmo-
spheric N deposition can be reduced to background levels.
ammonia inputs into semi-natural ecosystems of conservation value
(e.g. Wyers and Erisman, 1998; Neirynck and Ceulemans, 2008).
Collaborative international projects have sought to integrate and
extend these interests, making the comparison between ecosystem
types and looking at the interactions (e.g. Sutton et al., 2009a).
The first European collaborative project dedicated to ammonia
exchange was ‘EXAMINE’. Attention was given to quantifying
ammonia exchange with a range of European ecosystems, under both
experimental and field conditions (e.g. Sutton et al., 1995; Schjoerring
et al., 1998; Neftel et al., 1998; Meixner et al., 1996; Nemitz et al.,
2009b), including analysis of the surface gas-particle interactions
between ammonia, nitric acid and hydrochloric acid (Nemitz and
Sutton, 2004). As part of EXAMINE a major collaborative analysis was
made in the North Berwick experiment, which provided a uniquely
detailed examination of the processes controlling ammonia exchange
with an oilseed rape canopy (Husted et al., 2000; Nemitz et al.,
2000a,c; Sutton et al., 2000a,b).
In the second major European collaboration dedicated to
ammonia, the GRAMINAE project analyzed the processes controlling
ammonia exchange with grassland ecosystems across Europe (Sut-
ton et al., 2001). This included assessment of both the bi-directional
fluxes of ammonia with agricultural grassland – as these affect
atmospheric ammonia balance (e.g. Milford et al., 2001a; Mosquera
et al., 2001), and with semi-natural grasslands as these are impacted
by the atmosphere (e.g. Horváth et al., 2005). These studies
were complemented by the LIFE project, which added long-term
ammonia flux data for a number of grassland, moorland and forest
ecosystems (e.g. Flechard and Fowler, 1998; Erisman et al., 2001;
Spindler et al., 2001).
As understanding of ammonia exchange has improved and
scientific ambition developed, increased attention has been given to
integrating the different drivers of ammonia exchange processes. This
has, for example, been reflected in the Braunschweig Integrated
Experiment of GRAMINAE (e.g. Sutton et al., 2002, 2008a, 2009a,b),
which linked a wide range of biospheric, atmospheric and manage-
ment interactions as these control ammonia exchange with managed
grassland. This integration has developed substantially under the
NitroEurope Integrated Project (Sutton et al., 2007), in which inter-
actions between the different components of nitrogen fluxes,
including ammonia and oxidized nitrogen and their effect on the net
greenhouse gas balance have been investigated. In parallel, major
advances have been made in spatial modelling of ammonia fluxes,
from individual forest edges to global scales (Theobald et al., 2004;
Dentener and Crutzen, 1994; Hertel et al., 2006; Bleeker et al., 2006).
3.2. Advances in measurement methods
Before considering the developments outlined above in more
detail, it is important to highlight that the advances have been
critically dependent on improvements in measurement technology
(See Table 1). At the start of the 1990s, ammonia flux measure-
ments were still being made using wet chemistry and manual batch
sampling with time integration of typically 2 h (e.g. Sutton et al.,
1993a; Duyzer, 1994). The most important advance was the intro-
duction of continuous wet chemistry methods for measuring
ammonia profiles, including the AMANDA wet rotating denuder
(Wyers et al., 1993) and the mini-Wet Effluent Diffusion Denuder
(e.g. Blatter et al., 1993; Neftel et al., 1999). Although these tech-
niques are liable to malfunction, with effort and careful operation
they have produced many key datasets over the last 15 years
(e.g. Erisman and Wyers, 1993; Sutton et al., 1995, 1997; Fowler
et al., 1998; Flechard and Fowler, 1998; Neftel et al., 1998; Milford
et al., 2001a,b) and still represent the state-of-the-art as regards
precise measurement of small ammonia fluxes (Wichink Kruit et al.,
2007; Neirynck and Ceulemans, 2008; Sutton et al., 2008b).
A unique inter-comparison of four continuous wet chemical
systems was made at the GRAMINAE Braunschweig Experiment
(Sutton et al., 2007, 2009b; Milford et al., 2009), which highlights
the potential and limitations of the approach. Fig. 3.1 shows the
ammonia flux measured before and after cutting an agricultural
grassland, and following subsequent fertilization with calcium
ammonium nitrate. The measurement systems were able to detect
the wide range of ammonia fluxes, but the degree of agreement
varied greatly between days. This was a result of varying perfor-
mance of the different analysers, highlighting the need for highly
intensive instrument maintenance.
Despite the improvements that have been made in the automation
and reliability of the continuous wet chemical gradient methods (e.g.
Wichink Kruit et al., 2007; Flechard et al., 2007; Sutton et al., 2007),
their remain several limitations, which have encouraged researchers
to seek alternative ammonia flux measurement approaches. In prin-
ciple, many refinements have allowed the automated wet chemical
methods to become more reliable and comprehensive (such as being
able to measure aerosol and acid gas gradients simultaneously, Trebs
et al., 2006). However, the use of many moving parts can be consid-
ered as inherently liable to faults. Similarly, the response times of
these instruments are typically >5 min, which means that they
are normally limited to the measurement of mean concentration
differences and vertical gradients.
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267 5207

Table 1
Practical suitability of systems to measure ammonia biosphere–atmosphere exchange.

Chemical approach Advantage Disadvantage Application References

Box AGM REA EC

Simple, cheap, high
Batch filter packs Uncertain gas – aerosol split, batch J J L L Sutton et al. (1993a,b)
air volume

Simple, cheap good

Batch denuders Low air volume, batch J J L L Duyzer (1994)
gas-aerosol split

Automated batch Automated in field, medium High laboratory processing cost, J J L L Loubet et al. (2006, 2009)
annular denuders cost, precise, high air volume only hourly, need two
systems for fluxes

Continuous annular Automatic sensitive, Cost, complexity, fault liable, JJ JJ L L Wyers et al. (1993), Erisman and Wyers (1993),
denuders precise, high air volume gradient only Sutton et al. (1995, 2000b, 2001a)
and Nemitz et al. (2001b)

Continuous parallel Automatic, sensitive,

Cost, complexity, fault liable J J JJ L Nemitz et al. (2001a) and Hensen et al. (2008)
plate denuders high air volume REA

Continuous Automatic, Cost, complexity, fault liable J JJ J L Hensen et al. (2008)

mini-WEDD sensitive, precise

Continuous Automatic, sensitive, Cost medium complexity J JJ J L Flechard et al. (2007) and Hensen et al. (2008)
membrane precise, reliable
denuder AIRmonia

Photo-accoustic Automatic, sensitive, Cost, complexity, not reliable JJ J L L Whitehead et al. (2008)
in principle reliable

Tunable diode laser Automatic, sensitive, Very high cost, complexity, J J L J Shaw et al. (1998), Famulari et al. (2004),
fast response (>10 Hz) maintenance Twigg et al. (2005) and Whitehead et al. (2008)

AGM: Aerodynamic Gradient Method; REA: Relexed Eddy Accumulation, EC: Eddy Covariance.

The benefits of quantifying ammonia fluxes using the gradient

technique have been clearly demonstrated by the many papers
published using this approach. In terms of informing our under-
50
standing of ammonia exchange processes and model development,
NH3 flux (ng m s )

Pre-cut
-1

CEH
this has almost exclusively been provided by measurements
-2

25 FRI
using the aerodynamic gradient method (90%), with a few studies
0 (in continental climates) applying the modified Bowen Ratio
method (5%). By contrast, the key disadvantage of this method is
-25 that it depends on micrometeorological stationarity, with no
change in the vertical flux with height. These flux/gradient methods
-50
are not suitable for the study of exchange fluxes where advection of
-75 ammonia from local sources is of interest (e.g. Loubet et al., 2001,
NH3 flux (ng m s )

2006) and where gas-particle ammonia–ammonium interactions

-1

22/05/00 23/05/00 24/05/00 25/05/00

Post-cut are significant (e.g. Brost et al., 1988; Nemitz et al., 1996, 2004b).
-2

CEH
FRI
FAL-D
To address some aspects of advection and air chemistry interac-
500
FAL-CH tions, determination of fluxes at a single height offers a way forward.
If this can be achieved, in principle, deployment of replicate
measurement systems at several heights could then be able to
0 determine vertical flux divergences (Sutton et al., 2007). Both the
Eddy Covariance (EC) method and Relaxed Eddy Accumulation (REA)
allow fluxes to be determined from measurements at one height, and
31/05/00 01/06/00 02/06/00 03/06/00
NH3 flux (ng m s )

have therefore been the subject of several recent studies. The

-1

6000 Post-fert
advantage of REA is that slow response ammonia measurements can
-2

CEH
FRI be combined with fast response switching, as has recently been
FAL-D
4000 demonstrated in an inter-comparison of 4 REA systems for ammonia
FAL-CH
(Hensen et al., 2008). A further advantage is that programmed
2000 periods of random switching between air up- and down-drafts
allows automatic zero checks and the correction of any bias (Nemitz
0 et al., 2001a; Hensen et al., 2008). By contrast, the challenge for REA
06/06/00 07/06/00 08/06/00 09/06/00 and ammonia is that the concentration differential to be measured is
typically much smaller than for the gradient method, which to a large
Fig. 3.1. Inter-comparison of continuous profile systems for measuring ammonia fluxes extent cancels the benefit of auto-referencing.
by the aerodynamic gradient method (AGM), from the GRAMINAE Braunschweig
Experiment. Although highly scattered, this flux inter-comparison is unique and repre-
sents the current state-of-the-art in chemical detection systems for ammonia fluxes.
Several recent studies have demonstrated the potential of fast
Increased emissions due to cutting of the underlying grass sward (29 May) and the effect response tunable diode laser absorption spectroscopy (TDLAS)
of N fertilization with (100 kg N ha1, 5 June) are clearly shown (Sutton et al., 2007). for measurement of ammonia fluxes by eddy covariance
5208 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
1200
TDLAS
1000 QC-TDLAS
Flux NH3 (ng m-2 s-1)
800
600
400
200
0
-200
29/04/2005 29/04/2005 30/04/2005 30/04/2005 30/04/2005 30/04/2005
14:24 20:24 02:24 08:24 14:24 20:24
Date, Time (GMT)
Fig. 3.2. Fluxes of NH3 measured by eddy covariance over intensively managed
grassland (Easter Bush, Scotland) several days after the application of liquid manure to
the grassland (Sutton et al., 2007).
(Shaw et al., 1998; Famulari et al., 2004; Whitehead et al., 2008).
In principle, reliable flux measurements can now be made for
periods of large ammonia fluxes (e.g. after manured application),
as has recently been demonstrated in an inter-comparison of
two laser systems (Fig. 3.2). However, there was little correlation
for fluxes <50 ng m2 s1, while the AMANDA systems have been
shown to be able to measure <10 ng m2 s1 (e.g. Sutton et al.,
1998). Table 1 provides an overview of these and other systems
for measuring ammonia fluxes. In principle, TDL and EC has the
potential to be rated as high as the continuous gradient methods,
but this still needs to be demonstrated by a more substantial body
of published measurements, particularly over longer time
periods and of a suitable quality for testing of models.
3.3. Key controls on biosphere atmosphere exchange of ammonia
Fig. 3.3 summarizes the main processes affecting the net
exchange of ammonia with the atmosphere (Sutton et al., 2007).
The primary driver of ammonia exchange is the difference
between the atmospheric ammonia concentration and the
Fig. 3.3. Summary of the key issues affecting the net land–atmosphere exchange of
ammonia. Each of these interactions can lead to ammonia fluxes changing with height
above the ground. Ideally, flux measurements, based on e.g. relaxed eddy accumulation
or eddy covariance, made at several heights above the canopy would be used to
quantify these effects, though until now such assessments have had to focus on the use
of vertical profiles in mean ammonia concentration.
average concentration in the ecosystem canopy, both of which
vary in time and in space (e.g. Sutton et al., 1995; Asman et al.,
1998). Within the canopy, several sources and sinks combine
together to determine the average ammonia concentration in the
canopy, including exchange with plant tissues through stomata,
with leaf cuticles and with decomposing leaf litter and the soil
surface (e.g. Denmead et al., 1976; Sutton et al., 1993b, 1998).
Ammonia within or immediately above the canopy airspace may
undergo chemical reactions, for example forming particulate
matter, while depletion of gases within a plant canopy coupled
with altered microclimate can lead to evaporation of ammonium
containing aerosol (Brost et al., 1988; Nemitz et al., 2004b).
Finally, the complex nature of ammonia sources and sinks in rural
landscapes means that strong horizontal gradients of ammonia
occur. The result is that ammonia is not simply deposited from
above, but fluxes are often significantly influenced by advection
effects, for example where advection from a ground level source
beneath a micrometeorological reference height adds substan-
tially to a net deposition flux (Loubet et al., 2001, 2008, 2009;
Milford et al., 2001b).
It is relevant to summarize the main influences on the primary
drivers of exchange, the atmospheric ammonia concentration and
the mean concentration of ammonia within the canopy. The first
of these is influenced partly by dispersion from adjacent
ammonia sources and partly by exchange with the surface itself.
Over a surface which acts as an ammonia sink, above-canopy
ammonia concentrations are depleted relative to background
concentrations, while above canopy concentrations may be
significantly enhanced if the surface is a net source (e.g. Sutton
et al., 2000a).
The mean ammonia concentration of the canopy itself results
from the resolution of competing emission and deposition
processes with leaf cuticles, through stomata and with the ground
surface. The concept of ‘compensation point’ concentrations has
often been used to describe these relationships. The earliest view of
a compensation point for ammonia related it to exchange through
plant stomata with the leaf apoplast (Lemon and Van Houtte, 1980;
Farquhar et al., 1980). Under this interpretation, net ammonia
fluxes would depend on the difference between what has since
been termed the ‘stomatal compensation point’ (cs) and the
atmospheric concentration (ca). By contrast, subsequent studies
highlighted the fact that ammonia deposition rates were often
faster than feasible by stomatal uptake, demonstrating the impor-
tance of ammonia deposition to leaf cuticles (e.g. Sutton et al.,
1993a,b; Duyzer, 1994). The resolution between these positions was
provided in the development of the concept of the ‘canopy
compensation point’ (cc), which accounts for both bi-directional
stomatal exchange and deposition to leaf cuticles (Sutton and
Fowler, 1993; Sutton et al., 1995). Such canopy compensation point
concepts have since been further developed to include bi-direc-
tional exchange with leaf surfaces and exchange with the ground
surface under the canopy (e.g. Sutton et al., 1998; Flechard et al.,
1999; Nemitz et al., 2001b).
These inter-relationships are developed quantitatively in a two-
layer canopy compensation point model (Nemitz et al., 2001b). One
of the key points to note about ammonia compensation points is
that they depend on the net solubility of ammonia in aqueous
solution, which is largely dependent on its equililbrium with
ammonium ions. By combining the temperature dependence of the
Henry equilibrium and the ammonium dissociation equilibrium,
the gaseous ammonia concentration can be compared with a given
ratio of [NHþ þ
4 ]/[H ], which has been termed G (Nemitz et al., 2000c,
2001a; Sutton et al., 2000b). On this basis, G can be used to provide
temperature-normalized compensation points, for example
cs ¼ f(T, Gs) where Gs ¼ [NHþ þ
4 ]apoplast/[H ]apoplast.
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
3.4. Effects of ecosystem type on ammonia
biosphere–atmosphere exchange
It has long been established that ecosystem type affects net
ammonia fluxes (cf., Denmead et al., 1976; Horváth, 1983; Sutton
et al., 1993b, 1995; Duyzer, 1994). Overall, unfertilized ecosystems,
such as forest and moorlands are generally sinks for atmospheric
ammonia, while fertilized and grazed agricultural ecosystems tend
to show bi-directional fluxes with some periods of deposition and
some periods of emission. Of course, the distinction is not absolute,
as smaller ammonia emissions may also occur from semi-natural
ecosystems (e.g. Sutton et al., 1995; Flechard and Fowler, 1998).
However, such a general difference is clear, and can be explained by
the increase in cs and cground that occurs in fertilized and grazed
ecosystems. Two recently published examples of ammonia exchange
provide a useful basis to highlight these differences.
Neirynck et al. (2005) report ammonia flux measurements made
using the AMANDA technique (Wyers et al., 1993) over a coniferous
forest in Belgium. Their forest site occurs in an area of intensive
livestock rearing, so that ammonia concentrations from some wind
directions are very large (5–25 mg m3) while for other wind sectors
ammonia concentrations were more moderate (2–4 mg m3). Even
considering the effects of canopy wetness, in all conditions the
mean diurnal profiles show consistent net deposition to the forest
canopy. Curiously, the largest deposition fluxes occurred in dry
conditions, which is unusual, as Rw would be expected to be smaller
when the canopy is wet (Sutton et al., 1995; 1998; Nemitz et al.,
2001b). Although this difference is partly explained by different
values of Fmax during conditions of different canopy wetness, this
does not to fully explain the difference. Further analysis by Neir-
ynck et al. (2005) showed differences in the overall canopy resis-
tance (Rc) for ammonia deposition with different canopy wetness
and temperature, and with larger values of Rc occurring at higher
ammonia concentrations.
Neirynck et al. (2005) did report periods of net ammonia
emission from their forest canopy (Fig. 3.4). These were recorded
during periods with winds from the high ammonia wind sector and
found to only happen at very large ammonia concentrations, which
occurred when air temperatures were larger than 15  C and relative
humidity less than 60%. Fig. 3.4 presents an intriguing result, since
according to the concepts of ammonia compensation points
a different picture should emerge, namely that periods of ammonia
emission occur when atmospheric ammonia concentrations are
small. By contrast, such a relationship is possible when emissions
from a canopy are strong (and not compensation point driven), so
that it is the emissions from the surface that generate increased
ammonia air concentrations. This phenomenon was also observed
following harvest of an oilseed rape field (Sutton et al., 2000a,b).
Fig. 3.4. Dependence of ammonia flux on concentration in the high ammonia wind
sector during warm daytime conditions with dry canopy (Neirynck et al., 2005).
5209
It is feasible that these emission periods represent events
of desorption of previously deposited ammonia occurring in
dry conditions. Conversely, it is also feasible that they represent
apparent ‘emissions’, being an artefact whereby horizontal
ammonia concentration gradients away from an adjacent ground-
based ammonia source (e.g. manure spreading, farms etc) lead to
an advection error. This would reduce the measured deposition
rate and could explain apparent ammonia upward fluxes in this
context. This illustration emphasizes the complexity of measuring
ammonia exchange processes and highlights the need for further
investigation of each option.
The above example of mainly ammonia deposition to a forest
ecosystem may be contrasted with recently published measure-
ments of ammonia fluxes over an intensively managed grassland in
the Netherlands (Wichink Kruit et al., 2007). The diurnal patterns in
ammonia concentration and net exchange flux are illustrated
in Fig. 3.5. Hourly ammonia concentrations in the air at this site
were again very large, 1–50 mg m3, with an overall mean of around
10 mg m3. In this case, net emission occurred for around 40% of the
diurnal period (10:00–20:00), with net deposition at other times.
Wichink Kruit et al. (2007) also estimated the canopy
compensation point (cc) based on profile estimation of c (zo0 ). They
then combined this with estimates of surface temperature to esti-
mate G(zo0 ) or ‘Gc’ from the measurements (Fig. 3.6). Estimated
values of cc were in the range 1–30 mg m3, which is comparable
with other studies for managed grassland (e.g. Milford et al., 2001a;
Sutton et al., 2001; Loubet et al., 2006), and substantially smaller
than the upper values implied for the forest in Fig. 3.4. Normalized
for canopy temperature, the values of Gc were in the range
200–11,000 through a period of May to October 2004, with a mean
value of just over 2000.
3.5. Modelling surface–atmosphere exchange of ammonia
Over recent years, the canopy compensation point approach has
become the standard technique to model bi-directional ammonia
surface–atmosphere exchange. Starting with the 1-layer models
offsetting bi-directional stomatal exchange against deposition to
leaf surfaces (Sutton and Fowler, 1993; Sutton et al., 1995, 2007),
subsequent models have developed in several directions. The main
subsequent developments can be summarized as follows:
Treatment of multiple canopy layers: In addition to ammonia
exchange with the top part of the canopy, leaf litter and the soil
surface have been shown to be important sources of ammonia
emission into the plant canopy (e.g. Nemitz et al., 2000a). For an
oilseed rape canopy Nemitz et al. (2000b) also highlighted the
importance of an upper and lower part of the main foliage, dis-
tinguishing the main foliage from an over canopy of oilseed ‘siliques’.
In practice this three layer model becomes complex to parametrize,
and there has now developed consensus that a two-layer model
represents an appropriate balance of realistic description while
avoiding excess complexity. A recent implementation of the 2-layer
model is that of Personne et al. (2009) for the GRAMINAE Integrated
Experiment (Sutton et al., 2009b). They used measured bioassay
estimates of Gs and Glitter (Mattsson et al., 2008a,b; Herrmann et al.,
2008) combined with an energy balance approach to calculate
component resistances, showing close agreement with measured
ammonia fluxes (Fig. 3.7).
Treatment of cuticular fluxes: The initial parametrisations of
the cuticular resistance (Rw) allowed only for deposition, depen-
dent on relative humidity (Sutton and Fowler, 1993; Sutton et al.,
1995) or vapour pressure deficit (Nemitz et al., 2000c, 2001b). As
noted above for the forest example, ammonia deposited to a canopy
surface may also be re-emitted to the atmosphere, particularly
under drying conditions. A first approach to simulate this effect
5210 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267

Fig. 3.5. NH3-concentration (upper panel) and NH3-flux (lower panel) measurements above managed grassland in The Netherlands from 18 July until 15 August 2004 (summer
period). The horizontal axis represents time of the day (UTC). Local time is UTCþ2. The vertical axis represents the NH3-concentration (mg m3) or NH3-flux (ng m2 s1). Diamonds
A are calculated values for the half-hourly NH3-concentration or NH3-flux; the solid line (dd) (with vertical 25 and 75 percentile bars) is the median of all half-hourly fluxes for
that time. The dashed line (- - -) in the lower panel is the mean leaf wetness signal during this period (Wichink Kruit et al., 2007).

treated the leaf surface as a humidity dependent capacitance
(Qd), which would be in equilibrium with a non-zero leaf surface
concentration (cd) (Sutton et al., 1998). In this case an adsorption/
desorption resistance (Rd) is also defined. This first dynamic
approach had the advantage of being able to simulate ammonia
charging and discharging of the cuticle, but had the disadvantage
that the leaf surface pH needed to be specified as an input. The
approach was further developed by Flechard et al. (1999) who
considered the full aqueous chemistry on leaf surfaces, dependent
on multiple air pollutant inputs and potential leaching of base
cations from leaf surfaces. In this model, leaf surface pH is solved by
ion balance, and the model is able to take account of the effects of
other trace components such as SO2 on ammonia fluxes. Burkhardt
et al. (2008) have recently extended this model to incorporate the
two-layer approach with bi-directional exchange for each of the
leaf surface, stomata and ground surface. The cuticular resistance
clearly responds to the chemistry of the liquid film on vegetation
and the combination of reactive gases present (Flechard et al.,
1999). Even in the absence of additional reactive trace gases, the
cuticular resistance declines with increasing NH3 concentration.
In a series of chamber experiments Jones et al. (2007) quantified
the relationships between ambient NH3 concentration and the bulk
canopy resistance for a range of moorland vegetation as shown in
Fig. 3.8 in which the non-stomatal ‘cuticular’ resistance is seen to
increase lineary with NH3 concentration, leading to much smaller
deposition at high concentrations than if deposition velocity
remained constant with concentration as is usually assumed.
3.6. Dynamic simulation of ecosystem C–N cycling
and ammonia fluxes
A disadvantage of the compensation point scheme for simu-
lating ammonia fluxes outlined above is that empirical values of
G must be provided. The only way forward from this position is to
develop models of carbon–nitrogen cycling that can simulate
G values for the different pools based on an understanding of the
pool dynamics (cf. Massad et al., 2008). To date, the only such
model to attempt this coupling is the PaSim model of Riedo et al.
(2002). The model distinguished plant nitrogen pools into struc-
tural nitrogen, substrate nitrogen and apoplastic nitrogen (a sub-
pool of substrate nitrogen), linking these with plant uptake and
growth processes. The model was parametrised based on measured
fluxes for a Scottish grassland (Milford et al., 2001b) and has
recently been tested for the Braunschweig Experiment (Sutton
et al., 2009b). Overall, the model was able to simulate the larger
net emissions that occurred after cutting and after fertilization, as
well as the decline in the 10 day period following fertilization. By
contrast, the component fluxes were less well described. Bioassays,
chamber measurements and within-canopy profiles during the
Braunschweig Experiment (Mattsson et al., 2008a,b; Herrmann
et al., 2008; Nemitz et al., 2009b) highlighted leaf litter as being
a key source of emission following cutting. This source is currently
not simulated in PaSim, which simulated that increased emissions
after cutting were due to an increase in apoplastic ammonium. The
bioassays indicated that the foliage was more likely to be a sink of
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Fig. 3.6. Derived canopy compensation points (cc ¼ c(zo0 )) (upper panel) and ratios between NHþ
end of October 2004 (diamonds) and the constant value (2200) that is normally assumed for modeling (line) (Wichink Kruit et al., 2007).
soil/litter ammonia emissions, highlighting the need for improved
ecosystem modelling of ammonia exchange that accounts for litter
decomposition processes (Sutton et al., 2000b).
3.7. Integrating ammonia exchange processes
The preceding sections have highlighted the many processes
and interactions that combine to regulate ammonia fluxes between
vegetation and the atmosphere. It thus becomes a major challenge
to integrate each of these processes to develop a holistic view. It is
necessary to quantify the interactions in each case in order that
valid conclusions can be obtained. This creates a major challenge
for experimentalists to be able to address all the questions in the
field. For example, in the absence of measurements of horizontal
concentration profiles, it is difficult to quantify the potential for
advection effects to have influenced the results presented in
Fig. 3.4. Similarly, it remains an open question in most studies
whether gas-particle interactions have a significant influence on
measured ammonia fluxes.
It was with such interactions in mind that the GRAMINAE
Integrated Experiment was designed. A number of findings from
this experiment have already been mentioned, but the experiment
demonstrates both the challenges and the power of developing an
integrated approach. Fig. 3.9 summarizes each of the issues and
measurement methods that were investigated during this experi-
ment (Sutton et al., 2008a). The key conclusions from this study
have been summarized by Sutton et al. (2009b) and include:
5211
þ 0
4 and H concentration (Gc ¼ G(zo )) (lower panel) from the end of May until the
1. That unreplicated ammonia flux measurements in most studies
are highly uncertain and need to be considered with caution
when compared with model estimates.
2. That advection effects can significantly influence measured
ammonia fluxes, both due to dispersion away from nearby
point sources (correction for advection effects increases net
deposition) and due to emissions from an emitting field itself
(correction for advection increases net emission).
3. That gas-particle interactions had a minor effect on measured
ammonia fluxes, though the relative effect on calculated aerosol
deposition rates was significant (being the cause of apparent
aerosol emissions).
4. That reasonable agreement can be made between relaxed eddy
accumulation for ammonia and the aerodynamic gradient
method, though measurements are not yet sufficiently precise
to detect flux divergence (except for possible cases of extreme
advection errors).
5. That net emissions from this grassland canopy are controlled by
the recapture of leaf litter ammonia emissions by overlying
foliage and the interaction of cuticular exchange pools with
mainly stomatal uptake of ammonia from the leaf litter emis-
sions. Net emissions increase following cutting due to exposure
of the litter and cutting induced senescence, with a similar
recapture process affecting net emission following fertilization.
A range of models is able to simulate the dynamics of net
ammonia exchange with the managed grassland, but further
5212 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267

4500 key challenges include the climate dependence of net ammonia

Measured flux
4000 emission and deposition, and the characteristic fluxes of other
Modelled flux (Gamma Litter)
3500 ecosystems in the world.
NH3 fluxes (ng m s )
-1

In principle the models of ammonia exchange incorporate the

3000
-2

main features of environmental conditions and could therefore be

2500
2000
1500
1000
500
0 Although there have been many studies of ammonia emission from
-500
22-May 29-May 05-Jun
Fig. 3.7. Comparison of ammonia fluxes simulated by a two-layer canopy compensa-
tion point model (SURFATM-NH3) with measured fluxes (Fmg) during the GRAMINAE
Braunschweig Experiment. For this model scenario, the ground emission is assumed to
originate from leaf litter based on measured Glitter (Personne et al., 2009).
attention is needed to develop dynamic treatments of ammonia
emissions from leaf litter decomposition.
3.8. Future challenges for ammonia exchange
The results from the GRAMINAE Integrated Experiment provide
a microcosm of some of the key challenges to measure ammonia
fluxes and model the process interactions. In a wider perspective
applied in different climates. Here the limitations include the lack of
available data for empirical factors such as G values and the back-
ground data to extrapolate to conditions with different climates.
Currently, the estimates of G have mainly been derived for cool
European conditions and for a very limited number of ecosystems.
fertilized tropical systems, such as rice and maize, there are few
12-Jun published studies of ammonia fluxes over semi-natural unfertilized
tropical ecosystems. The rates of ammonia deposition or emission
in these situations are thus highly uncertain. Given the differences
in biology of these systems, measurements are required to underpin
modelling approaches.
A modest degree of climate change (e.g. þ2  C) is a much easier
matter to simulate, for example based on the analysis of temperature
effects within existing datasets. The thermodynamics of ammonia
solubility and dissociation are rather straightforward, indicating for
example a doubling in cs every 5  C increase for a given value of
G (Sutton et al., 2001). However, caution is needed before making
climate change simulations on this basis. Analysis of the PaSim model
under different temperature regimes showed that net ammonia
fluxes for Easter Bush in Scotland (cf. to measured fluxes of Milford
et al., 2001b) were quite insensitive to temperature. For example,
increased temperature (in the absence of moisture limitation) led
to increased grass growth which diluted available nitrogen pools,
thereby reducing G values (Sutton and Milford, unpublished simu-
lations). Similarly, increases in wetness, while favouring smaller
values of Rw may also lead to increased rates of leaf litter decompo-
sition, favouring ammonia emissions. To take another example, in
colder conditions, NH3 from manure application to the land surface
tends to be emitted at smaller rates, but the emission lasts longer,
especially if a waterlogged or frozen soil conditions prevent infiltra-
tion. With these illustrations in mind, it becomes a major future
challenge to generalize how ammonia fluxes might change in the
future under different climatic regimes.

4. Sulphur dioxide

4.1. Introduction

There are three very different spatial scales relevant to the

Fig. 3.8. The relationship between ambient ammonia concentrations and the cuticular
resistance to deposition for moorland vegetation. A significant difference was found
between day and night for the bulk canopy resistance (Rc), which included both
stomatal uptake and deposition to the leaf surfaces. Once the effect of the stomatal
resistance (Rs) was accounted for, the cuticular resistance (Rw) was found to approx-
imately constant day and night (Jones et al., 2007).
exchange of SO2 at terrestrial surfaces, first the micro-scale, at which
the chemical and biological interactions occur (Fig. 1.1). Second is the
spatial scale at which most of measurement and interpretation
takes place, which is the field scale (averaged over 103–105 m2) for
measurements using micrometeorological methods. Lastly, the
application of knowledge of the surface exchange process is primarily
at regional to continental scales to characterise the fluxes and
budgets within chemistry transport models (CTM) and comparisons
with the concentration fields observable from satellites.
The measurements have mainly been made at the field scale
using micrometeorological methods, although there have been
some laboratory studies, mainly in the early days of SO2 dry
deposition research. The initial measurements were used to esti-
mate the regional scales of dry deposition, often using a fixed
deposition velocity as a key variable within long-range transport
models (e.g. Fisher et al., 1978). With larger datasets of measure-
ments covering a wide range of conditions, it is clear that rates
of dry deposition vary considerably in time and space (Fowler
and Unsworth, 1979) in particular because the sinks available at
terrestrial surfaces, including the stomata in vegetation, leaf
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Estimation of Advection of
farm-scale NH3 NH3 from nearby
emissions sources & effects
from plume on vertical fluxes
measurements
Effects of dew
& leaf surface
chemistry
on NH3 fluxes
Within-canopy
cycling of NH3 fluxes
Determination of
within-canopy
turbulent exchange
Soil chemistry interactions
with plant N uptake & NH3 fluxes
Fig. 3.9. Overview of issues addressed by the GRAMINAE Integrated Experiment (Sutton et al., 2008a).
surfaces and the presence of liquid water on vegetation from dew
or rain, present a variable absorbing surface. The data have shown
the role of atmospheric composition and surface leaf water chem-
istry in controlling canopy resistance.
Most dry deposition measurements of sulphur dioxide over the
last 30 years have been made in N. America and Europe, and have
served as a basis for the parameterisation of dry deposition models
(Erisman, 1994; Smith et al., 2000; Zhang et al., 2002), which in turn
have been applied to ecosystems in different parts of the globe.
However, most SO2 emission and deposition now occurs outside
N. America and Europe. Asia’s contribution in 1985 of 20% to global
anthropogenic SO2 emissions has doubled since then, reaching 37%
by the year 2000, of which 23% is emitted by China alone and 5% by
India.
Southern China is one of the world’s most sulphur polluted
areas. Paradoxically, in Northern China, where ambient SO2
concentrations are very large, rainfall is generally alkaline, and the
areas polluted by acid rain do not necessarily correspond to the
areas of high SO2 emissions. One of the reasons for this discrepancy
is the presence of alkaline soils (yellow sand) distributed over
the arid areas of N.W. China (e.g. the loess plateau and Gobi desert),
the windborne erosion of particles with high base cation concen-
trations can neutralize atmospheric acidity (Utiyama et al., 2005).
Loess soil, which covers vast areas of the Eurasian continent
extending from N.E. China to Central Asia, contains Ca in large
quantities, and calcium carbonate (CaCO3) reacts with atmospheric
SO2, to form calcium sulphate (CaSO4). Thus, even bare soil without
vegetation may be a significant sink (Sorimachi and Sakamoto,
2007), which may affect the regional SO2 budget if the process is
inadequately quantified in dry deposition models.
In this section we review research and monitoring from the last
decade, including SO2 dry deposition measurements from Asia,
North America and Europe, as well as findings from long-term flux
monitoring experiments. The current state of knowledge concern-
ing mechanisms of SO2 dry removal from the atmosphere is
reviewed, with consequences for temporal trends in atmospheric
concentration and deposition, and key future research areas are
identified.
5213
Quantification of Interactions with acid
energy balance & gases and ammonium
environ controls on particles & effects
NH3 exchange on net NH3 fluxes
Continuous
measurement of NH3
fluxes by gradient
and REA approaches
Effects of cutting
& N fertilization
events & choices
NH3 compensation
points of foliage
Plant bioassay
determination of
NH3 emission potential
Effects of leaf senescence
NH3 release from and plant species on
litter decomposition NH3 emission potential
4.2. Worldwide advances in SO2 flux monitoring and modelling
4.2.1. Asia
Sulphur dioxide dry deposition to vegetated surfaces is largely
controlled by non-stomatal processes, but in many arid ecosystems
and deserts of the world where vegetation is sparse, the nature and
pH of soils determine the sink strength. In Asia, substantial efforts
have for example gone into the characterization of SO2 uptake by
loess soils, given their large geographical representation in
Northern China, their alkaline nature and their ability to neutralize
atmospheric acidity and to serve as an oxidation medium for
SO2. Both micrometeorological and laboratory- or field-based
flow reactor methods were deployed. New micrometeorological
measurements over forests and short vegetation have also been
reported over the last 10 years in the region, reflecting the growing
concern over increasing sulphur emissions and deposition to
ecosystems.
4.2.1.1. Sulphur dioxide deposition to soils. Utiyama et al. (2005)
measured dry deposition to loess soil and dead grass in Beijing
using the aerodynamic gradient method, though in neutral condi-
tions 22% of the time. In stable or unstable thermal stratification,
they used a surface reaction concept for inferring dry deposition.
Two surface kinetics models were considered: either i) the reaction
occurs in soil pores and SO2 molecules diffuse through porosity
while reacting with alkaline sites on the pore surface; or ii) the
adsorption mechanism is of Langmuir–Hinshelwood type, where
the partial pressure of SO2 and its desorption pressure from the site
are in equilibrium. The model parameters are then fitted so that the
resulting (modelled) vertical SO2 concentration gradient matches
the observations. Measured deposition velocities (Vd) were in the
range 1–12 mm s1.
Sorimachi and Sakamoto (2007) conducted laboratory-based
flow-reactor measurements of SO2 deposition to soil samples from 12
sites in the arid loess plateau and deserts of Northern China. Canopy
resistances in the range 28–650 s m1 (with a mean of around
200 s m1) were found to be dependent on RH, as was S(IV) oxidation
to S(VI). It was hypothesized that Northern China soils, which are
5214 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
much more alkaline than in Southern China, are a greater sink for SO2
and a neutralizing buffer for acidifying atmospheric deposition
(Sorimachi et al., 2004). By comparison, in modelling SO2 deposition
to Asia, Xu and Carmichael (1998) used a fixed Rc for deserts of
500 s m1, which is clearly too high in the case of Northern China
deserts. A flow-reactor was also used by Sakamoto et al. (2004) to
determine SO2 dry deposition to yellow sand and soil-mediated SO2
oxidation by O3. The deposition velocity for SO2 increased with RH
due to the positive effect of RH on the SO2 oxidation rate.
4.2.1.2. Micrometeorological measurements over vegetated
areas. Matsuda et al. (2006) reported micrometeorological (aero-
dynamic gradient) flux measurements of SO2 and O3 over a tropical
(teak) forest in Northern Thailand in dry and wet seasons. The
deposition velocity for SO2 in the dry season was rather low, in the
range 1–3.1 mm s1 in daytime and 0.8–1.1 mm s1 in night-time.
In the wet season, however, Vd was much higher due to enhanced
non-stomatal uptake in wet conditions, with values in the range
9.5–13.9 mm s1 in daytime and 2.6–4.2 mm s1 in night-time. The
data were compared with a recent non-stomatal resistance scheme
(Zhang et al., 2003a), and it was concluded that extended experi-
mental SO2 dry deposition studies are needed in the tropics, while
Zhang et al. (2003a) recommend more studies to quantify the
different effects of dew and rain on SO2 deposition.
Sulphur dioxide dry deposition was also measured by Matsuda
et al. (2002) over a red pine forest located in Oshiba Highland,
Nagano, Japan, using a Bowen ratio technique. The median daytime
(12:00 to 14:00) deposition velocity was 9 mm s1. Measurements
compared favourably with estimates by an inferential model for
wet conditions, but for dry or mixed wet-dry surfaces there were
large differences between model and measurements. The authors
ascribed the discrepancy to a relative humidity threshold value
used in the inferential scheme to characterise canopy wetness, and
pointed to the need for a refined parameterisation of the cuticle or
external leaf surface resistance.
In a study of SO2 and O3 dry deposition to short grassy vegeta-
tion over an alkaline soil (pH ¼ 9.2) near Beijing, using the
aerodynamic gradient method, Sorimachi et al. (2003) measured
mean Vd values of 2 (1) mm s1 and 4 (2) mm s1 in late summer
and early winter, respectively. Although the grass was lush and
thick in the late summer, and senescent and leafless in the early
winter observation period, there was no difference in the mean Rc
(180  270 s m1 and 180  300 s m1, respectively), but the
uncertainties given reveal a large variability in measured Rc. The
difference in Vd stemmed from the higher aerodynamic (Ra) and
quasi-laminar sub-layer (Rb) resistances in late summer than in
early winter. The absence of vegetation and stomatal uptake in
early winter, which might otherwise have reduced the SO2 sink
strength, seems to have been compensated for by the soil alkalinity.
As the soil was more exposed and the in-canopy aerodynamic
resistance was reduced, the soil surface offered more adsorption
and reaction sites for SO2, with the result that the field was an
equally efficient SO2 sink in early winter as in summer.
The deposition velocity for SO2 was measured by Jitto et al.
(2007) during a 1-year experiment over a canopy of irrigated rice
paddy in Thailand using the Bowen ratio technique. The deposition
velocity was highest around noon and lowest at night. Seasonally-
averaged values of Vd were 6.7, 12.5, and 15.1 mm s1 in the winter,
summer, and rainy seasons, respectively.
4.2.1.3. Long-term deposition studies and inferential modelling. As
alternatives to costly and labour-intensive micrometeorological
measurements of dry deposition, several authors in Asia have esti-
mated long-term SO2 deposition using monitored concentration data
and inferential models, or long-term artificial collection devices.
The latter can only provide crude estimates of deposition rates, as
surrogate surfaces do not adequately account for the complexity of
natural surfaces, but they do allow continuous monitoring at
a number of sites and help to detect trends. The use of inferential
methods requires underpinning measurements of surface resistance
to representative surfaces to parameterise the models used. It is also
important to note that long-term changes in canopy resistance are
likely, especially in regions in which the relative ambient concen-
trations of SO2 and NH3 change with time, as for example in Europe
during the period 1990–2005 (Fowler et al., 2001c, 2007).
Ta et al. (2005) thus provided long-term sulphur dioxide dry
deposition estimates across Gansu Province, China, using K2CO3-
coated surrogate sulfation plates. Samples were taken monthly for
11 years at 48 sites distributed across 11 cities in the province.
The data showed that cumulative SO2 dry deposition fluxes were
closely related to local SO2 emissions, and had seasonal variations
with maxima in winter and minima during summer as a result of
higher winter and lower summer SO2 emissions and concentra-
tions. Monthly average SO2 deposition velocities, however, peaked
in April–July at 11–27 mm s1, and minimum values were observed
in January at 2–10 mm s1.
Inferential models (Erisman, 1994; Smith et al., 2000; Zhang
et al., 2002) may be used to estimate dry deposition at observation
sites, where single-height ambient concentration measurements
are available together with standard meteorological data. Model
parameters, however, have been largely derived from European and
N. American studies and may not necessarily be adequate for Asian
vegetation and soils, and numerical evaluations need to be carried
out. Thus Takahashi et al. (2002) simulated the dry deposition of
SO2 to a Japanese cedar (Cryptomeria japonica) forest located in
Gumma Prefecture, based on the results of 1-year’s concentration
measurements. The mean modelled Vd at this site was 8.8 mm s1
(Takahashi et al., 2001). The inferential estimate of the dry sulphur
deposition flux was 11.1 mmol m2 yr1 (3.6 kg S ha1 yr1), which
compared well with the net throughfall flux (12.4 mmol m2 yr1,
or 4.0 kg S ha1 yr1). Over a broadleaf forest on typical red soil of
Southern China, Xu et al. (2004) simulated Vd for SO2 and partic-
ulate SO24 , as well as their atmospheric deposition fluxes. The
simulations indicated that about 99% of the dry sulphur deposition
flux in the forest resulted from SO2, which contributed over 69% of
the total (wet þ dry) annual sulphur deposition.
By comparison, Wang et al. (2003) computed dry deposition
fluxes of SO2 and SO2 4 for 1 year to agricultural land over red soil
(pH ¼ 5.3–5.8) in the Jiangxi province of Central China. The crops
grown were rice paddies and oilseed rape. Sulphur dioxide
concentrations were measured 8 times day1, 7 days month1, using
a bubbler method. Annual mean modelled estimates of Vd were
3.8 (0.16) mm s1 for SO2 and 0.20 (0.12) mm s1 for SO2 4 .
Measured monthly mean concentrations ranged from 9 to
163 mg S m3 (6.7–121 ppb), with an annual mean of 64 mg S m3
(47 ppb). Estimates of total monthly wet and dry deposition of SO2
and SO2 4 ranged from 2.2 to 20.3 kg S ha
1
with an annual total
1
deposition of over 100 kg S ha , of which 83% was via dry deposi-
tion, accounting for over 90% of total S input to farmland in this area.
4.2.2. North America
Few long-term datasets of SO2 dry deposition monitoring have
emerged over the last 10 years, reflecting the declining importance of
SO2 as an acidifying input relative to NOy and NHx. Advances have
nonetheless been made in inferential modelling of SO2 uptake,
especially regarding the quantification of the non-stomatal (external)
leaf surface resistance, which serve as a basis for simulating regional
patterns of SO2 deposition (Zhang et al., 2002, 2003b).
Micrometeorological SO2 flux data from 5 sites (2 forests, a corn
field, a soybean field and a pasture) in eastern USA (Finkelstein et al.,

2000; Meyers et al., 1998) were compared with modelled data by
Zhang et al. (2003a), with the specific objective of evaluating the new
non-stomatal resistance scheme of the new Canadian model (Zhang
et al., 2002, 2003b). Over the forest sites, Finkelstein et al. (2000) had
noted that wetness tended to increase deposition velocity, but that
the nature of wetness (rain or dew) and its chemistry also controlled
canopy resistance. Non-stomatal surfaces like leaf surface, stem,
trunk and ground were important sinks for SO2, and the authors
concluded that a better understanding of surface chemistry and
water film chemistry was needed.
Dew formation has long been recognised as an important sink for
SO2 (Fowler and Unsworth, 1974, 1979). In more recent work Meyers
et al. (1998) show that dew is the reason for the relatively high early
morning deposition rates at 2 of the 3 low vegetation sites studied in
Eastern USA. Recognizing the weakness of existing North American
parameterisations (e.g. Meyers et al., 1998) in predicting SO2 depo-
sition rates to non-stomatal surfaces, especially in wet canopies,
Zhang et al. (2003a) demonstrate that the AURAMS scheme (Zhang
et al., 2002) performed well at these 5 sites, using different resistance
values for dew and rain. The revised non-stomatal resistance scheme
(Zhang et al., 2003b) includes a treatment of in-canopy transport, soil
and cuticle terms, and is a function of relative humidity, leaf area
index and friction velocity. For wet canopies, the cuticular resistance
is treated differently for dew and rain.
4.2.3. Europe
4.2.3.1. Long-term flux monitoring in the UK. Sulphur dioxide fluxes
have been monitored continuously since the mid 90s at two rural
sites in the UK, over agricultural land at Sutton Bonnington in the
English Midlands, and over moorland at Auchencorth Moss in
S. Scotland (Fowler et al., 2001c, 2005, 2007). The dry deposition
measurements have continued to bring surprises over the last 10
years. At Sutton Bonnington, the ambient concentrations have
declined from about 2.8 ppb in 1996 to current values close to
1.4 ppb and yet the deposition velocity continues to increase due to
continued reduction in the canopy resistance (Rc) (Fig. 4.1). Over
the monitoring period the canopy resistance has almost halved and
is now about 70 s m1. The consequence of the steady decline in
canopy resistance along with a decline in ambient concentration is
10
9
Mixing ratio (ppb)
8
7
6
5 NH
4 SO
3
2
1
0
1995
SO2 /NH3 molar ratio (ppb ppb -1)
0.6
0.5
0.4
0.3
0.2
0.1
0 0
1995
Fig. 4.1. Changes in the mean concentrations (ppbV) and ratio of ammonia and sulphur dioxide and in the May–July canopy resistance for SO2 deposition on Wheat at Sutton
Bonnington between 1996 and 2003.
D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267 5215
that the flux remained nearly constant. The measurements of the
atmospheric terms (Ra and Rb) revealed no trend, thus the trend in
Rc is not caused by changes in turbulence, and are clearly a conse-
quence of the chemical affinity of the surface changing with time.
These dry deposition measurements have proved valuable in
explaining the consistently larger decline in ambient SO2 concen-
tration than in emissions in Europe. In the absence of these flux
measurements it would be a matter of speculation as to the under-
lying cause of the faster decline in ambient concentration than
emission. Even with these measurements there remains the possi-
bility that SO2 oxidation rates have increased due to the growing
oxidizing capacity of the atmosphere and have contributed to the
relative changes in emission and deposition (non-linearity). It will be
necessary in the further analysis and interpretation of European
pollution climate data to carefully examine the relative importance
of the different contributors to the observed trends in concentration
and deposition and quantify the relative importance of changes in
dry deposition and oxidation rates in the long-term trends.
4.2.3.2. Other recent European datasets. The SO2 flux–gradient data
obtained over short vegetation by Feliciano et al. (2001), collected
over a period of 3 years in the mid 1990s at 3 different sites in
Portugal, were important in providing Rc estimates for the Medi-
terranean region of Southern Europe. The 3 sites had contrasting
pollution climates, with a coastal, oceanic, humid meadow in
N. Portugal, a hot and semi-arid pseudo-steppe and a site located in
a mostly dry, intensive agricultural area, both in S. Portugal. Median
canopy resistances varied from 140 s m1 to 200 s m1 and although
stomatal uptake was important when vegetation was biologically
active, the annual deposition was dominated by non-stomatal
mechanisms on wet surfaces. The night-time canopy resistance,
a proxy for the non-stomatal resistance, increased with decreasing
relative humidity at all 3 sites. A comparison of nocturnal Rc for the
southern sites showed that, for a given level of relative humidity, the
Rc at the intensive agricultural site was systematically lower than at
the pseudo-steppe site, which is used more extensively for grazing
and hay production. Although the authors make no mention of NH3
being measured at these sites, it might be hypothesized that a higher
NH3 concentration at the intensive agricultural site may have been
NH33
SO2
2
1996 1997 1998 1999 2000 2001 2002 2003 2004
140
120
SO2/NH3
SO2/NH3
Rc SO2 (s m-1)
100
Rc (Wheat)
80
60
40
20
1996 1997 1998 1999 2000 2001 2002 2003 2004
5216 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267

responsible for the observed lower nocturnal Rc, compared with the
extensively-managed, steppe-like grassland.
The development of low-cost systems for the long-term moni-
toring of SO2, NH3 and other trace gas fluxes holds promise for
widening the range of dry deposition datasets for comparison with
inferential models. Hole et al. (2008) present an 18-month dataset of
SO2 fluxes acquired with a conditional time-averaged gradient
(COTAG) system (Fowler et al., 2001b; Famulari et al., in press) in
a semi-alpine ecosystem in Southern Norway. The mean annual SO2
deposition velocity was 4.0 mm s1, although the dataset included
some negative deposition velocities (upward fluxes), and the annual
mean Vd was 13.0 mm s1 if only the positive values were included.
The authors report evidence of enhanced SO2 deposition rates during
an episode in November 2005 when the NH3/SO2 ratio was high, and
conversely of decreased SO2 uptake and increased NH3 uptake in
November 2004 when the NH3/SO2 ratio was low. Comparison with
the inferential model by Zhang et al. (2002, 2003b) was satisfactory
but the model could not reproduce the large observed variability in
exchange rates, which may result from NH3–SO2 co-deposition
processes not being included in their resistance scheme.
More experimental evidence of the mutual influences of
NH3 and SO2 concentrations on their deposition rates was obtained
by Derome et al. (2004), though not by micrometeorological
measurements but using bulk precipitation collectors and through-
fall measurements in Scots pine canopies in SW Finland. The study
was conducted over a 6-year period (1993–1998) in the vicinity of
a Cu–Ni smelter, which emitted large amounts of gaseous NH3. These
emissions were shown to have strongly enhanced the scavenging of
atmospheric SO2 by the pine canopy, resulting in increased levels of N
and S deposition and increased foliar N and S concentrations. In
an NH3 fumigation experiment, Cape et al. (1998) had previously
described similar findings over a Scots pine forest in Central Scotland,
with the canopy resistance for SO2 decreasing with elevated NH3
concentration. Although NH3 concentrations were not measured in Fig. 4.2. A schematic representation of the dynamic canopy compensation pollution
the Finnish study (Derome et al., 2004), they were likely higher than model for SO2 and NH3 exchange over vegetation (from Flechard et al., 1999).
normally encountered in the countryside, except near animal
housing in areas of intensive agriculture, where such processes could
be significant. increased to 2 mg m3 to provide sufficient NH3 to neutralize the
acidity from the ambient SO2 oxidation in solution. The conse-
4.3. Control of surface uptake rates by leaf cuticular chemistry quence of the increase in ambient NH3 is to decrease the canopy
resistance for SO2 and increase the deposition rate of SO2 to the
A number of authors have addressed the issue of the chemical maximum under the prevailing atmospheric conditions. Demon-
control of surface pollutant uptake rates (e.g. Flechard et al., 1999). strating a close link between SO2 deposition and ambient NH3 is not
The most important finding for SO2 deposition is that the rates of new, as this was predicted in earlier work in the Netherlands (Van
deposition are controlled mainly by the chemistry at the vegeta- Hove et al., 1989). However, this work quantified the process
tion–atmosphere interface, and that as the surfaces are wet most of
the time, the processes are regulated by chemical processes within
the thin film of moisture. In principle, many compounds influence 10
the chemistry of this surface layer, including plant exudates and soil
0
SO2 flux (ng m s SO2)

derived compounds, but the key reactant for SO2 is NH3. Thus the
ambient concentrations of SO2 and NH3 essentially regulate the pH -10
-2 -1

of the surface moisture and thus control the uptake of SO2. The -20
full surface chemistry of the process has been incorporated into Meas. FSO2
-30
a dynamic mechanistic model shown in Fig. 4.2 (Flechard et al., Mod. FSO2 (χNH3 = ambient)
1999). The chemistry of the surface water film is initialised in the -40 Mod. FSO2 ( χNH3 = 2 μ g m-3)
model using measured precipitation chemistry, the model then -50 FSO2, max
simulates the dynamic responses of the net land–atmosphere
-60
exchange of SO2 as the ambient concentrations of the reactive trace
21/03/95 12:00

22/03/95 00:00

22/03/95 12:00

23/03/95 00:00

23/03/95 12:00

24/03/95 00:00

24/03/95 12:00

25/03/95 00:00

25/03/95 12:00

26/03/95 00:00

26/03/95 12:00

gases and meteorological conditions change. The model has been

shown to provide good agreement with observed 30 min average
fluxes for several days. An example is provided in Fig. 4.3, for a five-
day period at Auchencorth Moss in the Scottish Borders. The
general agreement between measured and modelled fluxes is Fig. 4.3. A comparison between measured and modelled SO2 fluxes at Auchencorth
excellent during the three-day period, 21st March to 23rd March Moss over the period 21-3-95 to 26-3-95 showing the influence of increasing ambient
1995. From the 24th March, the observed NH3 concentrations are NH3 concentration on SO2 flux (from Flechard et al., 1999).
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
correctly for the first time, demonstrated the effects in field
conditions at ambient concentrations and provided a mechanistic
model incorporating the full chemical scheme.
4.4. Advances in deposition modelling
The magnitude of dry deposition at the national and regional
scales requires that process-based, rather than empirical, parame-
terisations be implemented in atmospheric models, accounting for
variations in surface chemical characteristics driven by local pollu-
tion climates. The observation of changes in deposition velocity from
the European SO2 deposition studies of the 90s is now widely known
and is being used by EMEP to explain growing discrepancies in the
model-measurement comparisons over Europe. The work has led to
modifications of the EMEP model (Simpson et al., 2003) to simulate
the temporal trends, resulting in an increase in Vd for SO2 over
many parts of the continent, and driven by the long term, large scale
decrease in the SO2/NH3 ratio (Fig. 4.4). The new scheme, for non-
stomatal resistance of both NH3 and SO2, incorporates an acidity to
alkalinity (SO2/NH3) molar ratio as a scaling factor for resistances. For
SO2, two non-stomatal resistances Rns,wet and Rns,dry are calculated as
a function of the SO2/NH3 ratio, and a function of relative humidity is
used for the transition from dry to wet when the surface cannot be
considered fully wet or fully dry.
The EMEP non-stomatal deposition scheme has also been used
in field-scale inferential modelling of N and S dry deposition as part
of the NitroEurope project, using low-cost, long-term atmospheric
trace gas and aerosol DELTA samplers (Tang et al., 2009). Another
implementation of the parameterisation was made by Zimmer-
mann et al. (2006) for the simulation of atmospheric deposition to
Norway spruce, using the SPRUCEDEP SVAT model, and comparison
with throughfall measurements and a canopy base cation budget
model. The agreement between (inferential & canopy budget)
modelling and observations was very good for S and oxidized
N. Here, the contribution of dry to total (dry þ wet) deposition was
around 60% for S and for both reduced and oxidized N.
The Dutch IDEM model (Bleeker et al., 2004; Erisman, 1994) also
uses an NH3/SO2 molar ratio as a proxy for surface acidity. For NH3,
a range of default Rext values are used for 3 classes of the N/S ratio (very
low, low and high), depending on surface wetness, land-use and time
of day, while for SO2 the only effect implemented is to add 50 s m1 to
the non-stomatal resistance when the N/S ratio is very low (<0.02).
The large reduction in European SO2 emissions and ambient
concentrations over the last 25 years, and the relative stagnation in
NH3 emissions and concentrations in Western Europe over the same
Fig. 4.4. Modelled (EMEP) dry deposition velocity of SO2 (cm s1) over Europe for 1980 and 2000, taking into account the effect of the change in the SO2/NH3 ratio on the canopy
resistance (Fagerli pers com).
5217
period has meant that the SO2/NH3 ratio has decreased dramatically,
resulting in a reduced Rc for SO2 (Fig. 4.1). The data for Fig. 4.1 are of
course site specific and the footprint of the measurements in Not-
tinghamshire is only 104–105 m2, but this trend may be regarded as
representative for the regions in which ambient SO2 concentrations
have declined by up to an order of magnitude since 1970 and
includes much of central and eastern England and the industrial
regions of Germany, France, the Netherlands and Belgium. While
ambient SO2 was a relatively good proxy for total atmospheric and
leaf surface acidity 15 or 25 years ago, the relative share of SO2
compared to other inorganic atmospheric acids (e.g. HNO3 and HCl)
is now much smaller. The NitroEurope network of 56 DELTA
samplers across the European continent currently provides monthly
mean concentrations of HNO3 and HCl as well as SO2 and NH3 and
2-
aerosol NHþ 
4 , NO3 and SO4 (Tang et al., 2009), with a view to vali-
dating European concentration fields of concentration and deposi-
tion for these species. The data show (Fig. 4.5) that the geometric
mean mixing ratios of SO2, HNO3 and HCl across the network are 0.4,
0.35 and 0.15 ppb, respectively, so that, on average, SO2 makes up
only about 40% of the sum of acids (SO2 þ HNO3 þ HCl). Further, the
data indicate that at some sites (e.g. most Danish, French and Italian
sites), the acidity is largely dominated by HNO3 and HCl, which are
considered in most models (e.g. Simpson et al., 2003) to be deposited
at the maximum rates allowed by turbulence (Rc w 0 s m1). Under
such conditions, the proxy (SO2 þ HNO3 þ HCl)/NH3 would seem
more appropriate to quantify the relative importance of surface
acidity and alkalinity in model parameterisations, than the ratio of
SO2 alone to NH3. Clearly the surface affinity for SO2 uptake will
depend on the presence of fast-depositing, strong acids as the acidity
is no longer SO2-dominated, and this needs to be accounted for in
extended surface resistance parameterisations.
4.5. Future challenges
The principal controls over SO2 deposition to terrestrial surfaces
have been identified from field, mainly micrometeorological
measurements. These studies have enabled the controlling steps in
the deposition pathway to be separated and their response to
environmental variables quantified. In turn the data and responses
have been used to develop process-based models and applied to
quantify regional deposition budgets at country and continental
scales. There have been surprises, notably in the last decade. The
largest surprise has been the recognition that long term (w1 year)
average deposition velocities change with time due to changes
in the chemical climatology at the regional scale. Thus a few
5218 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267

2.5
HCl

2 HNO3
SO2
Concentration (ppb)

1.5

0.5

0
CZ-BK1

NL-Ca1

PT-Mi1
CH-Oe1

FI-Hyy

FI-Lom
DE-Gri

DE-Hoe

NL-Spe
FR-Pue

IT-Col

PL-wet

UK-EBu
UK-ESa
DE-Hai
DE-Kli

FR-Gri

IE-Dri

IT-BCi

IT-Cas
DK-Ris

ES-VDA

FR-LBr

IT-MBo

IT-SRo

SE-Nor

DE-Meh
FR-Lq2

NL-Loo

SE-Sk2
UK-AMo
DE-Geb

ES-ES1

FR-Fon

HU-Bug

IT-Amp

PT-Esp
IE-Ca2

IT-Ren
IT-Ro2
BE-Vie

DE-Wet
DE-Tha
CH-Lae

DK-Lva

UA-Pet
FI-Kaa
BE-Bra

ES-LMa

RU-Fyo
FI-Sod

UK-Gri
FR-Hes

NL-Hor
BE-Lon

DK-Sor

3.5
SO2/NH3
Acid/NH3 ratio (ppb ppb-1)

3 (SO2+HNO3+HCl) / NH3

2.5

1.5

0.5

0
CZ-BK1
CH-Oe1

DE-Tha

ES-ES1

FI-Hyy
DE-Wet

FI-Lom
BE-Vie

ES-VDA

PL-wet

SE-Nor

UA-Pet
DK-Sor
DE-Gri
DE-Hai
DE-Kli

RU-Fyo

UK-EBu
FI-Sod

UK-Gri
DK-Ris

FR-Gri

IE-Dri

IT-BCi
IT-Col

NL-Hor

IT-Cas
BE-Bra
BE-Lon

FR-Hes
FR-LBr

IT-Ro2
CH-Lae

DE-Geb

FR-Pue

PT-Esp

UK-ESa
HU-Bug

IT-MBo

IT-SRo

NL-Loo

NL-Spe
DE-Meh
FR-Fon

FR-Lq2

IE-Ca2

IT-Amp

IT-Ren

NL-Ca1

SE-Sk2
UK-AMo
PT-Mi1
FI-Kaa
DK-Lva

DE-Hoe
ES-LMa

Fig. 4.5. Top: Annual mean concentrations of SO2, HNO3 and HCl across the NitroEurope network; Bottom: Annual mean Acid/NH3 molar ratios calculated from SO2 alone or from
SO2 þ HNO3 þ HCl.

measurements of SO2 deposition rates to parameterise models will
not be satisfactory in the long term if emissions of any of the acifi-
fying or alkaline gases change. It is necessary therefore to underpin
estimates of regional SO2 deposition with measured deposition
fluxes and estimates of the surface resistance to quantify the long-
term trends. The same logic means that deposition velocities from
one region will not necessarily apply elsewhere. The most important
region globally for sulphur emissions and deposition is currently
East Asia, and China specifically. While the methodologies and
models developed in Europe and North America are applicable for
measurements of SO2 deposition, the use of parameters deduced in
Europe or North America are not applicable, and measures fluxes
and surface resistances in these regions are necessary to underpin
the assessments.
5. Ozone
5.1. Introduction
Ozone is a gaseous, phytotoxic secondary air pollutant with
widespread effects on human health, vegetation and materials. It is
also a greenhouse gas (GHG), third behind CO2 and CH4 in impor-
tance. Its deleterious effects on plants pose a large-scale risk to crop
production and forest vitality in many regions of the Northern
Hemisphere (Fowler et al., 1999; Cape, 2008), which have been
widely studied in Europe and North America (e.g. Hayes et al., 2007;
Karnosky et al., 2007), there is also evidence of ozone impacts in Asia,
Africa and Latin America (e.g. Ashmore, 2005).
Ozone deposition to external surfaces of vegetation is important
as a removal pathway for ground level ozone but is of little
consequence for plant effects. The primary potential for injury to
vegetation, requires stomatal uptake of ozone molecules (Fig. 5.1)
followed by reaction with the internal plant tissue generating
highly reactive oxidants that interfere with physiological processes
(e.g. Matyssek et al., 2008). As ozone is a strong oxidant, it can also
react with leaf cuticles and other external plant surfaces or with
volatile compounds emitted by vegetation and non-stomatal ozone
deposition is a substantial fraction of the total flux. In addition to
vegetation, ozone molecules may be deposited at any surface
providing a chemical sink or acting as a surface for heterogeneous
decomposition (Cape et al., 2009). Quantifying the stomatal uptake
rates is central to understanding the ozone-induced risk to vege-
tation, but the non-stomatal deposition needs to be quantified to
correctly partition the total deposition flux.
Over terrestrial surfaces ozone, confined within the atmospheric
boundary layer, has a relatively short lifetime scale of the order of
one day due to dry deposition at the surface (Wesely and Hicks,
2000). Thus surface removal represents an important control on the
near-surface ozone concentrations, and is the main cause of diurnal
variation in rural areas (Garland and Derwent, 1979). Dry deposition
constitutes a major term in the global mass balance of tropospheric
ozone, the mean global dry deposition sink calculated with 20
chemistry-transport models (CTMs) (1000 Tg y1) clearly exceeding
the net stratospheric input (550 Tg y1) (Stevenson et al., 2006).
The first measurements of ozone deposition fluxes were made
in the 1950s using the micrometeorological gradient method
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Fig. 5.1. The sinks for ozone at terrestrial surfaces and processes regulating the exchange.
(Regener, 1957). The earliest investigations were aimed at quanti-
fying the surface sink term of the tropospheric ozone budget. Based
on these, Galbally (1971) concluded that bulk surface resistance (Rc)
of dry soil and short grass surfaces was approximately 100 s m1.
These and other pioneering studies (e.g. Turner et al., 1974) showed
that vegetation and soil constitute important pathways by which
ozone is removed from the atmosphere, while water and snow
surfaces are rather inefficient sinks. However, the early studies
provide rather little information about the processes that control
ozone deposition to terrestrial or marine surfaces.
There has also been an interest in measuring surface fluxes
prompted by ecological concerns. The importance of environ-
mental conditions on plant injury due to ozone through the regu-
lation of stomatal uptake was recognised in 1960s by Mukammal
(1965), who observed that the presence of high concentrations was
not a sufficient condition for plant injury. Indeed, a few years later
the close coupling between ozone and water vapour fluxes was
demonstrated by Rich et al. (1970). However, while ozone effects on
vegetation have been closely associated with stomatal uptake for
decades, only recently have practical risk assessment methods been
formulated in terms of stomatal uptake rather than ambient
concentration (UNECE, 2004).
Micrometeorological techniques have been in use since the
first flux measurements. In the late 1970s, Eastman and Stedman
(1977) developed a fast-response ozone sensor that facilitated
direct ozone flux density measurements by the eddy covariance
method. This resulted in a series of measurement campaigns in
the eastern United States, including various vegetated and
other surface types (Wesely, 1983). These studies improved the
understanding of deposition processes and formed the basis for
the detailed surface resistance parameterisation of Wesely
(1989). This parameterisation has been implemented into
numerous CTMs. In Europe, the eddy covariance technique was
adopted somewhat later, but rapidly became popular with the
introduction of a commercial fast-response ozone sensor
(Güsten et al., 1992).
5.2. Deposition rates
Early estimates of ozone dry deposition were obtained from
measurements of the diurnal cycle of ozone in rural areas
5219
(Garland and Derwent, 1979). The first long-term measurements
showed a seasonal cycle over vegetated surfaces that followed the
growing season of the plants (Colbeck and Harrison, 1985), leading
to the assumption that ozone deposition is mainly controlled by
stomatal uptake and deposition to non-vegetated surfaces is
constant, only depending on the material and surface area. More
recent studies have shown that although deposition rates are partly
governed by stomatal uptake over a plant canopy, it only accounts
for ca 40–60% of total deposition on average and that the non-
stomatal component is not constant (Fowler et al., 2001a; Coyle
et al., 2009; Hogg et al., 2007). These observations are described in
more detail in the following sections.
5.2.1. European forests
Ozone deposition fluxes to forests, as well as other vegetated
surfaces, are largely controlled by the physiological activity and
associated gas exchange of the vegetation, with solar radiation, air
temperature, air humidity and soil moisture as the main controlling
variables. Thus the deposition velocities (Vd) observed above forests
typically exhibit diurnal and seasonal cycles that depend on the
structure, physiological responses and phenological state of the trees.
According to present understanding, however, there are other signif-
icant processes in addition to stomatal regulation of gas exchange that
control the magnitude and variation of the ozone deposition efficiency
of forests (Altimir et al., 2006; Cieslik, 2004; Dorsey et al., 2004;
Goldstein et al., 2004; Hogg et al., 2007; Lamaud et al., 2002; Tuovi-
nen, 2000; Tuovinen et al., 2008a; Zhang et al., 2002).
The temporal patterns are clearly demonstrated by the long-
term flux measurement data available from a few sites, such as
those reported for a temperate spruce forest by Mikkelsen et al.
(2004) and a boreal pine forest by Keronen et al. (2003) and Altimir
et al. (2006). In the boreal region in winter, the dormancy of
vegetation and below-zero temperatures result in low and rela-
tively stable deposition rates (Vd z 0.1 cm s1, Fig. 5.2a), while the
mean diurnal cycle at the temperate forest shows a weak midday
enhancement related to gas exchange superimposed on a relatively
high and seasonally invariable base level (Vd z 0.5 cm s1). The
decrease of Rc in spring correlates with the onset of photosynthesis,
and a well-defined, symmetrical diurnal cycle ensues in summer,
with a Vd maximum of 0.7–0.9 cm s1 (Keronen et al., 2003; Mik-
kelsen et al., 2004). However, Altimir et al. (2006) observed that the
5220 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267

a Boreal Pine Forest Median b Temperate Oak Forest

0.7 Winter (Nov-Feb) 1.4
0.6 Summer (May-July) 1.2 July -A ug
0.5 1.0

vd [cm s-1]

vd [cm s-1 ]
0.4 0.8
0.3 0.6
0.2 0.4
0.1 0.2
0.0 0.0
:00
:00
:00
:00
:00
:00
:00
:00
:00
:00
:00
:00
:00

:00
:00
:00
:00
:00
:00
:00
:00
:00
:00
:00
:00
00
02
04
06
08
10
12
14
16
18
20
22
00

01
03
05
07
09
11
13
15
17
19
21
23
c Potatoes d Temperate Grassland
1.4 0.7
1.2 July-Aug 0.6 Apr-Sep
vd [ cm s -1 ]

1.0 0.5

vd [cm s -1 ]
Oct-Mar
0.8 0.4
0.6 0.3
0.4 0.2
0.2 0.1
0.0 0.0
0 1:00
0 3:00
0 5:00
0 7:00
0 9:00
1 1:00
1 3:00
1 5:00
1 7:00
1 9:00
2 1:00
2 3:00

0 0:00
0 2:00
0 4:00
0 6:00
0 8:00
1 0:00
1 2:00
1 4:00
1 6:00
1 8:00
2 0:00
2 2:00
0 0:00
Fig. 5.2. Median diurnal cycles in deposition velocity at (a) boreal scots pine forest, Hyytiala, Finland, 2002–2003 (Altimir et al., 2006), (b) oak forest, Alice Holt, England, 16th
July-05–18th August-05 (Coyle et al., 2006), (c) potatoes, Gilchriston, Scotland, 9th July-06–3rd Aug-06, (Coyle et al., 2009) (d) intensively managed lolium perene grassland, Easter
Bush Scotland, 2002–2003 (Coyle, 2005).

correlation with physiological activity is poorer in autumn and
concluded that the deposition rate is modified by the frequent
wetting of the forest canopy. Both Mikkelsen et al. (2004) and
Altimir et al. (2006) attribute a major part of the total annual ozone
deposition to non-stomatal pathways.
High non-stomatal fluxes are also observed in Mediterranean
forests (Gerosa et al., 2005, 2008). However, the diurnal and
seasonal variations differ from those of the northern forests in many
aspects. The measurements above oak forests in central Italy
(Gerosa et al., 2005, 2008; Cieslik, 2009) and south-eastern France
(Michou et al., 2005) show that dry and hot conditions can signifi-
cantly affect the diurnal courses of Vd and Rc. On the other hand, in
this region there is a potential for high deposition rates throughout
the year, and higher stomatal uptake may take place during winter
than summer months, in spite of the lower ozone concentrations in
winter (Cieslik, 2009).
During dry periods stomata are either almost completely closed
or the cycle of stomatal conductance (Gst ¼ R1 st ) is less symmetrical,
with a rapid increase from the nocturnal levels to a maximum in
the morning, rather than around noon, and a gradual decrease
towards the evening. The latter behaviour may take place in more
northern forests as well, if leaf temperatures reach sufficiently high
levels (e.g. Dorsey et al., 2004; Tuovinen et al., 2008a). At the French
site, Vd starts increasing very early (at 3–4 a.m. local time) and it
was suggested that this could be related to either stomatal response
to blue light, resulting in uptake already in the predawn hours, or to
non-stomatal deposition enhanced by surface wetness (Michou
et al., 2005). At the Italian site, however, the maximum (in Gst)
occurs later and seems to have a non-stomatal origin, possibly due
to the reaction with the NO accumulated within the forest canopy
(Gerosa et al., 2005) or leaf wetness (Gerosa et al., 2008). Similarly,
the measurements taken by Coyle et al. (2006) in an oak forest
in England in summer show a steep increase to the maximum at
8 a.m. (Vd z 1.0 cm s1) and a approximately linear decrease to
a nocturnal level (Vd z 0.1 cm s1), Fig. 5.2b.
In addition to the phenological development of plants, the
seasonal cycle can be strongly influenced by the soil moisture
conditions, especially in southern Europe. Consequently, there may
be large annual variations in ozone uptake rates depending on the
occurrence and persistence of drought. For example, in August
2003 the mean Gst derived for the Italian oak forest by Gerosa et al.
(2008) was only 35% of that in the cooler and wetter August of
2004, and the effect of drought persisted even after soil water was
replenished by rainfall.
5.2.2. Crops
For agricultural crops, ozone deposition rates exhibit pronounced
seasonality that results from the distinct phenological stages of the
growing season. The flux measurements above an Italian barley field
by Gerosa et al. (2004) demonstrate how Vd increases during the first
growth stages (seedling growth, tillering, stem elongation). The
maximum is reached soon after anthesis, during the grain filling
period, when photosynthetic activity is at its highest level. Gerosa
et al. (2004) observed an average Rc of about 75 s m1 for this period,
while the bulk stomatal resistance (Rst) was about 150 s m1. After
that, deposition rates decrease gradually with ripening of the crop
and leaf senescence, as Rst increases, and are further reduced by
harvest. A slightly higher minimum Rc but a similar decrease was
observed at the same site for wheat. In this case, the decline was
amplified by the rapid drying of soil (Gerosa et al., 2003).
For both barley and wheat, the diurnal cycles of Vd and surface
conductances were symmetrical during the photosynthetically
active period with a maximum (Vd z 0.7–0.9 cm s1) around noon
(Gerosa et al., 2003, 2004). During the latter part of the growing
season, the midday deposition rates are strongly reduced, due to
increased Rst, resulting in an earlier maximum and a diurnal course
that is skewed towards morning. In the afternoon, values compa-
rable to those after harvest were observed for the barley field
(Gerosa et al., 2004).
For other crops, data are rather limited. Michou et al. (2005)
report a symmetrical diurnal cycle for the Vd measured over
a rapidly growing maize field, with a mean minimum of 0.05 cm s1
and a mean maximum of 0.50 cm s1. In an earlier North American
study, a similar diurnal cycle, with slightly higher values throughout
the day, was observed over a maize field during the period of most
active growth (Meyers et al., 1998). During senescence, the hourly
mean Vd only reached 0.2 cm s1 in the morning. The patterns were
also similar for soybean, but the Rc of soybean seems to be
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
significantly lower than that of maize, as the maximum mean
hourly Vd was almost 1 cm s1 during the active growth period
(Meyers et al., 1998). Coyle et al. (2009) reported an asymmetrical
diurnal cycle in Vd over a potato field during the phase of tuber
initiation and growth through to harvest, with a median value of
0.6 cm s1, day-time values from 0.5 to 2 cm s1 decreasing to
0.4 cm s1, or less, at night (Fig. 5.2c).
As was the case with forests, stomatal uptake rates derived from
the evapotranspiration fluxes only explain a part of the total ozone
flux and a significant proportion must be attributed to non-stomatal
sinks. Even during the active growth period, no more than 50–60%
of the total flux to a wheat field was stomatal, and this fraction
decreased during the senescence (Gerosa et al., 2003). The same was
true for barley, and even though the day-to-day variation in the
inferred non-stomatal flux fraction is large, the corresponding non-
stomatal surface conductance remains relatively stable throughout
the summer (Gerosa et al., 2004). Similar results were obtained for
onion, but in this case the variation can be explained by irrigation
that clearly enhanced both stomatal and total fluxes (Cieslik, 2009).
In the case of potatoes, the non-stomatal component was only w15%
when the canopy was well-watered but increased to w80% when the
crop became senescent. (Coyle et al., 2009).
5.2.3. Grasslands
Grasslands can be used to describe a wide variety of habitats
from intensively managed pastures that are usually dominated by
a single species, such as Lolium perenne, to natural grasslands which
contain a rich diversity of grasses, forbs and legumes and are often
of high conservation value. The canopies that have been studied to
date all exhibit similar patterns of deposition as forests and agri-
cultural crops in that they have phenologically driven seasonal and
diurnal cycles. There are few long-term measurements of ozone
deposition to grasslands reported in the literature at present
(Colbeck and Harrison, 1985; Grünhage and Jäger, 1994; Pio et al.,
2000). All these studies measured during winter and summer so
that the growing season and dormant periods were observed. The
results of several short-term campaigns over active and dormant or
dry grasslands have also been reported and are summarized below
(Bassin et al., 2004; Garland and Derwent, 1979; Meyers et al., 1998;
Sorimachi et al., 2003).
Over active, green grasslands the daytime Vd is only 0.5 cm s1
on average, decreasing to w0.1–0.2 cm s1 at night, although peaks
over 1 cm s1 are often observed (Fig. 5.2d). The diurnal cycle is
often symmetrical with a steady increase in the morning after
sunrise and decrease is the afternoon as light and temperatures
decrease. However (Grünhage and Jäger, 1994) reported an asy-
metrical diurnal cycle in Vd with a steep increase after 6 a.m. until 9
a.m. when it steadily declined. This is attributed to an increase in
water vapour pressure deficit (VPD) at midday and the afternoon
causing stomata to close, as has been observed for many other
canopies. Where measurements have been made over dormant
(i.e. during winter) or dry grasslands the diurnal cycle is far less
pronounced with daytime Vd only reaching w0.2 cm s1 although
night-time values are similar at all times of year (Fig. 5.2d).
Coyle, (2005) showed that non-stomatal uptake was w60% of
the total budget over an improved grassland in Central Scotland.
Pleijel et al. (1995) found that the non-stomatal sink is enhanced by
surface wetness while the work of Coyle (2005) also demonstrated
that the non-stomatal component was not constant but varied with
wetness, surface temperature, solar radiation and wind speed as
has been suggested for other canopies.
Ozone deposition to forests has also been extensively studied in
North America, and in recent years a unique study in elevated CO2
using a Free Air Enrichment Experiment (FACE) has demonstrated
strong interactions between O3 and CO2, the former decreasing
5221
primary productivity at modest O3 exposure concentrations
(King et al., 2005).
5.2.4. Other vegetated surfaces
Measurements have been made over a variety of other plant
canopies from moorlands and subartic mires to tropical forests. They
all exhibit diurnal and seasonal cycles driven by variations in
stomatal activity and climate, as described for the previous canopies.
For example Fowler et al. (2001) for moorland reported summer
diurnal cycles ranging from w0.3 cm s1 at night to w0.6 cm s1
during the day while in the winter the afternoon peak was only
w0.4 cm s1 with night-time values also w0.3 cm s1. Tuovinen et al.
(1998) measured a small diurnal cycle over flark fen, 300 km north of
the Artic circle in the late summer, ranging from 0.1 to 0.15 cm s1 at
night to only w0.2 cm s1 during the day. For tropical forests there
are often two seasons, wet and dry: During the wet season, Rummel
et al. (2007) reported diurnal cycles over Amazonian rain forest
ranging from w0.4 cm s1 during the night to w1 cm s1 at day, with
a symmetrical diurnal cycle.
5.2.5. Non-vegetated surfaces
Deposition to the soil underlying the vegetation layer may signifi-
cantly contribute to the vertical ozone flux observed above the canopy
(e.g. Dorsey et al., 2004). Especially in arid regions, the surface resis-
tance of soil (Rsoil) is the key determinant of the surface removal of
ozone (e.g. Michou et al., 2005). As the literature review by Massman
(2004) and the more recent data of Sorimachi and Sakamoto (2007)
indicate, Rsoil is highly variable, ranging from 10 to >1000 s m1. It has
been observed that Rsoil decreases with increasing organic content
and porosity of soil. Clearly, wet soils have a considerably higher Rsoil
(w500 s m1) than dry soils (w100 s m1) (Galbally and Roy, 1980;
Massman, 2004), as increasing the moisture content of soil decreases
its porosity and thus reduces the area of reactive surface available to
ozone molecules (Sorimachi and Sakamoto, 2007). However, it is
difficult to disentangle individual effects based on the current data, and
the situation is further complicated by biogenic NO emissions from
soils. Removal through the reaction with NO potentially constitutes
a significant sink for ozone, especially in forests at night (Pilegaard,
2001; Dorsey et al., 2004), even though this reaction does not take
place specifically at the air–soil interface.
5.2.5.1. Snow. The dry deposition velocity over snow- and ice-
covered surfaces and water is known to be smaller than 1 mm s1.
However, the measurement data are highly variable. It is possible
that the measured Vd is affected by chemical reactions taking place
in the snowpack, which, combined with dynamic transport
processes, can result in the observed variability. Helmig et al.
(2007) modelled ozone concentrations in high northern latitudes
with different values of Rc and demonstrated how even small
deposition rates, if effective over large areas, can significantly affect
the near-surface concentrations and that a high Rc is required for
snow in order to reproduce the observed concentrations; the best
agreement was obtained when limiting Vd to 0.01 cm s1.
5.2.5.2. Water. For water surfaces, current understanding of
controlling processes is more coherent, involving both turbulent and
molecular mixing, and chemical reactions. It has been observed that
wind-induced turbulence greatly enhances deposition rates by
increasing atmospheric mixing, surface roughness, wave breaking
and spray generation (e.g. Gallagher et al., 2001). The observations of
Rc range from 1000 to 10,000 s m1 (Gallagher et al., 2001). At low
wind speeds, Vd increasingly depends on the molecular gas transfer
near the air–water interface. Even in the absence of turbulence,
significant deposition rates are possible, since the chemical reactions
taking place in the aqueous phase enable more efficient deposition
5222 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
than the solubility of ozone alone would suggest. The modelling
results of Fairall et al. (2007) show that the oceanic turbulent mixing
also plays an important role in enhancing ozone deposition by up to
a factor of three. Iodide (Chang et al., 2004) and chlorophyll (Clifford
et al., 2008) have been suggested as the main reagents controlling
ozone destruction in the organic surface microlayer. As the distri-
bution of these compounds in water bodies is related to that of
phytoplankton, the chemical enhancement of ozone deposition can
be expected to be highly variable both temporally and spatially.
Similarly, coastal ozone deposition to the iodide-rich macroalgae
surfaces depends on the tidal phase, and fluxes can be further
enhanced by photochemical destruction of ozone during the iodine-
mediated particle formation events (Whitehead et al., 2009).
5.3. Non-stomatal deposition processes
Although the stomatal uptake of ozone is an important sink over
vegetated surfaces it accounts for only a fraction (typically 1/3–2/3) of
the total deposition. In most studies it has been assumed that the
non-stomatal sink is constant, depending only on the surface mate-
rial and area, although it was expected that the presence of surface
water would inhibit deposition as the solubility of ozone is quite
small. However, field measurements have indicated that surface
temperature, solar radiation, surface wetness and wind speed may all
influence the magnitude of the non-stomatal flux. The influence of
wind speed is simply explained, as when wind speed increases more
air will penetrate the canopy, increasing the surface area available for
deposition. The mechanisms that have been proposed for the other
parameters are:
C Temperature: thermal decomposition ozone on plant surfaces,
mediated by waxes and other substances on the surface
(Coyle et al., 2009; Hogg et al., 2007; Fowler et al., 2001; Cape
et al., 2009)
C Solar radiation: ozone photolysis also mediated by the surface
(Coyle et al., 2009; Hogg et al., 2007 and references therein)
and reaction with VOCs emitted by vegetation (Hogg et al.,
2007; Coyle, 2005)
C Surface wetness: aqueous reactions in water-films on plant
surfaces (Coyle et al., 2009; Altimir et al.,)
Principal component analysis of data from several field
campaigns indicated the following order of precedence: tempera-
ture, surface wetness (measured as vapour pressure), solar radia-
tion then wind speed although for forests temperature and wetness
were of almost equal importance (Coyle et al., 2008a).
Some preliminary work exposing wax coated and metal surfaces to
ozone in controlled environment chambers (Cape et al., 2009) showed
that Vd is temperature dependent. An Arrhenius analysis of the change
in reaction rate with temperature is shown in Fig. 5.3 (the natural
14
12
ln(Rns)
10
8 Potatoes
6 Grassland
4
0.39 0.4 0.41 0.42
1000/RT
Fig. 5.3. Arrenhius relationship analyses for ozone deposition to various surfaces: stainless steel, Aluminium foil, paraffin wax and beeswax from Cape et al. (2009); moorland
Fowler et al. (2001); potatoes Coyle et al. (2009); Grassland and Forests, Coyle et al. (2008a).
logarithm of the surface resistance in s m1 is taken as the inverse
reaction rate). The results for four vegetated canopies are also plotted
in Fig. 5.3 and the slope of their linear regression lines is of the
same order of magnitude as the artificial surfaces. This shows that the
dependence on temperature and activation energies are similar for all
surfaces but the absolute reaction rates differ. The simplest conclusion
is that heterogeneous decomposition of ozone to molecular oxygen is
the underlying process responsible; hence the similar activation
energies in Fig. 5.3 and the variation in reaction rates can be attributed
to differences in effective surface area (Cape et al., 2009).
Cape et al. (2009) also tested the hypothesis that the surface
reactivity of vegetation may be enhanced by reaction of biogenic
volatile organic compounds (BVOCs) dissolved in cuticular waxes
and showed no enhancement due to surface reaction. However,
ozone does react in the gase phase with BVOCs emitted by vege-
tation, with gas-phase reaction rate coefficients varying between
1018 and 1016 cm3 molec1 s1, potentially leading to apparent
non-stomatal deposition velocities of similar magnitude to those
measured in the field (Coyle, 2005). The emission of BVOCs by
vegetation is also light and temperature dependent, increasing
with both parameters which may explain some of the variation in
non-stomatal deposition. Nevertheless, most measurements indi-
cate that the concentrations or reactivity of the emitted BVOCs are
not sufficient to explain the magnitude or variation in non-stomatal
deposition in all circumstances. In can be concluded that although
BVOCs may play a part in the non-stomatal deposition they are only
significant for species that emit currently unidentified compounds
that react very rapidly with ozone (Hogg et al., 2007).
Although some studies have shown surface water inhibits
ozone deposition to a vegetated canopy the consensus is now that
it increases deposition (Hogg et al., 2007; Coyle et al., 2008a) in
most circumstances. Although Fuentes (1992) found more organic
compounds in water from maple leaves compared to poplar, specific
compounds that may be responsible have not been identified.
Coyle et al., (2009) suggested that non-stomatal deposition is gov-
erned by three main regimes: ozone deposition increasing as the
temperature and solar radiation increases on a dry surface due to
thermal decomposition; decreased deposition on surfaces with
a thin film of water present as thermal decomposition is blocked by
the water film; enhanced deposition on a fully wetted surface due to
aqueous reactions in the water.
While non-stomatal deposition has become widely recognised
as an important sink, the concept of stomatal uptake at night is less
widely appreciated and this complicates the simplistic view of day–
night differences in ozone sinks in vegetation (Grulke et al., 2004).
5.4. Model development and validation
The recent European measurement data on ozone fluxes have
been used for testing and improving the DO3SE deposition
stainless steel y = 40.1x - 3.28, R2 = 0.84
aluminium foil y = 24.9x + 0.14, R2 = 0.29
paraffin wax y = 22.8x + 0.85, R2 = 0.18
beeswax y = 16.1x + 2.18, R2 = 0.44
moorland vegetation y = 36.4x - 9.62, R2 = 1
y = 49.9x - 14.84, R2 = 0.06
y = 52.6x - 16.26, R2 = 0.06
Forests y = 56.2x - 16.56, R2 = 0.14
0.43
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267 5223

module, which has been incorporated into the Unified EMEP CTM AOT40 is still the most common risk indicator used in Europe for
developed for European policy-making applications (Tuovinen setting environmental objectives and defining the so-called critical
et al., 2001, 2004, 2008b; Emberson et al., 2007). DO3SE makes it levels, Ashmore and Fuhrer (2000). For a proper application of AOT40,
possible to calculate stomatal and non-stomatal ozone fluxes to ozone concentration must be known at the height of the canopy
different vegetation types, taking into account both plant top (UNECE, 2004). This means that the concentration determined
phenological and meteorological factors (irradiance, temperature, above this height (as is typically the case with measurements) must
humidity, soil moisture) on an hourly basis (Simpson et al., 2007; be transformed to the correct reference height, because of the
Emberson et al., 2000, 2007). Many of the validation studies deposition-sink generated vertical concentration gradient; a failure
have been focussed on the leaf-scale stomatal conductance of to correct for this gradient may seriously overestimate the risk
a specific plant species only, since parameterisations of this kind are metrics (Tuovinen and Simpson, 2008b). Even if the profile correction
needed to relate the ozone uptake to plant response (e.g. Pleijel compensates for a significant bias, the near-surface concentration
et al., 2007). There are also smaller-scale CTMs covering a part of may prove a poor surrogate for the effect-inducing flux. High ozone
Europe, which have been used for high-resolution mapping of ozone concentrations are frequently connected with conditions that poten-
fluxes (e.g. Lagzi et al., 2004), and local-scale soil–vegetation– tially limit the stomatal uptake, such as high temperature and VPD
atmosphere-transfer models that include ozone (e.g. Grünhage and (e.g. Solberg et al., 2008). This co-variation means that the concen-
Haenel, 2008). Inferential modelling (IM) has been used for tration at leaf surface is not necessarily connected with a proportional
calculating regional ozone budgets (Coyle et al., 2003) and mapping stomatal uptake and therefore plant response (Cieslik, 2004). This is
exposures and doses on a high (1–2-km) spatial resolution for one reason for the different accumulation rates of AOT40 and stomatal
national-scale risk assessment of ozone effects (e.g. Keller et al., uptake observed in many studies (Fig. 5.4).
2007). As a compromise between the less data demanding exposure
The global-scale CTMs (Stevenson et al., 2006), as well as many indices and the more realistic dose metrics, solutions based on an
regional models (e.g. Vautard et al., 2005), typically include a variant ‘effective’ concentration have been suggested (e.g. Gerosa et al.,
of the parameterisation of Wesely (1989). This parameterisation 2004; Karlsson et al., 2004; Pleijel et al., 2004). Common to all these
does not include the stomatal effect of soil moisture conditions, is the idea that the concentrations for AOTX are first modified to
which has been shown to be a significant modifier of ozone fluxes, accommodate environmental factors controlling stomatal uptake,
especially in the Mediterranean region (Gerosa et al., 2008), yet such as VPD in the definition of the modified AOT30. In some cases,
proved challenging to model within CTMs (Emberson et al., 2007). all the main modifiers, such as those in the DO3SE model, are
Another key problem with large-scale CTMs is related to the aggre- considered (Gerosa et al., 2004; Pleijel et al., 2004). However, this
gated land cover classes, making it difficult to parameterise sub-grid
processes. For example, the dry deposition module of the recently
developed global Modular Earth Submodel System (MESSy) does not
differentiate between different vegetation types, even though a soil
moisture stress function is included (Kerkeweg et al., 2006).
The non-stomatal deposition processes are parameterised in
CTMs and IM systems in a much simpler way than the stomatal
component, typically by defining constant values for the relevant
resistances. However, a preliminary parameterisation has been
developed for the EMEP CTM for surface wetness effects for
northern European coniferous forests (Tuovinen et al., 2008). This
parameterisation is derived from the observations of Altimir et al.
(2006) and represents a gradual increase in the surface sink with
increasing surface wetness, parameterised as a function of relative
humidity. This results in higher and more variable ozone removal
rates within the model. In the future, integrated models are needed
to couple the surface exchange of energy, carbon and trace gases.
In particular, a multi-layer structure facilitating an explicit simu-
lation of vertical mixing and other in-canopy processes would be
useful for interpreting flux measurements (e.g. Duyzer et al., 2004;
Simon et al., 2005a).

5.5. Risk assessment methods

European abatement strategies are founded on effects-based

approaches, which involves different numerical indicators for
different air pollution effects on vegetation and human health
(UNECE, 2004). For potential ozone effects on vegetation, the
AOTX (Accumulated exposure Over a Threshold of X ppb) expo-
sure index replaced simpler concentration averages in the 1990s
(Fuhrer et al., 1997). Present definitions also include a metric
based on the stomatal uptake flux, AFstY (Accumulated stomatal
flux Fst above a threshold of Y nmol m2 s1), which represents
the absorbed dose and is thus considered biologically more
meaningful than the concentration-based AOTX (UNECE, 2004).
AFstY is more complex than AOTX in that it entails modelling the Fig. 5.4. Accumulation of AOT40 and stomatal dose over a Holm oak forest (6 August–11
stomatal conductance. October) in 2003 and 2004 in Italy (Gerosa et al., 2008).
5224 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
approach is very close to actually calculating the stomatal flux, as it
involves a multiplicative stomatal conductance model. Even the
profile corrections required for AOTX are based on flux–gradient
relationships of ozone and thus entail deposition modelling (Tuo-
vinen and Simpson, 2008b). From a micrometeorological point of
view, it would thus appear natural to aim at developing accurate
parameterisations for partitioning the total ozone flux into the
stomatal and non-stomatal components and applying flux-based
risk metrics because of their superior biological basis.
The model calculations of Simpson et al. (2007) indicate that
AOT40 and AFstY (for both crops and forests) show very different
regional patterns of exceedance of critical levels across Europe with
much smaller south–north gradients and larger exceedance area
for AFstY (Fig. 5.5). Even though there are still numerous uncer-
tainties involved in this kind of modelling, there is evidence that
the flux-based risk maps better correlate with observed plant
damage (Hayes et al., 2007).
5.6. Potential effects of climate change
Changes in the climatic conditions and chemical composition of the
atmosphere are expected to have a wide range of effects on the
interactions between tropospheric ozone and the biosphere. First,
ozone exposures are changing globally due to changes in precursor
emissions. Second, the long-term changes in meteorological condi-
tions affect atmospheric transport patterns and the rates of tropo-
spheric chemical reactions and dry deposition processes, and also
modify plant phenology. In addition to the rising temperature and
changes in precipitation distribution, elevated CO2 and ozone
concentrations may act as significant modifiers to stomatal exchange
(e.g. Ashmore, 2005). Finally, the characteristics of vegetation cover
and land use may be altered on various scales as a result of human
activities, effects of climate and ozone on plant species composition
and ecosystem function, and natural disturbances, all of which
potentially generate feedbacks to the surface removal of ozone.
So far, few studies have addressed the projected changes beyond
the ozone precursor emissions and atmospheric dynamics. In the
multi-model ensemble simulations of future concentrations by
Stevenson et al. (2006), the projected Vd was only altered by the
meteorological responses, neglecting the effects of water stress and
elevated CO2 concentrations, for example. In some studies, indi-
vidual, uncoupled effects have been included in the models. For
example, Sanderson et al. (2007) investigated the impact of the
stomatal conductance changes as directly induced by the rising CO2
levels. In this experiment, a global CTM was run with an assumed
reduction in Gst due to a doubling of CO2 concentrations, but with no
Fig. 5.5. Ratio of the AOT40 (left) and AFst1.6 (right) risk metric to the corresponding critical level for forests (not shown for values < 1) (Simpson et al., 2007).
changes in the meteorological input data. This resulted in
a decreased dry deposition sink, which increased the near-surface
ozone concentrations by 2–8 ppb on a seasonal basis. However,
a reduction in Gst, due to increased CO2 or any other effect, does not
proportionally reduce the stomatal uptake flux. This results from the
effect of decreased surface removal on the overall mass balance, with
higher concentrations partly compensating for the suppressed Gst.
While it would seem plausible that in warm climates increasing
temperatures reduce stomatal exchange, the opposite is true for
cooler regions. However, based on a modified version of the DO3SE
model, Karlsson et al. (2007) concluded that in northern Scandinavia
the most significant impact of the higher temperatures may be
related to an earlier onset of the growing season and the associated
phenological development, rather than their direct enhancement of
Gst. This together with elevated and increasing ozone concentrations
in spring may amplify the risk of negative ozone effects on vegeta-
tion in these areas. On the other hand, there may be a counteracting
effect on the stomatal uptake mediated by the concurrent higher
VPD (Karlsson et al., 2007; Harmens et al., 2007).
The summer of 2003 was exceptionally warm in Europe, espe-
cially in the central part of the continent, and may be taken as an
analogue of the future summers to be expected in the latter part of
the 21st century. A series of heat waves produced meteorological
conditions highly favourable for the net formation of ozone and its
build-up over large areas; indeed, record-high near-surface concen-
trations were observed in many locations (Solberg et al., 2008). It is
very likely that reduced dry deposition played a significant role in the
formation of the ozone episodes in 2003. The high temperatures and
soil moisture deficits (SMDs) most probably decreased the Gst of
vegetation and thus ozone removal from the atmosphere in central
and southern Europe, as indicated by the Italian eddy covariance
measurements (Gerosa et al., 2008) discussed above. Fig. 5.4 shows
that the ozone dose absorbed by a Holm oak forest in August–
September 2003 was less than 50% of that during the same period in
2004, in spite of the much higher concentrations in 2003.
The sensitivity runs with a global CTM by Solberg et al. (2008)
demonstrate the potentially large effect of dry deposition on near-
surface concentrations. Similarly, doubling of Rc within the model-
ling study of Vautard et al. (2005), partly because of the expected
increase in SMD which is not taken into account in the deposition
parameterisation, improved the model performance by increasing
the modelled concentrations. Considering the accumulation of
ozone dose of plants over the whole growing season, the significance
of drought periods much depends on their timing with respect to the
phenological stage of plants and the occurrence of elevated ozone
concentrations (Harmens et al., 2007). In addition, prolonged
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
drought stress may result in sustained impairment of the hydraulic
conductivity of plants, challenging the traditional dry deposition
models (Gerosa et al., 2008).
It has been estimated that exposure of plants to even the current
levels of ozone may significantly increase water use of forest trees
(McLaughlin et al., 2007) and reduce plant productivity in the most
polluted areas of the world, with exacerbating effects projected for
the future (Felzer et al., 2005). With elevated ozone concentrations,
the reductions in carbon sequestration may also lower soil carbon
formation rates and alter the below-ground carbon cycling (Loya
et al., 2003). Sitch et al. (2007) suggest that the ozone-induced
suppression of the global land-carbon sink gives rise to additional
accumulation of anthropogenic CO2 emissions in the atmosphere
and thus should be considered an indirect radiative forcing, which
could exceed the direct radiative forcing due to ozone increases.
6. Biogenic volatile organic compounds (BVOC)
6.1. Introduction
Biogenic volatile organic compounds (BVOC) are emitted by
almost all plants. In higher plants, emissions range from close to zero
to 10–20% of the carbon fixed by photosynthesis. Global emissions
have been estimated at around 800 Tg C y1 although this figure
has been regularly revised based on improvements in scaling up of
laboratory results, spatial and temporal integrations, and large-scale
monitoring at whole ecosystem levels (Lathiere et al., 2006; Arneth
et al., in press). Approximately half of the emissions are believed to
be isoprene (Guenther et al., 2000, 2006). Monoterpenes, the other
large class of volatile isoprenoids, contribute another 10–15% of the
total BVOC emissions. Sesquiterpenes, a third class of isoprenoids,
are emitted in small quantities from non-stressed vegetation, except
from flowers. The remainder is emitted as oxygenated volatile
compounds, including alcohols, aldehydes and ketones, particularly
during periods of plant development or in response to environ-
mental stress (Heiden et al., 2003; Seco et al., 2007).
6.1.1. Volatile isoprenoids
Volatile isoprenoids have been extensively studied compounds
because of their relevant functions in plant vs. environment inter-
actions and their role in the atmosphere. Isoprene and mono-
terpenes are formed in plastids via methylerythritol phosphate
(MEP) pathway (Lichtenthaler, 1999).
While isoprenoid emissions mainly rely on newly synthesized
photosynthetic metabolites in chloroplasts, extra-chloroplastic
sources can feed carbon to sustain isoprene or monoterpene
biosynthesis, including xylem-transported sugars and chloroplastic
starch (Karl et al., 2002a; Kreuzwieser et al., 2002) as well as
refixation of respired CO2 (Loreto et al., 2004). These additional
carbon sources of isoprenoid biosynthesis can become significant
especially when photosynthesis is constrained by environmental
stresses. Under extreme stress conditions, such as drought stress,
the leaf carbon budget can become negative, as leaves release more
carbon in the form of isoprenoids and respiratory CO2 than they
gain through photosynthesis (e.g. Brilli et al., 2007; Schnitzler et al.,
2004).
Monoterpenes and sesquiterpenes are active compounds in plant
interactions with other organisms. Monoterpenes may either attract
or deter herbivores or carnivores, and attract pollinators (Gershenzon
and Dudareva, 2007). Indirect evidence suggests that isoprene
and monoterpenes as lipid-soluble molecules may protect plant
membranes from thermal and oxidative stress (reviewed by Sharkey
and Yeh, 2001). This favourable action can also assist in adapting
isoprenoid-emitters to increasing oxidative pressures (Lerdau, 2007).
5225
6.1.2. Oxygenated volatile compounds
While the production and emission of volatile isoprenoids, and
in particular isoprene and monoterpenes, is strongly species-
specific, all plants emit oxygenated volatiles. At the global scale, the
emission source strength of these compounds is generally smaller
than that for volatile isoprenoids, and many of these oxygenated
compounds are less reactive than isoprenoids in the atmosphere.
However, the emissions of oxygenated compounds, which may
be induced by developmental and stress factors, may be large at
certain periods of the year and by certain vegetation types (see also
flux measurements below).
Methanol, acetaldehyde and C-6 compounds are often emitted in
large quantities, especially in the presence of mechanical wounding
or other stresses (Loreto et al., 2006). Methanol formation is prob-
ably due to the demethylation of pectins in cell walls (Galbally and
Kirstine, 2002) and does not have any known protective role for
plants. The release of methanol into the atmosphere is therefore
associated with cell wall damage occurring because of wounding
(Karl et al., 2001a). Methanol is also emitted by growing plant tissues
(Nemecek-Marshall et al., 1995; Harley et al., 2007; Hüve et al.,
2007), and senescing tissues (Fall, 2003). Large fluxes of methanol
could be measured, as an example, from rapidly expanding leaves of
the Mediterranean vegetation during the spring ACCENT–VOCBAS
2007 campaign (see below).
Large fluxes of acetaldehyde have been observed in conditions
of root anoxia such as under waterlogging stress. Short-lived bursts
of acetaldehyde are sometimes also observed from darkened leaves
(Karl et al., 2002b). Interestingly, acetaldehyde is also emitted
following wounding (Fall et al., 1999) and ozone stress episodes,
and large fluxes of this compound can be observed under natural
conditions (Lathiere et al., 2006).
Finally, C-6 oxygenated compounds are emitted from leaves
subject to various stresses such as wounding, e.g. as a consequence of
cutting hay, insect feeding, ozone stress and heat stress (Hatanaka,
1993). Aldehydes, (Z)-3-hexenal, (E)-3-hexenal and (E)-2-hexenal
with characteristic green leaf (‘cut grass’) odour are formed first,
and then transformed into corresponding alcohols by alcohol
dehydrogenases. Esters such as hexenolacetates can also be formed
and emitted during these processes. Proton-transfer reaction mass-
spectrometry has provided detailed insight into the associated
time-sequence of events (Beauchamp et al., 2005).
6.2. Environmental controls on BVOC emissions
6.2.1. Physiological and physico-chemical controls of emissions
Models of BVOC emissions consider that emissions are controlled
either by physiological factors (‘‘isoprene’’ algorithm) or by physico-
chemical factors (‘‘monoterpene’’ algorithm) (Guenther et al.,
1993). By considering only physiological factors, the synthesized
compounds are immediately released from the foliage. In contrast,
by considering only physico-chemical factors, the compounds are
emitted from specialized storage structures such as resin ducts
present in conifers, glandular trichomes in species from Lamiaceae
(peppermint), and oil glands in Rutaceae (lemon, orange) and
Myrtaceae (eucalypts).
Physiological controls operate at the level of compound
synthesis. Light and temperature, the key environmental drivers,
affect the rate of intermediate production; temperature also affects
the activity of flux controlling enzymes (Fig. 6.1, Niinemets et al.,
1999) Over the longer term, synthesis and turnover of rate-limiting
enzymes can control the flux rate (Monson et al., 1994; Lehning
et al., 2001; Fischbach et al., 2002). In species with large storage
pools, the emissions can be independent of the rate of compound
synthesis, being controlled by temperature effects on the
5226 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267

Fig. 6.1. The emission of volatile organic compounds from plants is limited by both physiological and physico-chemical characteristics. Physiological factors control the rate of
synthesis of VOC and operate at the level of intermediate production and the activity of flux controlling enzymes such as isoprene synthase or terpene synthases for volatile
isoprenoids. Physico-chemical factors, in particular, low compound volatility and rate of diffusion, can limit the release of synthesized VOC from the leaves and determine the degree
to which the synthesized compound can be stored in the leaves.

evaporation and diffusion of compounds from the storage pools concentration and atmospheric reactivity in morning hours. Current
(Fig. 6.1, e.g. Tingey et al., 1991). steady-state models predict zero nightime monoterpenes emissions
Often there is no clear separation between physiological and for species lacking specialized storage structures.
physico-chemical controls. Although it is generally belived that
only evaporation from pools controls the emissions in species with 6.2.3. Uptake and release of volatile compounds by vegetation
specialized storage pools, there is increasing evidence that the A relevant implication of the non-specific storage is the uptake of
emissions can be partly controlled by physiological factors also in volatile compounds from ambient air when air concentrations are
classical ‘‘storage’’ species. On the other hand, physico-chemical higher than those in equilibrium with plant liquid and lipid phases.
controls on emissions often interact with physiological controls in The compounds taken up during the periods with high atmospheric
species without specialized storage pools for BVOC (Fig. 6.1). BVOC concentrations may be released back into the ambient air
when air concentrations are small if they are not metabolized or
6.2.2. Physico-chemical controls of emission in species lacking translocated to the roots. The uptake of water-soluble compounds
specific storage structures is expected to scale with leaf water content, while the uptake of
Every BVOC species can be non-specifically stored in leaf liquid lipid-soluble compounds with leaf lipid content (Noe et al., 2008a).
and lipid phases, with the non-specific storage capacity depending on Thus, even species considered ‘‘non-emitting’’ can emit several
the compound physico-chemical traits such as the gas/liquid aqueous BVOCs at trace level from the non-specific storage built up from
phase partition coefficient (Henry’s law constant, H) and lipid/liquid ambient sources.
phase partition coefficient (octanol/water partition coefficient, KOW).
For instance, compounds that are highly water-soluble such as
methanol and ethanol can accumulate in leaf aqueous phase, espe-
cially if gas-phase diffusion out of the leaves is hindered due to limited
opening of stomatal pores. Although the rate of compound synthesis
may respond very quickly to environmental perturbations, a build up
of water-soluble compounds reduces the sensitivity of the emission
responses to variation in environmental factors.
Analyses of the emissions of strongly lipid-soluble BVOC species
such as non-oxygenated monoterpenes indicates that the non-specific
storage of these compounds, mainly in leaf lipid phase, significantly
alters the emission kinetics in species lacking specialized mono-
terpene storage pools. In these species, to reach steady-state rates of
monoterpene emission can take from minutes to hours depending
on monoterpene physico-chemical characteristics (Niinemets and
Reichstein, 2002; Noe et al., 2006).
The delayed emission responses due to non-specific storage can
also result in modified sensitivity of the emissions to environ-
mental factors. For instance, a sigmoidal light-response curve can
result if non-specific storage pools have not yet reached a steady-
state with each light level. Under such experimental conditions, the
emission rate recorded is lower than the monoterpene synthesis
rate. Given the long time periods, often on the order of 1 h required
to reach the steady-state, non-steady-state conditions are common
in monoterpene measurements.
In addition to alteration of the immediate environmental controls,
Fig. 6.2. Monoterpene emissions from Quercus ilex dominated forest in Castelporziano,
non-specific storage can modify the emissions at daily and weekly Italy for six days in June simulated using the standard Guenther et al. (1993) model and
timescales. Another important implication of the non-specific a model considering non-specific monoterpene storage in leaf liquid and lipid pools
storage is significant nocturnal emissions, which was observed e.g. in (modified from Niinemets and Reichstein, 2002; Niinemets, 2008). The standard emis-
the case of monoterpenes (Loreto et al., 2000; Niinemets et al., sion model predicts that the emission rate responds immediately to changes in light and
temperature, but non-specific storage of lipid-soluble non-oxygenated and water-soluble
2002b). Simulation analyses indicate substantial nocturnal emissions oxygenated monoterpenes results in time-lags between terpene synthesis and emission.
at the ecosystem scale (Fig. 6.2). Significant night-time BVOC emis- As the result of these time-lags, the emissions are predicted to continue also at night,
sions from non-specific storage can strongly influence OH-radical although synthesis has ceased.
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
6.2.4. CO2-Dependence of emissions
The classical Guenther (1993) algorithm considers strong light and
temperature dependencies of isoprene and ‘‘non-stored’’ mono-
terpene emissions. CO2 was not considered as an important factor in
controlling the emission of volatile isoprenoids. More recent labora-
tory and field studies have established that volatile isoprenoids are
sensitive to ambient CO2 and that the emissions decrease in plants
grown at CO2 concentrations higher than ambient (Loreto et al., 2001;
Rosenstiel et al., 2003). This effect may be observed at CO2 concen-
trations that are likely to be reached in the future (double or less than
double the current concentrations) and should be therefore addressed
in future modelling efforts.
There is now sufficient information to believe that the negative
effect of CO2 on isoprene emission is ubiquitous and not species-
specific. Arneth et al. (in press) included an empirical CO2-depen-
dence into the Niinemets et al. (1999) model, and predicted that
CO2 reduction of isoprene emission could partially compensate for
the emission increases with rising temperature. However, elevated
CO2 will enhance photosynthesis and growth of plants, in particular
vegetation leaf area, which may in turn increase the emission of
isoprene by vegetation. The net effect of these interactions await
experimental confirmation.
Monoterpene emissions are also likely to be influenced by CO2,
but there is less experimental evidence than for isoprene (e.g.
Loreto et al., 2001). More studies are clearly needed to assess
whether the different physico-chemical controls (see above) and
the presence of small internal pools buffer the effect of CO2 and
make monoterpenes less sensitive to CO2 control.
6.2.5. Induced emissions
In addition to the constitutive emissions, recent work demon-
strates that synthesis of volatile isoprenoids is induced in many
species in response to biotic (e.g. attack of herbivores and pathogens)
and abiotic (e.g. ozone stress, heat stress) stresses (Beauchamp et al.,
2005; Blande et al., 2005; Loreto et al., 2006).
Previous work has shown that the emissions of volatile organic
compounds are induced in response to stress in practically all plant
species, also in those not emitting volatile isoprenoids under optimal
growth conditions (e.g. tobacco and sunflower, Heiden et al., 1999;
Beauchamp et al., 2005). In constitutively emitting species, the
volatile isoprenoid blend differs between induced and constitutive
emissions. For instance, European aspen (Populus tremula) emits
isoprene as the main product in non-stressed conditions, but
induced emissions are dominated by monoterpenes limonene and
a-pinene and sesquiterpenes (Blande et al., 2005). In non-stressed
conditions, the emissions of the monoterpene-emitting species
Pinus pinea are dominated by limonene, but the emissions in
conditions of high temperature and low water availability are
dominated by linalool and ocimene; these emissions significantly
exceed the emission in non-stressed conditions (Staudt et al., 2000).
Current emission models do not consider ‘‘non-emitting’’
species, which, in addition to emissions from non-specific storage,
may have significant induced emissions. Furthermore, modification
of gene expression profiles in response to stress and upon adap-
tation to stress may in many cases explain the modified emission
compositions. Accordingly, understanding induction mechanisms
and consideration of induced emissions is crucial in explaining and
predicting emission profiles.
6.3. Contemporary difficulties in scaling BVOC emissions
from leaf to ecosystem
Parameterisation of models at ecosystem scales is bounded by
a series of uncertainties. A key uncertainty is currently the lack of
reliable information of emission potentials (Arneth et al., in press).
5227
Although the available emission information has been recently
collated, data for many key emitting species are still lacking. Recent
observations have indicated that several important species such as
cork oak (Quercus suber) (Staudt et al., 2004; Pio et al., 2005) and
European beech (Fagus sylvatica) (Moukhtar et al., 2005; Holzke
et al., 2006) previously considered non-emitters are moderate to
strong emitters of monoterpenes.
The emission potentials of many ornamental, alien species used
in urban landscaping and in gardens are missing (Owen et al., 2003;
Noe et al., 2008b). Understanding the emissions of ornamental
species is also important in light of potential changes in vegetation in
urban landscapes driven by global change and the growth of urban
areas. Global warming and associated increases of evergreen emit-
ting exotic species in northern urban landscapes of northern hemi-
sphere can importantly enhance the winter emissions (Niinemets
and Peñuelas, 2008).
In addition, stress- and time-dependent modifications of emission
potentials are only partly understood, but such adaptive responses can
vastly affect ecosystem fluxes. Apart from gradual changes in BVOC
emission capacity in response to day-to-day and seasonal differences
in weather conditions (Guenther,1999; Sharkey et al.,1999), emissions
triggered by biotic stresses such as herbivory or pathogen attack or
by abiotic stress factor such as elevated ozone concentrations
(e.g. Beauchamp et al., 2005), can potentially greatly influence whole
ecosystem fluxes.
6.4. BVOC fluxes over Europe, by compound and in relation
to the needs of photochemical oxidant models
6.4.1. Flux measurement techniques
The development of disjunct eddy covariance (DEC) methods
(Rinne et al., 2001; ) alongside the development of proton-transfer
reaction-mass spectrometry (PTR-MS, Lindinger et al., 1998) have
enabled direct flux measurements of multiple VOC species simul-
taneously. The PTR-MS has also been used in a more traditional
continuously sampling eddy covariance technique, in this mode the
flux of just one VOC species can be measured at a time (Karl et al.,
2001b, 2001c). The DEC methods have been utilized in different
European ecosystems (Rinne et al., 2007; Davison et al., 2008).
Inter-comparison experiments to validate these new techniques
have been conducted partly under ACCENT-BIAFLUX (Ammann
et al., 2006; Neftel et al., 2007; Rinne et al., 2008). For isoprene
there also exists a fast isoprene sensor (FIS) based on chem-
iluminescence enabling the application of eddy covariance
measurements (Guenther and Hills, 1998).
High reactivity of several plant BVOCs imposes significant diffi-
culties in determining whole canopy terpene emission fluxes by
micrometeorological techniques. In particular, some monoterpenes
and most sesquiterpenes have atmospheric lifetimes on the order of
minutes. High reactivity of these compounds can imply that before
reaching the BVOC detector, a significant fraction of the emitted
compounds has already reacted in the atmosphere, resulting in
underestimated emission fluxes (Rinne et al., 2007). To determine
the emissions of reactive terpenes, atmospheric chemistry models
have been inverted (Bonn et al., 2007). However, the lack of reactiion
rate coefficients for many terpenes and the dependencies of these on
humidity and temperature seriously hamper the overall assessment
of the rates of emission and contribution to atmospheric reactivity.
6.4.2. Isoprene
Isoprene is the most studied biogenic VOC. European isoprene
emissions have been studied at the ecosystem scale in a range of
landscapes. In some European ecosystems considerable isoprene
emission fluxes have been measured (Ciccioli et al., 1997; Davison
et al., 2008; Simon et al., 2005b). In contrast European boreal
5228 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
coniferous forests are generally very low emitters (Rinne et al., 1999).
In measurements conducted above homogeneous conifer forest, the
isoprene emissions from isoprene emitters concentrated in e.g.
ditches, lakeshores and roadsides, will not be observed. Landscape
scale emissions over southern Finland, estimated by a boundary
layer budget method, show much smaller isoprene than mono-
terpene emissions (Spirig et al., 2004). In general, measuring forest
sites, characterized by mixed composition, must account for the
plant species composition within the flux footprint. This has been
shown by Spirig et al. (2005), who observed the variation in
normalized ecosystem scale isoprene emission from a central
European mixed broadleaf forest to be dependent on the abundance
of Quercus robur, which is a high isoprene emitter, within the flux
footprint area.
Flux measurements of isoprene often correlate well with leaf-
level measurements, reflecting the relatively long atmospheric
lifetime of isoprene (w1 h) compared with other shorter lived
BVOCs. However, when the ecosystems are not homogenous,
correspondence between emissions at plant and ecosystem levels is
not straightforward. For example, the study conducted at Siikaneva
fen ecosystem using soil chambers (Hellén et al., 2006) and REA
technique (Haapanala et al., 2006) shows a considerable discrepancy
between the isoprene emissions measured by these two techniques.
The fluxes measured by Haapanala et al. (2006) under low CTCL
values were substantially smaller than the model values, which may
imply deeper penetration of PAR into the moss carpet at highlight
conditions; a simple light penetration model slightly improved the
correlation (Haapanala et al., 2006).
6.4.3. Monoterpenes
European ecosystems are substantial sources of atmospheric
monoterpenes and many flux measurement experiments have
concentrated on these compounds. The diurnal variations of the
monoterpene fluxes above boreal coniferous forests appear to be
relatively well reproduced by the temperature dependent Tingey–
Guenther emission algorithm (Guenther et al., 1993). Monoterpene
emissions from Mediterranean ecosystems are better described by
the light and temperature dependent isoprene emission algorithm
(Seufert et al., 1997; Schween et al., 1997), with important discrep-
ancies likely reflecting non-specific storage and stress-dependent
changes in emissions (Niinemets et al., 2002a, 2002b, see above).
At coniferous forest sites a diurnal concentration cycle with
highest concentrations at night are typical (e.g. Hakola et al., 2000;
Steinbrecher et al., 2000; Rinne et al., 2000, 2005). This is due to the
emission continuing during night-time, although at a lower rate
than during the day, and to considerably reduced turbulent mixing
at night. On the contrary, in the Mediterranean region, as well as in
Amazonian tropics, and in European mixed broadleaf forest, where
the night-time monoterpene emission is practically zero due to the
light dependence of the monoterpene emission, daytime maxima
are typical (Zimmerman et al., 1988; Schween et al., 1997; Rinne
et al., 2002; Spirig et al., 2005).
The major monoterpenes emitted by forest ecosystems in Europe
are a- and b-pinene and D3-carene. For example, monoterpene
emissions from Norway spruce forest consist of a- and b-pinene
(Christensen et al., 2000). However, in some Mediterranean ecosys-
tems limonene can form a significant part of the monoterpene
emission (Schween et al., 1997) and, in the case of orange orchards,
be the dominant monoterpene emitted (Christensen et al., 2000;
Darmais et al., 2000).
6.4.4. Sesquiterpenes
Due to the enhanced chemical reactivity of sesquiterpenes, atmo-
spheric concentrations of these compounds are very small, making
flux measurements extremely difficult. Enclosure measurements at
an orange orchard revealed substantial emission of b-caryophyllene,
while the flux measurements conducted by REA method show the
fluxes to be close to zero indicating rapid within and below canopy
chemical degradation (Ciccioli et al., 1999).
6.4.5. Methanol
The development of the DEC-PTR-MS has recently enabled
ecosystem scale flux measurements of methanol leading to
considerable progress in our knowledge of ecosystem scale emission
of this compound. Methanol seems to be emitted from all ecosys-
tems and also from drying and decaying plant material. Methanol is
typically the second or third most abundantly emitted biogenic VOC
after isoprene and monoterpenes in most ecosystems.
The measured ecosystem scale methanol emissions do not
generally fit the emission algorithms, used for monoterpene fluxes. A
recent empirical temperature dependent formulation has been pre-
sented for methanol by Harley et al. (2007). From a mechanistic
understanding of the physico-chemical control (see above), meth-
anol emission should be regulated by stomata, in contrast to isoprene
and monoterpene emission. In field flux experiments, this kind of
behaviour has not been generally observed. Brunner et al. (2007)
have observed the methanol emissions from agricultural grassland
ecosystem to be large in the morning relative to emissions in the
evening. A similar observation was found in the recent ACCENT–
VOCBAS campaign on the Mediterranean macchia of Castelporziano.
6.4.6. Acetone and acetaldehyde
Acetone and acetaldehyde in the atmosphere are the result of both
primary emissions from biogenic and anthropogenic sources and
secondary formation from other gaseous precursors. Fluxes of these
carbonyls have been observed to be emitted from coniferous forests in
Europe (Rinne et al., 2007) as well as in the US (Schade and Goldstein,
2001). Also the Mediterranean macchia ecosystem is observed to emit
these compounds (Davison et al., 2008). No emission of these
compounds from broadleaf deciduous forests has been reported.
Anaerobic conditions in root system have been observed to enhance
the emission of acetaldehyde from plant foliage (Kreuzwieser et al.,
1999) as also mechanistically explained above. However, no ecosystem
scale flux measurements of this compound, in conditions where the
root systems was anaerobic, have been reported.
6.4.7. Other compounds
The emissions of many compounds, other than isoprene,
monoterpenes, methanol, acetone and acetaldehyde, have been too
small to be measured by micrometeorological flux measurement
techniques. However, there are a few other compounds which
have been observed to be emitted by micrometeorological flux
measurement techniques in certain ecosystems. Some western US
pine forests have been shown to emit 2-Methyl-3-buten-2-ol (MBO)
in considerable amounts (e.g. Baker et al., 1999; Schade et al., 2000).
From European Pine species, no significant emissions of MBO have
been observed (e.g. Hakola et al., 2006). It is noteworthy that drying
hay was observed to emit (Z)-3-hexenal and (Z)-3-hezenol and
hexenyl acetates (Davidson et al., 2008a). These compounds appear
to be reliable markers of membrane damage and lipoxygenation, as
previously indicated (Loreto et al., 2006).
6.5. The EU large field campaigns in the Mediterranean area:
from BEMA to ACCENT
Pioneering campaigns around the world (e.g. the SOS 1999
campaign in North America, the LBA/CLAIRE 1999 campaign over the
Amazon, the SAFARI 2000 campaign in Southern Africa) highlighted
the predominance of isoprene as the most commonly emitted VOC by
vegetation, over different environments, and by different ecosystems,
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
spanning tropical to boreal forests. In Europe, however, a different
picture emerged. The BIPHOREP 1996–1997 campaign in boreal
Europe revealed the dominance of monoterpenes as the most abun-
dantly emitted VOC from European boreal ecosystems. In otherwise
clean northerly air masses, at least the growth, if not the formation, of
organic aerosol, seems to be strongly influenced by the presence of
biogenic VOCs. The most likely candidates contributing to this aerosol
growth are monoterpene oxidation products (Lee et al., 2006). The
BEMA (Biogenic Emission in the Mediterranean Area) 1996 campaign
highlighted the remarkable peculiarity of Mediterranean coastal
vegetation that is almost uniquely characterized by monoterpene-
emitting species (Loreto et al., 1998). The reason for this distinctive
trait of Mediterranean vegetation remains unknown.
A new campaign during spring 2007 in the Mediterranean area,
as part of the ACCENT and European Science Foundation programme
VOCBAS programmes took place. The campaign was deliberately
held on the same site of the BEMA campaign, the large peri-urban
natural preserved area of Castelporziano, in the conurbation of
Roma. This site has two main characteristics that make it an excellent
case of study for biosphere–atmosphere interactions. First, the
6000 ha wide preserved area of Castelporziano is a hot spot for
biodiversity in the Mediterranean, with more than 1000 plant
species represented in the flora of the area (Davison et al., 2009). The
main ecosystems going towards the sea are characterized by oak
(Quercus ilex, Q. suber, Quercus cerris) and pine (P. pinea) forests, often
associated with a rich understory vegetation. The part of the Estate
facing the Tyrrhenian sea is characterized by sand dunes and
a humid retrodunal area, with a large and extremely well preserved
area covered by Mediterranean ‘‘macchia’’ vegetation, prevalently
shrubs and small evergreen trees, such as Juniperus communis, Q. ilex,
Phillyrea latifolia, Arbutus unedo, Rosmarinus officinale, Erica arborea,
and Cistus incanus. Second, the preserved area is only distant 25 km
from the centre of Roma in the S-E direction. It is exposed to
a constant wind circulation that favours transport of air masses from
the city center during night-time, and from the sea during daytime.
This periodically exposes vegetation to urban pollutants and may
trigger formation of secondary pollutants that are contributed by
BVOC precursors (Chameides et al., 1988; Di Carlo et al., 2004).
The campaign (i) provided fluxes of BVOC from Mediterranean
vegetation, in a season during which plants are in optimal physio-
logical conditions prior to drought and heat stress conditions
experienced later in the year, but during which BVOC emisions are
thought to be constrained by leaf development limitations;
(ii) investigated, by coupling concentration and flux measurements,
the in situ extent of BVOC reactivity, and in particular whether in
situ BVOC oxidation could drive formation of secondary organic
compounds in the atmosphere; (iii) identified whether BVOCs can
act as precursors of photochemical smog; (iv) provided a second
assessment, ten years after the campaign organized by the
EC-BEMA project (Seufert et al., 1997), of BVOC emission in an
area largely affected by anthropogenic and climatic changes, thus
creating the foundation for a historical series of measurements
which may be especially important in view of current and future
climate change factors, and, in particular, of the simultaneous and
strong increase of temperature, drought and pollutants in the
Mediterranean area; and (v) fostered interdisciplinary collaboration
between the communities of biologists, atmospheric chemists and
physicists, further catalyzing research on the important roles of
BVOCs in the environment.
The campaign was run in the macchia strip placed between the
dunes and the main forested land inside the Castelporziano Estate.
The oak and pine forested area was extremely well characterized
during the BEMA campaign (1997) but the macchia vegetation
received only limited attention (Owen et al., 1997). The macchia strip
is characterized by a modest roughness of the terrain due to the
5229
presence of small sandy dunes, and by a gradient of soil humidity
due to the presence of freshwater sources.
6.6. Remote sensing of BVOC
Over the last decade space-based instrumentation, capable of
probing the lower troposphere, has reached the level of accuracy
necessary to quantify surface sources and sinks of trace gases from
observed variations in trace gas concentrations (Palmer, 2008). The
only non-methane BVOC measured in the lower troposphere from
space is formaldehyde (HCHO), a high yield product of VOC
oxidation that is measured from clear-sky backscattered solar
radiation at ultraviolet wavelengths (Chance et al., 2000). The main
sinks of HCHO are oxidation by OH and photolysis leading to
a tropospheric lifetime of several hours. Fig. 5.3 shows the global
distribution of HCHO columns observed by the Ozone Monitoring
Instrument during August 2006.
Oxidation of methane (CH4) by OH, the largest global source
of HCHO, provides a uniform HCHO background of w100 pptv,
reflecting the w8-year lifetime of CH4. The limit of detection of
HCHO from current space-borne instrument is approximately
4  1015 molec cm2 (Chance et al., 2000), which is close to the
source of HCHO from CH4 oxidation. Over the continental boundary
layer, oxidation of anthropogenic and biogenic VOCs provide an
additional source of HCHO that can reach on a local scale up to
several ppbv, equating to columns over an order of magnitude
determined by CH4 (Fig. 6.3). Observed variations in HCHO, deter-
mined by the oxidation of VOCs, therefore provide constraints on
emissions of the parent VOCs. Horizontal transport smears the
local relationship between VOC emissions and HCHO columns,
the extent of which is determined by wind speed and the time-
dependent yield of HCHO from the VOC oxidation (Palmer et al.,
2003). Over a number of global regions, variations in HCHO
columns are determined by isoprene (Palmer et al., 2006), due to
its rapid production and high molar yield of HCHO (Palmer et al.,
2006). Other reactive biogenic VOCs, such as monoterpenes, also
have short atmospheric lifetimes but they quickly produce acetone
with a high yield that has an atmospheric lifetime of weeks and
consequently slows down the production of HCHO (Palmer et al.,
2006). Long-lived VOCs such as CH4 and CH3OH, while being the
largest sources of HCHO, only contribute to the slowly varying
background of HCHO.
Early work showed that the magnitude and distribution of
GOME-derived isoprene emissions based on HCHO measurements
were more consistent with in situ measurements than either the
GEIA or BEIS2 isoprene inventories, based on Guenther et al. (1995)
(Palmer et al., 2003). Monthly mean distributions of HCHO, and
inferred isoprene emissions, during summertime are dominated by
high values over the southeastern states of the USA (Chance et al.,
2000) due to a large density of isoprene-emitting oak trees over the
Ozarks Plateau (Wiedinmyer et al., 2005). Examination of GOME
orbital data revealed large variations in HCHO, explained by
changes in surface temperature, which led to inferred monthly
mean isoprene emissions that were significantly lower than those
predicted by bottom–up models (Palmer et al., 2003). Later work
showed that the observed seasonal and year-to-year variability was
consistent with the MEGAN model (Guenther et al., 2006), but
GOME-derived isoprene emissions were 25% higher (lower) at the
beginning (end) of the growing season (Abbot et al., 2003; Palmer
et al., 2006). Both MEGAN and GOME show a maximum over the
Southeast US but disagree in the precise location, with implications
for modelling surface ozone (Fiore et al., 2005).
Isoprene emissions from tropical ecosystems have been esti-
mated to contribute 75% of the global isoprene budget, but are not
well quantified. Over tropical South America, the widespread
5230 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Fig. 6.3. Formaldehyde columns (1016 molec cm2) retrieved from the NASA Aura Ozone Monitoring Instrument (OMI) for August 2006, courtesy of Thomas Kurosu, Harvard
Smithsonian Center for Astrophysics.
extent of biomass burning in the dry season means that without
high-resolution data the only practical approach is to use data
over west Amazonia, which is largely unaffected by fires (Barkley
et al., 2009). There is a strong seasonal cycle of GOME HCHO
columns over this region reproduced each year during 1996–2001,
characterized by large values in the wet and dry seasons, sepa-
rated by low values in the wet-to-dry transition period (May–
July); this is consistent with in situ isoprene concentration
measurements (Palmer et al., 2007). This large-scale reduction in
isoprene emissions suggests a major temporary shift in underlying
meteorology or phenology, but its origin remains unclear. This
study found that MEGAN and GOME were in better agreement in
the dry season, when GOME isoprene emissions could not be
explained by changes in surface temperature. GOME isoprene
emissions in the wet season could be not explained by changes in
surface temperature, precipitation or soil moisture, suggesting
either an unexplained process that determines isoprene during
this season or noisy data (Barkley et al., 2009). These substantial
open questions will be readdressed with data from newer sensors
and should be the subject of extensive year-long ground-based
measurement campaigns.
There are a number of uncertainties associated with the HCHO
measurement and the approach used to infer surface emissions of
isoprene from these measurements (Palmer et al., 2003; Millet et al.,
2006), which lead to uncertainties that total more than 100% of
estimated emissions (Palmer et al., 2006). Work related to the anal-
ysis of GOME data has suggested that HCHO production predicted by
chemical mechanisms typically used by large-scale chemistry-
transport models are in error by more than 25% (Palmer et al., 2006).
Current studies that determine VOC emissions using HCHO
column data are already focusing on data from newer space-borne
sensors (e.g. Aura OMI and MetOp GOME-2) that have better spatial
(100 s km2) and daily temporal resolution, enabling more detailed
testing of current bottom–up inventories. The advances in resolution,
in particular, improve: 1) the probability of cloud-free scenes and
consequently lead a greater number of useful data points; 2) spatial
disaggregation of different HCHO sources, e.g. biomass burning and
biogenic VOC emissions over tropical regions, which can lead a better
description of land-surface processes; and 3) their usefulness in
planning and executing measurement campaigns. For example,
analysis of GOME-2 and OMI HCHO data, which have local overpass
times of 09:30 and 13:30, will allow us to develop a crude under-
standing of the diurnal cycle of BVOC emissions on continental scales.
Knowledge of the complex organic chemistry associated
with BVOC oxidation will only improve with a concerted effort to
increase the number of laboratory and field measurements. With
the rapid increase in available remotely sensed datasets that could
be brought to bear on estimating BVOC emissions (e.g. HCHO, leaf
phenology, land cover) there should be scope to develop new
functional descriptions of isoprene emission that are independent
of the assumptions made in traditional bottom–up models derived
from in situ measurements.
7. Deposition and resuspension of aerosols onto
and from terrestrial surfaces
7.1. Introduction
Aerosols present a complex multi-variate and multi-scale
problem to environmental research. They have strong impacts on
climate indeed they represent the largest uncertainties in our ability
to predict climate change (IPCC, 2007), human health and provide
a means for pollutant deposition to sensitive ecosystems (trans-
porting e.g. nitrogen, sulphur and toxic metals). A vital component of
the global aerosol cycle is deposition of many critical secondary
process-derived condensed phase compounds as well as primary
generated aerosols, both in the ultrafine and coarse modes. The
majority arise from the consequences of anthropogenic activities
associated with global industrialisation and urbanization where
large emissions of reactive nitrogen species lead to an increase in
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
nitrogen aerosol formation which is eventually removed by wet or
dry deposition. Sulphate aerosol remains an important issue in
the Eastern US and China. Over the last 150 years the atmospheric
particulate loading has changed from coal and other solid fuel
burning to modern combustion processes that liberate a greater
preponderance of submicron, ultrafine particles. This has initiated
a paradigm shift in some quarters of the relative importance of
coarse mode as opposed to fine mode particulates and their
behaviour for mainly health related reasons. This shift will likely
move into a third phase where emissions from nano-particle
technologies are starting to play an increasing role. In addition, it is
becoming obvious that particulate matter provides an area of policy
conflict: efforts to curb PM concentrations to protect human health
are likely to reduce global dimming and thus further accelerate
climate change, although there are also components, such as soot,
that have a negative impact on both human health and the climate
system. The primary aims of research into the biosphere/atmosphere
exchange of particles are:
(a) to improve our estimates of primary aerosol emissions from
diffuse sources and their parametrisations,
(b) to measure directly the contribution of particle deposition to
the deposition of compounds that are detrimental to ecosys-
tems or may accumulate in water, soils or crops (e.g. N and S
compounds, heavy metals and nano particles),
(c) to derive parametrisations of the deposition velocity (Vd) of
particles, for inclusion into CTMs e.g. aimed at predicting
deposition, human health impacts and climate impacts,
(d) to study aerosol formation and dynamics in the atmosphere.
If the models predict the size distribution of the aerosol explic-
itly, Vd needs to be parametrised as a function of particle diameter
(Dp). By contrast, where the models only deal with the bulk species,
Vd may be derived from measurements of the individual compounds
(e.g. Ruijgrok et al., 1997) or, more commonly, from a weighting of
Vd(Dp) with a typical size distribution of the aerosol component.
7.2. Review of new measurement approaches and instrumentation
Progress in the quantification and parameterisation of surface/
atmosphere exchange of particles and aerosol compounds is closely
related to developments in the measurement technology. In the
1970s and 80s measurements of aerosol dry deposition were made
in the wind tunnel or using surrogate surface collectors, such as
knife-edge collectors, inverted frisbee type dust deposition gauges
and moss bags. Although these techniques are still being used, they
have attracted serious criticism as their aerodynamic properties are
usually not representative for the surface for which deposition is to
be estimated. The lack of an understanding of the relationship
between deposition on these collectors and deposition to the
surrounding landscape reduce the value of the measurement to
trend detection. More recently, non-intrusive micrometeorological
flux measurement techniques have increasingly been extended
to measure surface/atmosphere exchange particle fluxes at the
field scale. Measurements of particle fluxes fall into two categories:
particle number fluxes (total or size-segregated) and chemically
resolved aerosol fluxes.
7.2.1. Flux measurements of particle numbers (size-resolved
or total), without information on chemical composition
These measurements are usually used to derive (size-dependent)
deposition velocities which can be used in atmospheric transport
and deposition models. Since the 1980s, fast optical particle counters
(e.g. OPCs such as ASASP-X/555X, Particle Measurement Systems;
FAST, Droplet Measurement Technologies) have been used for eddy
5231
covariance (EC) measurements of size-resolved aerosol number
fluxes (e.g. Duan et al., 1988; Gallagher et al., 1997; Nemitz et al.,
2002a; Sievering, 1983; Vong et al., 2004). The measurements
usually cover the size spectrum between 0.1 and 0.5 mm, but even in
this size range the particle statistics of these instruments have often
been marginal in deriving statistically significant fluxes. Several
studies have attempted to extend measurements to smaller and also
to larger sizes. Particles significantly <0.06 mm cannot be sized with
current optical techniques. Instead, recent studies have attempted to
measure size-segregated fluxes of smaller particles, either using the
relaxed eddy accumulation (REA) technique combined with size
selection using a differential mobility analyser or interpreting total
particle number fluxes during periods where a certain size-range
dominated the flux (Grönholm et al., 2007; Pryor, 2006). Due to
limited counting statistics, fluxes had to be averaged over many days
to obtain robust statistics and these measurement methods are
therefore not yet suitable to study short-term processes (Fig. 7.1).
Variability between measurements is likely to be linked to differ-
ences in turbulence, canopy morphology (including leaf area index)
and surface roughness length (cf. Section 7.4.1).
Size-segregated EC fluxes of larger particles are only possible
when these particles are abundant and occur as the result of specific
mechanisms, e.g. in dust storms, biomass burning or industrial
processes. High volume, closed path aerodynamic Mie scattering
time of flight optical particle counters, for sizes 0.5 < Dp < 20 mm,
and open path forward scattering optical particle counters have been
used to measure deposition rates of super-micron particles and fog
droplets (e.g. Beswick et al., 1991; Burkhard et al., 2002; Klemm and
Wrzesinski, 2007; Kowalski and Vong, 1999). As a result of current
instrument limitations, measurement evidence is sparse on depo-
sition rates in the important accumulation mode (0.3–2 mm),
which contains much of the mass of sulphur, nitrogen and secondary
organics. Recently developed mass-based flux measurement
approaches based on time-of-flight aerosol mass spectrometry (see
below) may go some way towards filling this gap in the future.
It is sometimes easier to measure super-micron emission fluxes.
For example, Fratini et al. (2007) reported measurements of desert
dust resuspension, and Nemitz et al. (2000c) presented urban
EC flux measurements in the range 0.8–10 mm, made with
3 Beech forest (mean)
dep. only, CPC (Pryor, 2006)
Beech forest (median), dep. only,
2 CPC (Pryor, 2006)
Scots pine, CPC nucleation event
(Gaman et al., 2004)
Scots pine, DMA REA
(Gronholm et al., 2007)
10
9
8
Vd [mm/s]
7
6
5
4
3
2
1
7 8 9 2 3 4 5 6 7 8 9 2
10 100
Dp [nm]
Fig. 7.1. Summary of measured size-segregated particle deposition velocities to forest
for particles with diameters < 100 nm.
5232 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
aerodynamic particle sizers (APS 3320, TSI Instruments), both made
in conditions where fluxes were large.
In general, better counting statistics can be achieved when
integrated particle number fluxes are measured over larger size
ranges. For example, condensation particle counters (CPCs) are now
more commonly used to measure total particle number fluxes with
a lower cut-off between 2.5 and 20 nm over ice, seawater, short and
tall vegetation canopies, as well as urban areas (e.g. Buzorius et al.,
1998; Buzorius et al., 2001; Dorsey et al., 2002; Held et al., 2006;
Martensson et al., 2002; Nemitz et al., 2002a; Nilsson and Rannik,
2001). CPC derived flux measurements are dominated by particles
in the range 10–100 nm, with smaller particles dominating during
nucleation events (Buzorius et al., 2001). Depending of the model
used, CPCs have a response time of around 1 s, which is sufficient to
measure fluxes from taller towers, but requires flux corrections for
shorter vegetation. An alternative EC flux measurement approach
that integrates overall particles was implemented by Fontan et al.
(1997) based on particle counting through a combination of corona
charging and detection by electrometers. Only very few gradient
measurements of small particle number fluxes have been reported
in the literature (Hummelshoj, 1994) due to the large errors
associated with these measurements. Work has started to extend
EC approaches to the measurement of particle fluxes from moving
platforms such as aircraft (e.g. Buzorius et al., 2006) and ships
(Norris et al., 2007).
7.2.2. Flux measurements of individual aerosol chemical species
Measurements of chemically resolved aerosol fluxes can be used
to quantify deposition inputs directly, to investigate effects of
aerosol composition on exchange rates and to understand apparent
emission fluxes. The number of studies that have applied micro-
meteorological approaches to measure fluxes of aerosol compounds
has been surprisingly limited. Up to the 1990s, the main option
was gradient measurement with labour intensive manual sampling
techniques based on filter packs or denuder/filter combinations
(Duyzer, 1994; Rattray and Sievering, 2001; Wyers and Duyzer,
1997), where a key challenge is to achieve the precision required to
resolve the very small aerosol gradients, which are often <3%.
Manual sampling techniques have also been used in REA approaches
to measure fluxes, e.g. of sulphate to a maize crop (Meyers et al.,
2006) and of ions and heavy metal above a city (Nemitz et al.,
2000d). A family of automated real-time gradient monitors, based
on gas and aerosol capture by continuously flushed wet rotating
denuders and steam jet aerosol collectors, respectively, and online
analysis by ion chromatography and/or flow injection analysis
(for NHþ4 ) (Thomas et al., 2009) has been used in a number of studies
to measure deposition of water-soluble inorganic aerosol compo-
nents (Nemitz et al., 2004b, 2000e).
Eddy covariance measurements of aerosol chemical species were
first presented for SO2 4 deposition to grassland, based on an analyser
with thermal conversion to SO2 (Wesely et al., 1985), with no further
studies until the advent of aerosol mass spectrometry offered the
prospect for fast measurement of a number of aerosol compounds.
Held et al. (2003) theoretically investigated the suitability of aerosol
mass spectrometers based on single-particle analysis by laser abla-
tion and ionisation for disjunct eddy covariance flux measurements,
dealing with the limited counting statistics and quantification issues
related to this instrument (De Carlo et al., 2006). An alternative
instrument, the Aerodyne Aerosol Mass Spectrometer (AMS),
which is based on thermal vapourisation coupled with electron
impact ionisation, averages over a much larger aerosol population
and is quantitative for submicron aerosol components that are non-
refractory, i.e. volatilise at the vapouriser temperature of w600  C. An
operational EC system using the quadrupole-based AMS (Q-AMS)
2
(Nemitz et al., 2008) has been used to measure fluxes of NO 3 , SO4
and organic aerosol to urban areas and forests (Nemitz et al., 2008;
Phillips et al., in preparation; Thomas, 2007; Thomas et al., 2009,
2007). The Q-AMS monitors only one single mass/charge ratio (m/z)
at a time. However, the quadrupole MS can be switched very rapidly
so that quasi-continuous time series of concentrations can be
established at typically 10 different m/z at 10 Hz, similar to the use of
the PTRMS for VOC measurements. Since >100 different m/z
contribute to the organic mass spectrum, with the Q-AMS, the total
organic aerosol mass flux has to be estimated from fast response
measurements at a few m/z. The arrival of the next generation AMS
based on a high-resolution time-of-flight mass spectrometers
(HR-ToF-AMS) (De Carlo et al., 2006) provides the prospect of
monitoring all m/z continuously at 10 Hz. This should enable a fully
quantitative flux measurement of the organic fraction and provide
data to apply statistical approaches, currently used to deconvolve the
organic mass concentration in different organic aerosol classes (e.g.
Ulbrich et al., 2009), to the flux measurement.
7.3. Area sources of particles
7.3.1. Resuspension
Resuspension of particles has been studied extensively, both theo-
retically, in the wind tunnel or through concentration measurements
(Braaten and Paw, 1992; Harrison et al., 2001; Nicholson, 1988, 1993;
Nicholson et al.,1989). A full review of the understanding of this process
is beyond the scope of this paper. Instead, we here focus on a recent
development involving the first application of micrometeorological
flux measurement techniques to the direct measurement of resus-
pension fluxes, and their potential to derive new parametrisations of
the process. Nemitz et al. (2000f) measured super-micron size-segre-
gated aerosol fluxes measured with an Aerodynamic Particle Sizer (APS
3320, TSI Inc.) from a tower, some 65 m above the city of Edinburgh,
Scotland. The measurements, binned according to diameter and wind
speed lead to a parameterisation of the form:
     
dFm Dp dlog Dp ¼ am Dp U bðDp Þ
     
am Dp ¼ exp 68:69þ73:39 1exp 0:730Dp ½mm
   
b Dp ¼ 20:12exp 0:506Dp ½mm ð1Þ
where U is wind speed measured at a height of 65 m.
The measurements show that above U (65 m) ¼ 6 m s1 resus-
pension becomes an important particle source in the urban envi-
ronment, with a mode centred around a Dp of 2.8 mm, which
increases with decreasing wind speed. An attempt to include traffic
activity in the parametrisation failed due to the overriding effect of
wind speed. This suggests that, although vehicle induced resus-
pension may be important to lift particles off the surface at street
level, high wind speeds are nevertheless required to flush these out
of the street canyons. It should be noted that the windy periods with
largest coarse particle emissions did not result in the largest
concentrations, due to increased dispersion during these periods.
Similarly, Fratini et al. (2007) measured coarse aerosol fluxes
during desert storms in the Alashan desert in Nothern China, using
an optical particle counter. The authors found that the dependence
of the resuspension flux (in mg cm2 s1) of PM1, PM2.5 and PM10 on
u* (in m s1) could be described by the power relationships of
F1 ¼ 469u3.11
* , F2.5 ¼ 6220u*
3.34
and F10 ¼ 47,500u3.36
* , respectively. It
should be noted that these two studies address different resus-
pension processes, reflecting road dust resuspension with vehicle
contribution, and natural saltation processes, respectively.
7.3.2. Urban emissions of aerosols
In recent years, flux measurement techniques have been
extended to the urban environment to quantify emission fluxes of
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
trace gases such as CO2, N2O, CO and VOCs (Nemitz et al., 2002b;
Velasco et al., 2005; Vesala et al., 2007), but also of particles. Total
number fluxes have been measured with condensation particle
counters over several cities (Dorsey et al., 2002; Martensson et al.,
2006; Nemitz et al., 2000f). Martin et al. (in press) recently compared
the pattern of particle number fluxes measured at four different
locations, three of which are shown in Fig. 7.2. Fluxes, typically
covering the diameter range 0.01 (or 0.003) to 2 mm, ranged from
5000 to 70,000 # cm2 s1 and showed a clear dependence on traffic
activity confirming the role of traffic emissions as the major source
of particles in the urban area. They derived a parametrisation for
the flux (FPred in cm2 s1) over each city based on friction velocity
(u* in m s1), sensible heat flux (H in W m2) and traffic activity (TA
in veh s1) of the form
h i
FPred ¼ C EFfriction u* þEFheat H þEFtraffic TAF0 ; (2)
which is shown in Fig. 6.3 for comparison. Here C is a site-specific
factor in the range 0.12–0.55. The emission factors are
EFfriction ¼ 4500 cm3, EFheat ¼ 6.53  106 W1 s1 and EFtraffic lies in
the range 9000–12,600 veh1 cm2, depending on the location of
the traffic census site. The sink flux (F0) ranged from 13,000 to
57,000 cm2 s1.
In the Edinburgh study of Nemitz et al. (2000f) aerosol number
fluxes were dominated by traffic activity, while the aerosol mass
emission fluxes were dominated by the wind-driven resuspension
described in the previous section This may be different for less windy
locations as demonstrated by Schmidt and Klemm (2008), who
presented flux measurements of super-micron particles made with
a novel disjunct eddy covariance system, based on an Electronic Low
Pressure Impactor (ELPI, Dakati, Finland), indicating net coarse-mode
deposition to the German town of Münster. During the measurement
periods, wind speed averaged 8.0 m s1 in Edinburgh and 4.4 m s1 in
Münster (Klemm O., personal communication). Donateo et al. (2006)
reported flux measurements of PM2.5 above an urban area made with
an optical detector calibrated against gravimetric PM2.5 measure-
ments. These measurements indicated continuous net upward fluxes
and represent a combination of Aitken, accumulation mode particles
and super-micron particles.
Chemically resolved flux measurements using the AMS EC
technique described above have now been made over a range of
Fig. 7.2. Summary of diurnal patterns of measured particle number fluxes (dotted lines)
and their parametrisation (solid lines) for three UK cities: M – Manchester; L – London;
E – Edinburgh; Win06 – winter 2006 etc.
5233
cities (Boulder, US; Mexico City; Gothenburg, Sweden; Manchester,
Edinburgh and London, UK) (Grivicke et al., 2007; Nemitz et al.,
2008; Phillips et al., 2007; Thomas, 2007). The AMS measures
total organic aerosol mass contained in particles with 60–800 nm
vacuum-aerodynamic diameter and volatilizes at typically 600  C.
More information on the organic aerosol classes can be obtained
from the organic mass spectrum, with statistical techniques
(e.g. Ulbrich et al., 2009), which can be used to separate the organic
mass flux into fluxes of (primary) hydrocarbon-like organic aerosol
(HOA) and (secondary) oxygenated organic aerosol (OOA), where
the OOA can often be divided into a more (OOA-I) and a less (OOA-
II) oxidized component. The measurements to date show clear
diurnal fluxes of HOA reflecting the pattern of the surface sources
(Fig. 7.3). However, the flux ratios of HOA/CO and HOA/CO2 vary
over the day, indicating that either (a) some of the HOA evaporates
at rates that vary over the day (e.g. Robinson et al., 2007) or (b) that
the fuel mix contributing to the emissions of HOA and CO varies
over the night. Measurements suggest that food cooking may
contribute to HOA emissions in the evening in London. Fluxes of
OOA-I appear to be mainly downwards consistent with its
production during long-term transport, while small upward fluxes
of OOA-II were measured, indicating that some OOA-II formation
occurs below the measurement height of typically 30–200 m. The
urban flux measurements indicate that SO2 4 is deposited to most
city centres. Apparently, with the introduction of ultra low sulphur
fuels, there are no primary sources of this compound. Fluxes of NO 3
were more variable: in Gothenburg, Edinburgh, London and
Boulder, net emission was observed, but fluxes were dominated by
individual, often cool or foggy days, indicating urban NO 3 forma-
tion under these conditions. By contrast, above Manchester and
Mexico City, the average flux was downwards.
7.4. Dry deposition of particles
7.4.1. Dry deposition rates to vegetation
Dry deposition of atmospheric particles can account for a large
fraction, sometimes more than half, of the total deposition of many
important chemical compounds in the atmosphere, (e.g. nitrate;
Lovett, 1994), contributing significantly to global biogeochemical
cycling. Understanding atmospheric deposition processes in relation
to the ever increasing sources of fine particles in particular is
therefore becoming a research priority. In general, both aerosol mass
and number, and, increasingly, surface area, must be determined
to assess the environmental impacts of anthropogenic activities.
Mapping between number and mass fluxes however requires either
a detailed knowledge of the aerosol mass size distribution at rela-
tively high temporal resolution or by direct measurement of the
aerosol deposition flux as a function of both size and chemical
composition. In this short summary we will critique the present level
of understanding from an observational perspective and identify the
current gaps in our knowledge. There have been a number of recent
reviews on the subject of atmospheric aerosol deposition which
have attempted to collate the sparse experimental results available
from the previous two and half decades. These consist of many
disparate and difficult to compare or even reconcile, methodologies.
The reviews, whilst achieving this difficult process in some
respects, have succeeded mainly in highlighting the general lack of
a systematic approach towards improved understanding of mecha-
nistic deposition processes and, despite best efforts, have simply
reinforced the view of continued large uncertainties. Reviews have
been very much focused on either a modelling (Petroff et al., 2007b;
Zhang and Vet, 2006) or a measurement perspective (Petroff et al.,
2007a; Pryor et al., 2007).
Many regional pollutant deposition models are currently
struggling to correctly incorporate physico-chemical properties of
5234 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267

400
40 Manchester
300 Manchester
20
200
0
100
-20
0
-40
-100 200
London 1200 London 150
HOA flux [ng m-2 s-1]

HOA flux [ng m-2 s-1]

NO3- flux [ng m-2 s-1]

100

NO3- flux [ng m-2 s-1]

800
50
400
0
200 0 -50
Boulder 40 Boulder
100
20
0
0
-100 120
Gothenburg 40
Gothenburg
80
20
40
0
0
-20
0 6 12 18 24 0 6 12 18 24

Fig. 7.3. Averaged diurnal cycles of the fluxes of hydrocarbon-like organic aerosol (HOA) and nitrate (NO
3 ) over a range of cities as measured by eddy covariance using an Aerodyne
Aerosol Mass Spectrometer (data from Nemitz et al., 2008a (Boulder); Phillips et al., 2007 (Manchester, London) and Thomas, 2007 (Gothenburg)). The grey range indicates the
5th–95th percentile.

aerosols using realistic coupled sectional approaches, particularly
with respect to secondary organic aerosols. However, it could be
stated that the scientific community has not delivered any signifi-
cant improvement in the accuracy of model predictive capabilities
for the atmospheric aerosol deposition pathway over the last two
decades, compare for example one of the first reviews of model
uncertainty, Ruijgrok et al. (1997), with e.g. Petroff et al. (2007b).
The aerosol modelling and composition community are pushing
ahead with such developments whilst seemingly unaware of the
poor state of knowledge of deposition processes and caution is
required to avoid simply wasting research effort here. Whether the
current level of understanding and uncertainty is acceptable
depends on the compound of interest and its position with the
aerosol mass size distribution prevalent in the atmosphere. Little
in the way of detailed sensitivity studies has been available since
Ruijgrok et al. (1997). Feedback of such sensitivity studies to the
measurement community would also appear to be an area that
requires improvement (Zhang and Vet, 2006).
There has also been little in the way of any new laboratory
investigation, at least for atmospherically relevant conditions, that
can usefully inform these communities on specific gaps in knowl-
edge that need to be pursued. While some progress is being made
to highlight gaps in knowledge with respect to models (Petroff
et al., 2007b), these again show that different model descriptions of
atmospheric particle deposition, which rely on very limited semi-
empirical data and highly tunable, collection efficiency parame-
terisations, are as variable or more so than the atmospheric
observations that do exist (e.g. Zhang and Vet, 2006). Some
improvements in relating natural surface morphology descriptions
to wind tunnel studies have been made.
In the following we explore the dependence of particle depo-
sition velocity (Vd) on key parameters, in comparison with
measurements. Most of these measurements were made over
forests, where they are generally easier to obtain than over short
vegetated surfaces for many reasons related to the micrometeoro-
logical flux technique. The fluxes have been determined using
mainly but not exclusively direct micrometeorological techniques
(cf. e.g. Pryor et al., 2008b). The data must be treated with
circumspection as (a) little account of particle composition is
provided in many of the studies reporting these data, (b) the sizes
reported are an ad hoc mixture of optical, electrical mobility, mass
and aerodynamic diameters with little quantitative information on
the influence individual measurement techniques may have in
altering actual depositing particle size (which will be particle
growth factor and hence composition dependent) and (c) system-
atic detailed information on the morphology of the surfaces is not
always reported which hinders model development.
7.4.1.1. Friction velocity (u*). Increased turbulence increases trans-
port in the turbulent part of the atmosphere, decreases the effective
thickness of the quasi-laminar sub-layer and increases the drag
coefficient. It is therefore not surprising that Vd increases with
increasing u*. Most modelling approaches and measurements indi-
cate a near-proportion relationship between Vd and u* for submicron
particles (Fig. 7.4).
7.4.1.2. Surface roughness length (z0) and canopy morphology. The
effect of the surface roughness length (for closed canopies:
z0 w 0.1  canopy height) extends beyond its effects on increasing
u*. Vd for forest tends to be by a factor of 5–10 larger than Vd for
grass, due to the increased height of the canopy and leaf area index
and the enhanced turbulence induced by forest canopies. Davidson
et al. (1982) showed theoretically that even for the same vegetation
type (grassland), Vd may change within a factor of 5, depending on
the exact morphology of the vegetation. Similar results were more
recently obtained by Petroff et al. (2007b) for forests, emphasizing
the influence of leaf dimensions and orientation on Vd. There is
measurement based evidence as well: Ould-Dada (2002) used wind
tunnel studies to investigate the dry deposition velocity of submi-
cron particles to model Norway spruce (Picea abies). A total canopy
deposition velocity of 5 mm s1 was found which is in line with
previous micrometeorological measurements to real forest cano-
pies reported in the literature. However, the deposition pattern was
found to be a highly complex function of height within the canopy.
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267 5235

tall vegetation:
10 forest (0.10-0.18 μm) (Gallagher et al., 1995)
forest (0.18-0.24 μm) (Gallagher et al., 1995)
forest (0.24-0.30 μm) (Gallagher et al., 1995)
forest (0.30-0.50 μm) (Gallagher et al., 1995)
forest (0.05 μm) (Gaman et al., 2004)
forest (0.05-0.75 μm) (Lamaud et al., 1994)
1
forest (0.05-0.06 μm) (Pryor et al., 2009)
forest (fog) (Vermeulen et al., 1997)
forest (sulphate) (Wesely et al., 1983)
Vd [cm s ]
-1 forest (< 0.02 μm) (Buzorius et al., 2001)

short vegetation:
0.1
grass (< 2 μm) (Allen et al., 1991)
grass (fog) (Dollard & Unsworth, 1983)
grass (sulphate) (Neumann & den Hartog, 1985)
grass (sulphate) (Nicholson & Davies, 1987)
grass (sulphate) (Wesely et al., 1985)
0.01 field/snow (0.15-0.30 μm) (Duan et al., 1988)
field/snow (0.50-1.0 μm) (Duan et al., 1988)
moorland (0.12-0.13 μm) (Nemitz et al., 2002)
moorland (0.15-0.16 μm) (Nemitz et al., 2002)
moorland (0.22-0.24 μm) (Nemitz et al., 2002)
moorland (0.4-0.5 μm) (Nemitz et al., 2002)
0.001 heathland (0.4-0.5 μm) (Nemitz et al., 2004)

0.0 0.2 0.4 0.6 0.8 1.0

-1
u* [m s ]

Fig. 7.4. Dependence of small particle deposition on friction velocity (u*) for a range of surfaces. Adapted from Pryor et al (2008b). Measurements over aerodynamically rough
vegetation are shown with bold lines and symbols, while thin lines and symbols are used for measurements over short vegetation. The greyscale of lines and symbols refers to the
measured or estimated particle size (darker shading referring to larger sizes).

More studies such as these are needed to improve model devel-
opment and in-canopy gradient measurements are needed to
validate multi-layer deposition models.
7.4.1.3. Particle diameter (Dp). Both theoretical approaches and
measurements show an effect of particle size on Vd: the main
deposition processes (Brownian diffusion, interception, impaction
and gravitational settling) are all size-dependent. Brownian diffu-
sion is responsible for high Vd for small particles (Dp < 100 nm),
while gravitational settling is the dominant process for Dp > 5 mm.
Interception and impaction are most effective in the intermediate
size range, but less effective than the other two processes. The
resulting trough in Vd(Dp) (Fig. 7.5) is partially responsible for
the survival of the accumulation mode in the atmosphere.
When comparing measurements of Vd(Dp) with each other or
with model results it needs to be borne in mind that different
instruments measure different types of diameter (i.e. geometric,
aerodynamic, vacuum-aerodynamic, electro-mobility and optical),
which are often difficult to compare without exact information
on particle shape and composition. Some instruments dry the

Fig. 7.5. Evolution of the deposition velocity Vd with the particle diameter Dp on grass and grass-like canopies (lhs) and coniferous canopies (rhs) for friction velocity between 0.35 and
0.56 m s1, as given by various measurement campaigns and six existing models from the literature. Canopy characteristics used by models are hc ¼ 0.07 m, z0 ¼ 0.01 m, LAI ¼ 4,
dn ¼ 3 mm, a ¼ 1.78 for grass and h ¼ 17 m, hc ¼ 7 m, z0 ¼ 1 m, LAI ¼ 22, dn ¼ 1 mm, a ¼ 3.81 for forest. Deposition velocities are recalculated at the same reference height zR ¼ ¼ 100z0.
The parameters of Slinn’s model (1982) are fIN ¼ 0.01, dr ¼ 20 mm, cv/cd ¼ 1/3, b ¼ 2. The model of Zhang et al. (2001) is applied on Land Use Categories #6 (grass) and #1 (evergreen-
needle-leaf trees), the corresponding parameters being, respectively, fIM ¼ 1.2 and 1, and fB ¼ 0.52 and 0.56; from Petroff et al. (2007b).
5236 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
particles, while others measure the wet size. The wet size at the
measurement height may not reflect the size at which they impact
with the surface, due to water uptake or release during the depo-
sition process, in a response to humidity gradients. Despite recent
advances in measurement technology, it is still not known how
particle composition, particle shape and particle hygroscopicity
influence micro-scale deposition mechanisms and collection
efficiencies onto and by different surface types with very different
microstructures, which are known to significantly influence e.g.
aqueous phase aerosol contact angle and therefore the likely
collection efficiency.
7.4.1.4. Atmospheric stability (z ¼ 1/L). There is strong evidence
from a range of studies that Vd can be greatly enhanced in
unstable conditions. Fig. 7.6 summarizes the findings from several
field studies, by exploring the dependence of Vd, normalized by
u*, on the inverse of the Monin–Obukhov length (L), a standard
measure of atmospheric stability. The cause for this enhancement
is not fully understood and therefore difficult to reproduce in
numerical models.
7.4.2. Parameterising and modelling deposition rates
The first detailed sensitivity study of aerosol deposition models
compared to field observations was conducted by Ruijgrok et al.
(1997). They reported a factor of 5 uncertainty in model predictions
for submicron aerosol deposition velocities based on input uncer-
tainty. Despite this there was general consensus that dry deposition
measurements (mainly by gradient filter pack and throughfall tech-
niques) yielded deposition rates significantly larger than analytical
models were predicting for forested surfaces compared to grasslands
(Erisman, 1993), which led to some improvement in aerosol collec-
tion efficiency descriptions in models. Later the first eddy covariance
measurements at the same locations tended to confirm this,
notwithstanding the sampling issues associated with aerosol growth
factors mentioned below (Erisman et al., 1996). The latest review
(Petroff et al., 2007b) suggests this uncertainty has now been
reduced, to around a factor of 3. Efforts to reduce this uncertainty
further are restricted by the quality of the measurements (as dis-
cussed in Section 6.4 below) and the completeness in the metadata
0.04
grass; Wesely et al. (1985)
forest; Gallagher et al. (1995)
heathland; Nemitz et al. (2004)
Dp = 0.1 μm
0.03 0.2 μm
0.3 μm
0.4 μm
0.5 μm
Vd / u*
0.02
0.01
0.00
-0.04 -0.02 0.00 0.02
-1
1/L [m ]
unstable stable
Fig. 7.6. Summary of the dependence of aerosol deposition velocity on the Monin–
Obukhov length (L), indicating a sharp increase of normalized deposition velocity (Vd/u*)
in unstable conditions; from Pryor et al. (2008b), modified.
reported with measurements (in particular on canopy structure). The
high sensitivity of the models to the canopy structure further adds
uncertainty to the application of simple generalized parametrisations
at the regional scale, where input parameters are limited.
7.4.3. Dry deposition rates to urban areas
Very little is currently known about deposition rates to urban
areas, despite their importance for estimating the contribution of
aerosol deposition to the soiling and weathering of buildings, and
for the atmospheric lifetime in the atmosphere (Pesava et al., 1999).
Although aerosol deposition measurements have been made in
cities, these were usually made with surrogate collectors (e.g. Yun
et al., 2002), which are unlikely to be representative of the uptake
by urban structures. Alternatively, the soiling of building has been
studied, which provides information of the aerosol deposition to
a particular receptor, but not on the net removal rate from the
atmosphere to the urban matrix (Horvath et al., 1996).
Application of micrometeorological flux measurement techniques
to the urban environment has now been demonstrated (see Section
7.2.2 above). However, the net flux of particles above urban areas is
dominated by emission sources from the city and deposition rates
can only be applied if a chemical aerosol species or size-class is found
which is not emitted from the city. Nemitz et al. (2000d) presented
initial measurements of chemically resolved aerosol fluxes at
a coastal site and showed that chloride was deposited at low wind
speeds, presumably reflecting deposition of sea salt, while it was
emitted during windy periods, probably reflecting wind-driven
resuspension of previously deposited material. Similarly, Nemitz
et al. (2008) measured SO2- 4 deposition fluxes to urban environment
with the Q-AMS EC system. These measurements suggest deposition
velocities in the range of 2–6 mm s1, but will need to be supported
with data from other cities. As mentioned above, Schmidt and Klemm
(2008) detected net deposition of PM2.5 to a German town, but these
fluxes almost certainly contain an upward component.
7.5. Uncertainties
7.5.1. Uncertainties in the application of micrometeorological flux
measurement techniques for deriving the local flux
Technical challenges in applying micrometeorological techniques
to the measurement of aerosol fluxes go beyond those encountered
for gas flux measurements. Aerosol fluxes are often small and
deposition rates slow, resulting in small concentration differences
that need to be resolved for gradient and REA measurements. Simi-
larly, the relative corrections, e.g. for density fluctuations (Webb et al.,
1980), may become large and can easily result in reversal of the sign
of the flux. A continuing challenge of particle flux measurements is
that, due to the limited counting statistics of the measurement,
standard data processing techniques, such as tests and corrections
based on co-spectral analysis, and non-stationarity tests are difficult
to implement. While most gas analysers respond to many thousands
of molecules per tenth of a second, aerosol counters may only detect
tens of particles resulting in statistical uncertainties (Fairall, 1984).
Similarly, in mass-based measurements the contribution from a few
large particles may greatly affect gradients and EC results. Different
aerosol measurement instruments respond to different parameters,
not all of which are conserved. For example, artificial fluxes may be
introduced if particles are sized according to their wet size which
responds to humidity fluctuations (Kowalski, 2001), and similar
problems are caused by volatilisation or formation in the atmosphere
which is discussed in more detail below. The exact effect on the
measurement depends on the setup and requires careful consider-
ation: most previously reported submicron aerosol number fluxes
have relied on optical particle counting techniques that use closed
path, high power active laser cavity scattering cells. Furthermore
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
most of these, but not all, adopt recycling dry particle free sheath air
flow with significantly lower RH than the ambient aerosol flow to
minimize contamination of the instrument optics. These instruments
therefore most likely provide a measure of the dry or partially dry
particle size and not the ambient particle size. Hence measurements
of submicron particle fluxes reported in the literature are likely
representative of ‘‘dry or near dry aerosol deposition velocities’’
of optical particle size and not the actual ambient deposition velocity,
whereas most large particle fluxes are likely a combination of both,
some being derived from closed path and other open path instru-
ments. Flux measurements using photometric techniques to deter-
mine total PM2.5 and PM10 mass fluxes may not be subject to these
effects and for routine measurement of total mass fluxes e.g. for
network applications may be the most appropriate when combined
with additional composition measurements.
Care needs to be taken that the inlet system does not respond in
a way that may be correlated with w. This could occur during non-
isokinetic sampling of coarse particles or during fast switching of
inlet flows in REA systems. There is also evidence that non-statio-
narities may affect aerosol exchange particularly often (Fontan
et al., 1997).
7.5.2. Relating measured fluxes to surface exchange: flux
divergence and the effect of chemical interactions
A further uncertainty of the flux estimation with micro-
meterological techniques is that, although the local flux at the
measurement height may be correct, it may differ from the actual
surface/atmosphere exchange. The most commonly applied form of
the scalar conservation equation is (Pryor et al., 2008b):
Here term (1) is the local change in concentration, term (2)
advection by the mean flow, term (3) represents the divergence of
the turbulent flux, term (4) vertical transport by diffusion, term (5)
vertical transport by sedimentation and term (6) concentration
changes due to sources or sinks.
Methods of estimating particle (and other scalar) fluxes at the
air–surface interface have typically relied on the assumptions of
horizontal homogeneity, steady state, the absence chemical source
or sink of the scalar, that the constant flux layer assumption applies
to the lowest tens of meters above the surface (Businger et al.,
1971), and that the turbulence responsible for transporting the
scalar of interest is locally induced (Monin and Obukhov, 1954;
Monin and Zilitinkevich, 1974). However, as described in this sub-
section, there are multiple causes of flux divergence (i.e. that the
flux observed at some height above the surface is not equal to that
at the surface). Three dominant sources of particle flux divergence
are described below along with methods for their identification and
quantification:
Non-conservative behaviour of the scalar under study (i.e. parti-
cles) due to the interaction of other particle dynamics processes with the
vertical exchange ði:e: Ss0Þ. The degree to which S deviates from 0 (i.e.
the magnitude of the vertical flux divergence due to phase transitions)
is determined by; the chemical climate (Nemitz and Sutton, 2004;
Nemitz et al., 2004b; Sutton et al., 2007), particle ensemble (Pryor and
Binkowski, 2004), and specific aspect of the particle ensemble being
observed. If Eq. (3) is applied to consideration of the mass of the entire
particle ensemble, then only mass transfer (i.e. evaporation and/or
condensation) can result in flux divergence. While if Eq. (3) is applied
to a size-resolved number particle ensemble for any given particle
diameter, could Ss0 derive from concentration changes resulting
from nucleation, coagulation, and condensation/evaporation. If Eq. (3)
5237
is applied to a chemically resolved (but not size resolved) particle
ensemble, evaporation/condensation and/or heterogeneous chem-
istry in/on particle surfaces could cause flux divergence. It can also
modify fluxes if it leads to growth or shrinkage across the cut-off size
of the particle probe. Apparent emission fluxes with a CPC setup above
a grassland fertilized with NH4NO3, attributed these fluxes to aerosol
growth due to NH3 and HNO3 uptake and used the fluxes to derive
particle growth rates across the 11 nm cut-off of the CPC (Nemitz et al.,
2008). This demonstrates that flux measurements can be used to infer
information on S and thus on aerosol processing, if the true deposition
rate can be estimated independently.
The partitioning of species between the gas and particle phase is
also associated with gas flux divergence (Soerensen et al., 2005) and
can change the net rate of surface uptake of, for example, nitrate if
the deposition velocities of the gas and particle phase species differ
substantially (Pryor and Soerensen, 2000). The likelihood of flux
contamination due to non-conservative behaviour can be estimated
using time-scale analysis (De Arellano and Duynkerke, 1992), and
can be quantified by deploying eddy covariance measurement
systems at multiple heights.
(i) Horizontal advection, due to the presence of large spatial
gradients in particle number, mass and/or composition. The
importance of horizontal advection has been extensively
evaluated in the carbon dioxide flux community (Baldocchi
et al., 2001; Hong et al., 2008) and is likely to be important to,
but with few exceptions (Vong et al., 2004) the horizontal
advection term has generally been neglected in most particle
flux studies. The potential influence of horizontal advection
can be quantified using a horizontally dispersed measurement
array.
(ii) The influence of non-local or ‘top–down’ processes in dictating
vertical exchange. Observed scalar fluxes near to the ground are
derived from two components: local surface-driven turbulence,
and non-local or ‘top–down’ processes such as entrainment of
air from above the mixed-layer which can cause fluxes that are
counter to local gradients (Holtslag and Moeng, 1991). The
importance of non-locally induced turbulence in dictating
observed fluxes has been documented in gas exchange studies
(Gao et al., 1989), but received less attention in the aerosol
community, despite evidence that it plays a substantial role in
dictating flux magnitudes and may provide an explanation for
upward fluxes in environments that have traditionally been
viewed as solely particle sinks (Pryor et al., 2008a). The potential
influence of ‘top-down’ processes on observed near-surface
fluxes can be identified using scalar correlations (Sempreviva
and Gryning, 2000) and quadrant analysis.
With the advent of techniques to measure compound-resolved
aerosol mass fluxes, there is growing evidence that particle depo-
sition velocities of NO þ
3 and NH4 to semi-natural vegetation tend to
exceed those derived for SO2 4 or from particle number flux
measurements (Nemitz et al., 2004b; Thomas et al., 2009) (Fig. 7.7).
The deposition rate of these compounds measured over heathland
and forest greatly exceed those predicted theoretically for short and
tall vegetation, respectively (Fig. 7.2). The likely cause is evapora-
tion of NH4NO3 near the ground during the deposition process,
where thermodynamic equilibrium favours the gas phase, due to
the depletion of NH3 and HNO3 by deposition of these reactive
gases to foliar surfaces and warm surface temperatures. Thus, the
flux measured well above the canopy is not limited by the physical
interaction of the particles with the vegetation surface, but reflects
the evaporation sink in the airspace above. This is supported by
the fact that the relationship between Vd and u* does not differ
between surfaces (Fig. 7.7), which implies that turbulent transport
5238 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
40
+
NH4 to heathland (Nemitz et al., 2004)
-
NO3 to oak forest (Thomas, 2007)
30
Vd [mm/s]
20
10
0 regimes. This size range is still poorly resolved by eddy covariance
0.0 0.2 0.4 0.6 0.8 1.0
u* [m/s]
Fig. 7.7. Apparent nitrate and ammonium deposition velocities derived from chemi-
cally speciated micrometeorological flux measurements. The large values are indicative
of an additional loss of ammonium nitrate near the surface, due to evaporation.
(which scales with u*) is the main constraint on the flux. Since NH3
and HNO3 deposit to semi-natural vegation much more effectively
than NH4NO3 aerosol, this shift to the gas phase increases
the deposition rate of total ammonium and total nitrate. Since this
evaporation only occurs close to the canopy, it represents a non-
resolvable (sub-grid) process in traditional transport models.
Future parameterisations of Vd should account for this additional
sink for highly volatile aerosol components.
7.5.3. Interpretation of measurements for model verification
Deposition is effectively a number dominated process which, is
subject to large uncertainties. Mapping from number to mass space
requires detailed knowledge of composition, size, shape and hygro-
scopicity. The hygroscopicity of aerosols can potentially generate the
largest uncertainty, not just in the measurement, but also in inter-
preting the measurements. For example, the size at which a particle
interacts with the vegetation surface often differs from its actual size
at the measurement height, which again may differ from the size
reported by a given instrument (dry vs. wet; geometric vs. optical
diameter etc.). Most previous studies of deposition have not
been sufficiently complete to address any of these uncertainties
with respect to a complete closure of aerosol number and mass for
model comparison through use of growth factors. As a consequence,
size-segregated and chemically speciated eddy covariance (and
related) aerosol flux measurement techniques cannot currently
provide unambiguous results of particle number or mass fluxes to
surfaces as a consequence of fluctuations in aerosol size distributions
on timescales that can lead to sampling biases. This sampling
ambiguity and the potential for bi-directionality in aerosol fluxes
limit the accuracy with which Vd can be determined and hence will
hamper improvement in model mechanistic descriptions of particle
deposition to natural vegetated surfaces.
7.6. Future research needs
7.6.1. Deposition measurements and reporting
7.6.1.1. Standardisation of eddy covariance approaches and data
analysis procedures. Comparisons between different measurement
systems are currently made difficult by the diverse approach used to
measure the fluxes as well as to analyse and present the data. For
example, some authors have derived parameterisations of Vd(Dp)
averaging over the negative (deposition) fluxes only, while other
authors have averaged over the entire datasets. The difference can
be large (Nemitz et al., 2002a). Often important parameters (e.g.
leaf dimensions) are not provided in the scientific papers to provide
the input parameters to apply the models to the measurement
datasets. Thus there is an urgent need to harmonise flux measure-
ment approaches as much as possible and to provide guidance
for auxiliary parameters that should be measured and provided with
the measurement datasets to maximise their potential for model
evaluation.
7.6.1.2. Improved measurements in the accumulation mode. There
are still significant gaps in observations, particularly with respect to
the critical size range associated with the transition between
Brownian and turbulent impaction dominated particle capture
techniques (w0.5 < Dp < 2 mm) as a consequence of few measure-
ments being available by any suitably characterized techniques and
the large errors associated with these. The predicted minimum in Vd
as a function of size in this transition regime can vary widely
between different models (Fig. 7.5) and this will have significant
consequences for long-term integrated dry deposited mass fluxes.
This is therefore seen as a key area in need of attention by both
models and field observations.
7.6.1.3. Understanding the effect of stability and leaf properties on
deposition velocities. Another serious issue is the lack of any
detailed testable hypothesis in models explaining the link between
increasing Vd and atmospheric stability and which most measure-
ments have reported in the literature for particle sizes Dp < 0.5 mm,
most clearly seen for Aitken and small accumulation mode sizes.
So far there are no wind tunnel studies of aerosol deposition to
vegetated surfaces that take account of atmospheric stability and
these are needed to allow further model development. Studies of the
hydrophobicity and anti-adhesion of non-smooth leaf surfaces show
that the morphology of plant epidermal cells and the morphology
and distribution density of epicuticular waxes significantly affect
their hydrophobicity and anti-adhesion properties and potentially
the adhesion of aerosol particles following impaction and inter-
ception, Ren et al. (2007). The microstructure of plant surfaces has
been well documented but an interesting phenomenon which might
have potentially serious implications for some studies of dry and wet
deposition is the so-called self-cleaning mechanism of some leaf
structures (referred to as the ‘‘Lotus Effect’’). Some plant leaves are
completely lacking in microstructures while others can have sunken
or raised nervatures which as a consequence cause super hydro-
phobic behaviour. This in turn leads to a remarkable self-cleaning
process whereby fog droplets e.g. rolling down the leaf surface pick
up aerosols and remove them from the leaf surface. Experiments
whereby leaf surfaces have been artificially contaminated with
radioactively tagged aerosols and then subjected to artificial fog
droplets have been used to determine the retention rate of aerosols
to plant surfaces and these can range from over 90% to less than 10%
depending on the species examined and which were linked to
differences in leaf microstructure and orientation (Neinhuis and
Barthlott, 1997).
Considering the many inherent uncertainties in field flux
measurements more wind tunnel studies are needed under better
controlled conditions of stability, surface morphology and aerosol
composition. The question is how detailed should a model be to
describe adequately the surface interactions with aerosols (whether
they be ‘‘dry’’ or ‘‘wet’’ aerosols)? And more importantly how can
their importance be measured? What information should be
reported on surface morphology for future model development in
order to attempt inclusion of these effects in future? These questions
are best tackled by revisiting wind tunnel studies coupled with
modern particle measurement techniques.
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
7.6.1.4. Filtering or accounting for chemical interactions and water
uptake. A particular aspect of the data processing is the correction for
aerosol dynamics due to water equilibration and/or chemical inter-
actions. A growing number of datasets indicates that size-segregated
particle number fluxes are affected by chemical effects (Nemitz et al.,
2004a,b) and this is confirmed by the first results from the chemically
resolved mass fluxes from the Q-AMS eddy covariance system, which
indicates that often some chemical aerosol components may be
emitted at the same time as others are being deposited. Although
some modelling studies have been successful in qualitatively
reproducing the observations both for bulk chemical fluxes and size-
segregated fluxes (e.g. Nemitz and Sutton, 2004; Van Oss et al., 1998),
standardized operational procedures for correction have not yet been
developed. Indeed, we do not currently have the strategies in place
to test whether a particular dataset may be affected by chemical
interactions. It is unclear whether correction procedures will ever be
sufficiently accurate to fully correct for these effects, given the small
value of the deposition rates.
7.6.2. Deposition models
7.6.2.1. Migration to a probabilistic approach. Comparison of
measured deposition velocities as a function of size with different
regional scale model descriptions show large differences. Hence,
unacceptable errors will very likely be incurred in annual cumulative
mass deposition values. A detailed sensitivity analysis between
different deposition schemes used in current regional models with
observations has not yet been undertaken. Given the large apparent
difference between measurements and model schemes, it may be
more appropriate to move towards a probabilistic approach in deriving
deposition estimates, by exploring a range of possible solutions,
together with statements on their probability. For this purpose, prob-
ability density function distributions for aerosol deposition velocities
need to be developed which can be used to test sensitivities to these
factors in regional transport and global climate models.
7.6.2.2. Improvement of modelling approaches. New modelling
approaches compare favourably with the available measurement
database, with the caveats on the data quality mentioned above.
Fig. 7.5 demonstrates that the model of Petroff et al. (2007b) in
particular appears to be successful, similar to earlier modelling results
of Davidson et al. (1982). Both models have in common that they
include a detailed description of the canopy morphology. This intro-
duces additional requirements for input parameters and further
degrees of freedom for adjustments to make the model match the
measurements. However, good agreement is achieved with measured
canopy characteristics, increasing the confidence in the modelling
approach. However, the model of Petroff et al. (2007b) needs to be
simplified for application in operational chemical transport models
and standardized characterizations for the different vegetation classes
need to be developed.
7.6.2.3. Impact of surface anisotropy on suspension & deposi-
tion. Spatial organisation of vegetation on sub-grid scales can
influence aerosol surface exchange properties by introducing
significant perturbations to mean wind flows by altering the
probability density functions for turbulence velocities above that
surface which in turn can alter the magnitudes of aerosol surface
exchange fluxes. The impact of this surface anisotropy is often seen
in observations of dust suspension fluxes over surfaces where
elongated regions may occur which are free of vegetation (e.g.
Gillette and Chen, 2001). As a result of this, neighbouring surfaces,
which have the identical vegetative indexes, can produce dust
fluxes that differ from one another by as much as a factor of 4–8
(Okin, 2005). Recently models have been developed that capture
and demonstrate the importance of sub-grid cell isotropic spatial
5239
variability however these have focussed on dust suspension and
the subsequent impact on both horizontal and vertical dust mass
fluxes, which can be considerable (Gillette and Chen, 2001).
As deposition mechanisms for submicron aerosols are
controlled by turbulent interaction with surfaces, and are highly
sensitive to particle size and micro-scale structures, it is likely that
deposition velocities too are also affected by surface anisotropy and
the manner in which this links to the microstructure. The notion of
a mean aerosol deposition velocity in this context has little value
(much as it is now thought to be for suspension fluxes) (Okin, 2005)
and a probabilistic approach must be used. Unfortunately, unlike
dust emission mass fluxes, there are virtually no observations of the
impact of sub-grid scale surface anisotropy on aerosol deposition.
Initially, a theoretical model study could explore the likely impact
of anisotropy on effective dry deposition rates, for example
adopting the concept of a lateral cover parameter (l) as a measure
of the vegetative canopy area intercepted by the wind and its
contribution through surface drag to the surface roughness, from
which an effective aerodynamic roughness length for the landscape
can be calculated (1993). In parallel, as a first step to improving
understanding in this area (which has been relatively moribund for
some considerable time) (Pryor et al., 2008b) the community needs
to collect high quality micrometeorological aerosol flux measure-
ments over a number of different surfaces with very different
anisotropic variability. The observations should focus on deter-
mining the frequency distribution function, f(Vd (Dp)) of aerosol
deposition velocities.
7.7. Conclusions – aerosols
After little progress in the understanding of surface/atmosphere
exchange of aerosols in the 1980s and early 1990s, the development
of novel instrumentation suitable for flux measurements has led to
new investigations into the surface exchange, extending micro-
meteorological flux measurements to the urban environment
and the sea. For example, new developments in mass spectrometry
have enabled the first eddy covariance flux measurements of
2
aerosol components (NO 3 , SO4 and organics) above urban areas
and vegetation, providing new information on sources, sinks and
chemical processing, together with deposition rates of the accu-
mulation mode and the potential of studying deposition rates in
relation to particle composition. Furthermore, size-segregated
particle flux measurement approaches have now been extended to
the sub-100 nm size range, providing the first data for model
evaluation. The first long-term flux measurements of total aerosol
number provide increasingly robust datasets of removal rates.
As more detailed flux measurements as a function of size and
composition have become available, it is becoming clear that size-
segregated particle number flux measurements are often influenced
by hygroscopic growth and chemical processing. This highlights the
need to minimize or to filter/correct for these effects when the data
are used for model validation. Apparent upward fluxes have been
used to study the formation of NH4NO3 or biogenic SOA formation.
Measured effective deposition rates of NH4NO3 to semi-natural
vegetation greatly exceed those of other aerosol compounds, indi-
cating that new sub-grid parameterisations need to be developed to
account of the additional deposition mediated through the evapo-
ration of volatile aerosol components (e.g. NH4NO3).
Theoretical developments demonstrate that models of dry
deposition need to account for canopy structure and small-scale
morphology. Existing models are now capable of reproducing selected
measurements, but will need to be simplified for operational appli-
cation in transport models and incorporate effects of atmospheric
stability. The data available for model validation are highly dispersed
in terms of quality, approaches, diameter measured and auxiliary
5240 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267

information provided. Harmonised approaches in data processing and Table 2

presentation are needed. More sensitivity studies and probabilistic Estimates of global N2O and CH4 budgets (Tg y1).

approaches are needed to explore the range of possible deposition N2O sourcea Tg N2O–N y1 CH4 sourceb Tg CH4 y1
estimates. In addition, the potential of modelling concepts that Natural sources
account for small-scale spatial variability (increasingly applied for Oceans 3.8 (1.8–5.8) Oceans 4 (0.2–20)
resuspension) should be explored to estimate dry deposition. Here Atmosphere 0.6 (0.3–1.2) Termites 20 (2–22)
Soils 6.6 (3.3–9) Wetlands 100 (92–232)
a new series of targeted, high-quality wind-tunnel experiments,
Othersc 21 (10.4–48.2)
coupled with the improved measurement technology would help
decrease remaining uncertainties. Anthropogenic sources
Agriculture 2.8 (1.7–4.8) Rice cultivation 60 (25–90)
Biomass burning 0.7 (0.2–1) Biomass burning 50 (27–80)
8. Ecosystem–atmosphere exchange of the radiatively Energy & industry 0.7 (0.2–1.8) Energyd 106 (46–174)
active gases – N2O and CH4 Otherse 2.5 (0.9–4.1) Ruminants 81 (65–100)
Waste disposal 61 (40–100)
8.1. Introduction Total sources 17.7 (8.5–27.7) 503 (410–660)

Atmospheric concentrations of the three main greenhouse gases
CO2, CH4 and N2O have increased since the industrial revolution in
the 18th century due to anthropogenic activities. Increased fossil fuel
burning, land use change and the intensification of agriculture
facilitated by the manufacture of synthetic nitrogen and conse-
quently population growth are the main causes. Increased fossil fuel
combustion is the main cause for rises in CO2, whereas microbial
processes in soils, sediments, and waters and rumens of animals, are
responsible for the bulk of the observed increased atmospheric CH4
and N2O concentrations. In this section, current understanding of
CH4 and N2O exchange at the surface, and especially of the biological
processes, measurement methodologies and models, are reviewed.
The wider consideration of the global biogeochemical cycles of these
trace gases are provided in outline for context only, as these would
take the review substantially beyond the focus on surface–atmo-
sphere exchange.
8.2. Global budgets of N2O and CH4
Atmospheric N2O and CH4 concentrations have risen from back-
ground levels prior industrialisation from 270 to 320 ppb N2O and
from 700 to 1782 ppb CH4 in 2006 (http://www.esrl.noaa.gov/gmd/
aggi/). Nitrous oxide concentration has increased at a relatively
uniform rate, with a mean annual growth rate over the last 10 years of
0.76 ppb year1 (Hirsch et al., 2006). By contrast, the growth rate in
CH4 concentration has changed considerably since the early 1990s
from a steady monotonic increase of approximately 15 ppb year1 in
the later decades of the 20th century until the early 1990s, following
which annual rates of change varied between increases of
5 ppb year1 to decreases of a few ppb year1 (IPCC, 2007). These very
large and inter-annual variations in CH4 concentration remain unex-
plained and present an important challenge to the research commu-
nity (IPCC, 2007).
The global budget of N2O is constrained by the sink strength in the
stratosphere and atmospheric increase (http://www.esrl.noaa.gov/
gmd/aggi); hence, the global source strength is 15. 8–16 Tg N2O–
N y1 (Crutzen et al., 2008, Hirsch et al., 2006. Cicerone, 1989).
There are some indications that also soils may significantly act as sink
for atmospheric N2O and that the soil N2O reduction has decreased
within the last decades (Chapuis-Lardy et al., 2007; Conen and Neftel,
2007). However, this is so far not considered in any global estimate.
The atmospheric increase is largely attributed to agricultural
activity (Table 2). Natural sources of N2O, the oceans, tropical and
temperate forests and grasslands/savannahs, are unlikely to have
changed much since pre-industrial times except where land use
has changed significantly.
The CH4 budget is constrained by measurements of the major
sources and d13C signature to a global total of 430–600 Tg y1
(Wuebbles and Hayhoe, 2002, IPCC, 2007). Anthropogenic sources
contribute 70% of the total budget. Natural sources (wetlands,
Sinks
Stratosphere 12.5 (10–15)f Stratosphere 40 (32–48)
Soils 1.5–3g Soils 30 (15–45)
Tropospheric OH 445 (360–530)
Total sinks 14 (11.5–18) 515 (430–600)
a
Sources are estimates for the 1990s as provided by IPCC (2007), Table 8.7.
b
From Wuebbles and Hayhoe (2002).
c
Others ¼ marine sediments, geological sources and wild fires.
d
Energy ¼ natural gas, coal mining and other fuel related sources.
e
Atmospheric deposition, aquatic systems, sewage.
f
Hirsch et al. (2006).
g
Cicerone (1989).
oceans, termites) are also large and dominated global emissions until
the 20th century (Table 2). Increased livestock production and fossil
fuel use are the main reasons for the atmospheric increase of CH4
(IPCC, 2007). Soils are are a minor sink for CH4 and accounts for
approximately 6% of the global budget; the dominant removal
process for atmospheric CH4 is oxidation by OH, mainly in the
troposphere.
8.3. Biological sources of N2O and CH4
8.3.1. The biology of production and consumption
of N2O and CH4 in soils and sediments
Microorganims are the dominant sources of N2O and CH4 in the
troposphere. A knowledge of the underlying processes and micro-
bial community structure is essential to improve global estimates of
N2O and CH4. The main microbial reactions involved (nitrification,
denitrification, methanogenesis and CH4 oxidation) are ubiquitous
to all live containing ecosystems and are all sensitive to anthro-
pogenic activities (e.g. irrigation, drainage, fertilization) and
climate (temperature and precipitation).
Nitrous oxide is a by-product of aerobic nitrification and an
obligate intermediate in the denitrification pathway, and is emitted
by both nitrifiers and denitrifiers. Production and consumption
of N2O is regulated by oxygen partial pressure; nitrification is
additionally controlled by the concentration of NHþ 4 , while deni-
trification is also controlled by availability of carbon and NO 3
(Conrad, 1995). Denitrification is the main biological process
responsible for returning fixed N to the atmosphere as N2, thus
closing the N cycle (Philippot et al., 2009). This reduction of soluble
N to gaseous N represents a loss for agriculture, since it can deplete
the soil of NO
3 , an essential plant nutrient. The denitrification N2O/
N2 product ratio is variable, and N2O may even be the dominant end
product. However, denitrification also provides a valuable
ecosystem service by mediating N removal from NO 3 polluted
waters in sediments and other water-saturated soils (Mosier et al.,
1998). Denitrifiers can be sinks for N2O. Sink activity appears to be
stimulated by low availability of mineral N (Chapuis-Lardy et al.,
2007; Conen and Neftel, 2007).
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Methane is produced by methanogenic archaea in anaerobic soil
(Philippot et al., 2009). The organisms require low redox conditions
as well as on the fermentative production of precursors for the
methanogens. The main terrestrial CH4 sources are wetland ecosys-
tems, where both methanogens and methanotrophs are present and
active. Methane is consumed by methanotrophs active in the aerobic
layers of most soils; undisturbed soils are largest CH4 sinks.
8.3.2. Distribution of active microbial populations in soils
Although many different microbial species can produce and
consume N2O and CH4, information on the microbial biodiversity can
provide useful insight into the health and functioning of the soil. The
development and recent automation of molecular methods have
made it possible to characterise the abundance and function of soil
microbial populations relatively quickly. One of these methods is the
analysis of the Phospholipid Fatty Acid (PLFA) composition of the
microbial membrane (Bach et al., 2008). The method, together with
analysis of microbial biomass carbon, Gram staining, N mineraliza-
tion rates, N2O, NO and CH4 fluxes, was applied to soils from arable,
grassland, wetland and forest ecosystems from the main climate
zones in Europe as part of the NitroEurope Project (http://www.
nitroeurope.eu). The PLFA composition provided an overview on
the distribution of functional microbial groups in soils of different
landuses. There was a good separation between microbial commu-
nities from wetlands and forests, but a closer similarity between
microbes from grasslands and croplands (Fig. 8.1). The ratio of two
marker PLFAs, cyclic fatty acids and precursor monounsaturated
fatty acids, is an index of bacterial stress. In this study, the stress
parameter correlated with soil NO emissions and these were related
to N-deposition rates and soil acidity (Pfeffer et al., personal
communication). N2O emissions correlated positively with the
abundance of gram-negative bacteria, potential N-mineralization
rates and microbial biomass carbon. This can be explained by the fact
that gram-negative bacteria contain many microbial groups impor-
tant for the N-cycle, such as nitrifiers, free-living N2-fixers and
several denitrifiers.
8.3.3. N2O and CH4 fluxes from the main global ecosystems
Biosphere atmosphere exchange of N2O and CH4 has been
studied for over 30 years. The data available are biased towards the
large N2O and CH4 emitting ecosystems in highly developed
Fig. 8.1. Principal component analysis of microbial communites, determined as PLFAs
(nmol g1 soil dry weight) of 13 NitroEurope sites representing different landuses.
Abbreviations: AM: arbuscular mycorhiza fungi; Sites: Forests: FI-Hyy ¼ Hyytiälä, FIN;
DK-Sor ¼ Sorø, DK; NL_Spe ¼ Speulder Bos, NL; DE-Hog ¼ Högelwald, DE; grasslands:
UK-Ebu ¼ Easter Bush, UK; CH-Oen ¼ Oensingen, CH; HU-Bug ¼ Bugac, HU; croplands:
DE-Geb ¼ Gebesee, DE; FR-Gri ¼ Grignon, FR; IT-Cas ¼ Castellaro, I; IT-BCi ¼ Borgo
Cioffi, I; wetlands: FI_Lom: Lompolojänkkä, FIN; UK-Amo ¼ Auchencorth Moss, UK;
Figure provided by B. Kitzler and M. Pfeffer (BWF, Austria).
5241
countries, principally northern Europe, the USA, Canada and Japan.
For N2O, studies on N fertilized agricultural soils dominate and for
CH4 studies on rice paddy fields and northern wetlands. Studies
from Asia, where N demand is increasing at a faster rate than
elsewhere, are now emerging. There are insufficient data from
agricultural systems in Central and South American and African
countries, from new emerging cropping systems, especially biofuel
crops, and land use change in temperate as well as tropical countries
to provide the detailed understanding required for model validation
and for inclusion in emission inventories.
8.3.4. Plant-mediated transport and production of N2O and CH4
The general view is that soil-based microbial production and
consumption of CH4 and N2O are the major processes involved in
regulating biosphere–atmosphere exchange of these two green-
house gases. Based on this perception, and combined with the lack
of appropriate methodologies, our current knowledge about their
exchange rates is almost exclusively based on observations ach-
ieved using shallow, soil anchored enclosures. For many ecosystems
such enclosures may exclude the vegetation (e.g. tall crops and
forests) and biases in emission estimates through omission of the
pathway through tall vegetation may result from this methodology.
It is well documented that soil–atmosphere transport of both
CH4 and N2O is mediated by aerenchymatic wetland herbaceous
species such as rice (e.g. Yan et al., 2000). Mangrove prop roots and
also wetland and flood-tolerant trees have been shown to mediate
CH4 and N2O transport from the soil to the atmosphere, e.g. through
the bark of black alder or from hybrid poplar seedlings (McBain
et al., 2004), but only under conditions when the root zone was
exposed to above ambient concentrations of the gas.
The role of non-aerenchymatic plants and in particular trees in
the exchange of CH4 and N2O between the soil–plant system and the
atmosphere has only been sparsely investigated. Recent investiga-
tions, however, have emphasized a non-negligible role of vegetation
in the biosphere–atmosphere exchange of greenhouse gases.
8.3.4.1. Methane from vegetation. In 2006 Keppler et al. reported
a very surprising observation that higher plants had the capability to
emit CH4 under aerobic conditions with a mean emission rate of
374 ng CH4 g1 dw h1. From their findings they calculated a global
CH4 source strength of 62–236 Tg y1 for living plants and 1–7 Tg y1
for plant litter, the sum of which equals c. 10–40% of the total global
CH4 source strength. Methyl-ester groups of pectin, an abundant
polysaccharide in cell walls of non-woody plant tissue, served as
a precursor for CH4 (Keppler et al., 2008). UV light appears to be
important in emissions of CH4 from plant material. Vigano et al. (2008)
demonstrated that in the absence of UV light CH4 was not produced
until the temperature reached 70–80  C; with UV light emissions
were significant already at room temperature with rates up to
67 ng CH4 g1 dw h1. McLeod et al. (2008) provided further evidence
that not only CH4 but also ethane, ethylene and CO2 are produced from
methyl-ester groups of pectin under UV irradiance, and that reactive
oxygen species (ROS) arising from environmental stress may have
a role in the formation of CH4 from pectin. By contrast, Dueck et al.
(2007) observed no significant CH4 emissions from photosynthesizing
or dark respiring leaves, adding evidence to speculations that
plant derived CH4 originates from abiotic processes. While processes
generating CH4 within on on the surfaces of vegetation have clearly
been identified, the up-scaling to large areas and to the global atmo-
sphere remains largely speculative and have not therefore been
shown to contribute significantly to the global inventory.
8.3.4.2. Nitrous oxide from vegetation. In a number of experiments,
especially crops, plant-mediated emission of N2O have been observed.
Chen et al. (1999) found N2O emissions up to 2.8 mg m2 d1 from the
5242 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
plants in a soil–rye grass (L. perenne) system, and plant-mediated N2O
emissions from maize, soybean and wheat contributed up to 11,16 and
62% to the total sum of N2O emissions, respectively (Zou et al., 2005). In
contrast, Müller (2003) found that presence of plants in old grassland
could induce N2O uptake. However, these studies did not identify the
mechanisms underlying the plant based N2O production or reduction
processes. Chang et al. (1998) observed that barley (Hordeum vulgare)
and oilseed rape (Brassica napus) emitted N2O from the shoots upon
irrigation with water containing N2O, and hypothesized that N2O was
conveyed by the plants from the soil to the atmosphere via the tran-
spiration stream. In contrast, Smart and Bloom (2001) found that N2O
emissions from wheat (Triticum aestivum) leaves was correlated with
leaf NO3 assimilation activity. They found that N2O was formed during
in vitro NO2 -reductase activity of the leaves and suggested that N2O
formation during NO 2 photo-assimilation could be an important
global biogenic N2O source. Conversion of 15NO 15
3 to N2O in a range of
aseptically grown plant species was reported by Hakata et al. (2003),
and increased N2O emission from soybean was observed concomitant
with an herbicide induced accumulation of plant NO 2 (Zhang et al.,
2000) providing further evidence for in planta production of N2O.
The potential for tree species to act as conduits for N2O emis-
sions were demonstrated in the work by Pihlatie et al. (2005). In
a laboratory experiment with beech (F. sylvatica) seedlings it was
found that fertilization with 15N-ammonium-nitrate (15NH15 4 NO3)
induced foliage 15N2O emissions and exposing the beech roots to
elevated N2O concentrations induced significant emissions of N2O
from shoots and leaves (Fig. 8.2). Pihlatie et al. also found that
concentrations of dissolved N2O in leaves in a beech forest canopy
exceeded ambient atmospheric concentrations, indicating a poten-
tial for canopy N2O emissions.
In summary, substantial evidence exist that plants contribute
directly to the emission of CH4 and N2O. Yet, most work has been
based on small-scale laboratory work and the scale of the fluxes
appears small. However, there is an urgent need for field-based
measurements and more detailed explanation of the underlying
processes.
8.4. New developments in measurements of N2O
and CH4 and denitrification
N2O and CH4 fluxes are measured at scales ranging from a few
grams of soil to several km. Each scale and method has contributed
to our current understanding of biosphere atmosphere exchange of
N2O and CH4 (Denmead, 2008). Our global understanding of N2O
Fig. 8.2. Nitrous oxide emissions (mg N2O–N m2 h1) from beech (Fagus sylvatica)
leaves after exposing the beech roots to different concentrations of N2O in the root
compartment solution. Bars indicate average (þSE) of two different beech seedlings.
Modified after Pihlatie et al. (2005).
and CH4 fluxes and their control by physical, chemical and micro-
bial processes has largely arisen from flux chamber measurements.
Recent development of high frequency instruments, that detect
very small concentration changes, has improved our knowledge of
N2O and CH4 biosphere atmosphere exchange at the field/land-
scape scale and at a high temporal resolution.
8.4.1. Flux chambers
Usually closed (non-steady state) chambers are used for N2O
and CH4 flux measurements, e.g. Butterbach-Bahl et al. (1997),
Conen and Smith (1998). Advantages of chambers over microme-
teorological techniques are that chambers are low cost and can be
used on small fields/plots. Disadvantages include limited spatial
averaging of a spatially variable quantity due to small area (usually
<1 m) of most of these enclosures. Recent developments in
chamber methodologies include:
1) an inter-comparison of the main chambers types employed for
N2O and CH4 chambers used within the European community
(Philatie personal communication 2008), similar to the inter-
comparison of soil respiration chambers (Pumpanen et al., 2004).
ACCENT has contributed towards the funding of this exercise;
2) the validity of the commonly used linear regression equation to
calculate fluxes from non-steady state chambers was ques-
tioned, as it may underestimate the true flux. An exponential
approach may be more accurate (Kroon et al., 2008),
3) development of the fast box method (Hensen et al., 2006)
facilitates chamber measurements from many spots within the
field and establish a picture of the spatial heterogeneity of N2O
and CH4 emissions very quickly. This method requires
combining manual chambers with sensitive fast response
analysis of N2O and CH4, for example using tunable diode laser
techniques.
8.4.2. Micrometeorological methods
The development of tunable diode lasers for CH4 and N2O provides
a method of measuring N2O and CH4 biosphere atmosphere exchange
by micrometeorological methods at high temporal frequency (30 min)
over surfaces where fluxes are reasonably large (approx 20 ng m2 s1
of N2O or CH4). This measurement approach is particularly valuable for
heterogeneous ecosystems, i.e. grazed grasslands, and soft surfaces,
where compaction by walking to a flux chamber may release gases
into the chamber, e.g. peat wetlands or dung heaps. Eddy covariance
measurements of CH4 for example were made over northern wetlands
in Finland (Rinne et al., 2007) and of N2O for example over grazed
grasslands in Scotland (Di Marco et al., 2004). For well-defined point
sources, such as manure heaps and landfill sites the Gaussian plume
method has been used to calculate the emission strength, by either
walking or driving through the emission plume (Skiba et al., 2006;
Hensen et al., 2006).
8.4.3. Comparison of eddy covariance with chamber methods
Scaling up to the field and regional scale is usually based on data
from small flux chambers. Several studies have been conducted to
establish the validity of this approach. It is interesting that for
N2O fluxes from grasslands and arable soils (Christensen et al., 1996)
chambers strategically placed within the footprint of the micro-
meteorological tower are in reasonable agreement with eddy
covariance. However for CH4 fluxes from rice paddies discrepancies
of a factor of 2–3 between chamber and micrometeorological
method, the chambers giving lower emissions, were reported
by Kanemasu et al. (1995) from the Philippines and Hargreaves
(personal communication) from a rice paddy field in the Po Valley,
Italy. These different observations suggest that more comparisons
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
need to be carried out and that chambers may well be suitable
for relatively firm surfaces, but not those of low bulk density or
complete waterlogged.
8.4.4. Recent methodological advances in measurements
of total denitrification rates
For a full understanding of the processes and accurate simulation
of observations using models, we need to know the removal rate of
N2O in the ecosystem. The only natural process of permanent
removal of excess N from ecosystems is denitrification to N2. The
very high natural background of atmospheric N2 hampers direct
quantification of total denitrification. A wealth of methods has been
developed in the past decades for quantification of total denitrifi-
cation (Groffman et al., 2006). Unfortunately, none is without
drawbacks and even today, there is no method that can be used at
the field scale or at high temporal resolution. The most common
method is the acetylene inhibition method (Balderston et al., 1976),
by which the terminal step of denitrification, i.e. the reduction of
N2O to N2 is inhibited by acetylene. Major drawbacks are that it is not
easy to achieve 100% diffusion of C2H2 to the active denitrification
sites, that nitrification is also inhibited by C2H2 and that C2H2
interacts with NO in oxic environments (Bollmann and Conrad,
1997). To overcome these problems a completely new concept of
replacing the background N2 during soil core incubations with
a noble gas (e.g. with a He:O2 mixture) has been developed and
facilitates direct measurements of N2O and N2 (Scholefield et al.,
1997; Butterbach-Bahl et al., 2002). The major drawback is the high
capital investment in equipment and the time-consuming flushing
procedure to remove N2.
The use of stable isotope analysis either in tracer studies with
isotopically enriched tracer compounds or at the natural abundance
level offer promising alternatives, but very little progress has been
made in the last 5 years. Application of 15NO 3 containing fertilizer
and monitoring 15N-labelled N2O and N2 provides a suitable tracer
for denitrification to N2 for agricultural N fertilized soils, but not in
N-poor environments. For these 15N tracers can artificially stimulate
N turnover, microbial immobilisation or dissimilatory reduction of
NO þ
3 to NH4 . For N-poor environments natural abundance of N and O
isotopes may offer an alternative, as due to kinetic isotope frac-
tionation the intermediates and the end product of denitrification
become increasingly depleted in 15N, whereas the remaining
15 18
soil NO 3 becomes increasingly enriched in N and O. If substrate is
not limiting, large kinetic N isotope fractionation factors of up
to 40& can be observed during denitrification (Groffman et al.,
2006). However, if denitrification is limiting or rates are small, as in
the case for N-poor ecosystems, the apparent N isotope fractionation
is too small to provide unambiguous interpretation of the data.
Dual-isotope labelling with 15N and 18O-enriched NO 3 can
identify nitrification or denitrification as source of N2O; this infor-
mation is desirable for the models (Wrage et al., 2005). However,
there are problems. At low pH NO 2 , intermediate of nitrification
and denitrification, rapidly undergoes O-isotope exchange with
water (Casciotti et al., 2007). This O-isotope exchange might lead to
misinterpretation of the results when stoichiometric relationships
in the different N2O formation pathways are assumed, and is very
likely the cause of O-isotope exchange between N2O and water, as
reported by Kool et al. (2009).
The most recent approach of quantifying denitrification rates and
differentiating between nitrification and denitrification as sources of
N2O is the analysis of N2O isotopomers. Intramolecular physico-
chemical site differences between terminal and central N atom lead
to differences in N isotope ratios between the two positions during
N2O formation and consumption. Differences in this so-called
15
N site preference have been attributed to N2O production during
nitrification and denitrification, respectively (Pérez et al., 2001),
5243
unfortunately microbial populations have a larger impact on the
isotopic and isotopomer signatures of N2O than the production
pathway itself (Sutka et al., 2003). Very recently, the 15N isotopic
abundance of soil-emitted NO was determined for the first time
(Li and Wang, 2008). The authors found very 15N-depleted NO with
d15N values down to 50& and could identify both nitrification and
denitrification as sources of soil-emitted NO.
It is concluded that many challenges of quantifying total deni-
trification and differentiating between N2O produced by nitrifica-
tion or denitrification remain.
8.5. Modelling of N2O and CH4 fluxes at site and regional scales:
approaches, applications and uncertainties
Signatory states to the United Nations Framework on Climate
Change (UNFCC) are required to produce annual national inventories
of greenhouse gas emissions from all anthropogenic sources,
including emissions from soils. With regard to CH4 and N2O, soils are
the main sources in their respective global atmospheric budgets. The
IPCC (2006) recommends three different approaches (Tier 1–Tier 3) to
provide emission inventories. Tier 1 represents the simplest way to
model or estimate GHG fluxes on site and regional scales. It is a purely
statistical approach, relating e.g. soil N2O emissions to the amount of
applied fertilizer. In the 2007 IPPC reporting guidelines (IPCC, 2006)
the default emission factor for direct N2O losses from soils following
N fertilization is 1%. However, even if one assumes that this factor is
representative on a global scale, which has been questioned in the
recent past (Crutzen et al., 2008), a fixed emission factor cannot
consider reported effects of climate, management or soil properties
on the magnitude of GHG exchange. Therefore, based on a detailed
survey on reported soil N2O emissions worldwide, Stehfest and
Bouwman (2006) developed a more detailed statistical approach for
calculation of emission inventories, which also considers general
environmental factors such as climate, texture and soil organic carbon
contents and management related factors such as fertilization rates
and crop types. However, beside the fact that the demand on required
input information is much larger, this approach also has its weak-
nesses: a) the high uncertainty of the developed statistical model,
b) the rough classification scheme (which is due to the limited
availability of field datasets describing GHG emissions for different
environmental conditions) and c) incomplete coverage of pulse
events, which may dominate annual site budgets.
To account for the huge spatial and temporal variability of GHG
fluxes on site to regional scales the development and use of process-
oriented models may at present be the most promising approach
(Butterbach-Bahl et al., 2004). These models simulate the GHG
exchange at a given site based on the underlying processes, i.e. by
simulating the dominant physico-chemical, plant and microbial
processes involved in ecosystem C and N cycling and associated GHG
exchange (Li et al., 2000). As a general assumption, one defines
that the controlling factors for e.g. microbial C and N turnover such
as temperature, moisture and substrate responses, are comparable
across different climatic zones and landuses and that by capturing
the major biogeochemical processes within an ecosystem it is
possible to predict the temporal variability of fluxes. Such models
require a thorough process understanding of the coupled C and
N (P) cycles, even though the level of process description may vary
between the models currently in use (e.g. Li et al., 2000). However,
these models also have the drawback, that modelling of ecosystem
processes involves a huge dataset of parameters needed to describe
heat transfer, water movement, plant and microbial growth or
anthropogenic management. In comparison to statistical approaches
mechanistic models often show an improved performance with
regard to reproducing observed differences in GHG fluxes between
sites, seasons and management practices (e.g. Kesik et al., 2006).
5244 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
However, the increasing use of mechanistic models also shows
that we still need to improve our process understanding, e.g. the
regulation of microbial processes and its dependence on microsite
variability of environmental conditions such as redox potential or
the feedback of temperature on organic matter decomposition.
A good example of the deficiencies in understanding N2 vs. N2O
production during denitrification is provided by (Groffman et al.,
2006). This gap in knowledge also precludes the parameterisation
of the denitrification process in biogeochemical models such as
DNDC or DayCent, which in consequence leads to a systematic
underestimation of N2 losses using either model.
Biogeochemical process models have recently been used in
a number of studies for calculating regional soil GHG emission
inventories (Fig. 8.3). Thereby regionalisation is achieved by
coupling of the models to GIS databases holding all the relevant
information needed for initializing (soil and vegetation properties,
management) and driving (meteorological conditions) the models
(Kesik et al., 2006). Such an approach partly neglects landscape
processes, such as e.g. lateral flow and transport of nutrients and
sediments via leaching or erosion. An increasing number of groups
are working on fully coupled landscape models, which do allow
consideration of interactions between the biosphere, hydrosphere
and atmosphere at landscape scales. National inventories for N2O
and/or CH4 emissions from soils using DNDC or DayCent have been
calculated for US, UK, China, Germany, India or Europe. Even on
a global scale, the GIS coupled Forest-DNDC model was used to
estimate N2O emissions from tropical rain forest soils (Werner
et al., 2007). Increasingly biogeochemical models have been used to
study potential strategies for mitigating GHG emissions from
soils on site as well as on regional scales (e.g. Li et al., 2006) or to
improve our understanding how future changes in climate or land
use may feedback on biosphere–atmosphere exchange of GHG
(Parton et al., 2007). Uncertainty in such emission inventories and
mitigation/feedback studies is associated with the uncertainties in
input parameters as well as with the uncertainties in model
parameters. However, in present studies the uncertainties in input
parameters have mainly been addressed using Monte Carlo tech-
niques (Kesik et al., 2006; Werner et al., 2007), whereas model
parametric uncertainty is often neglected (Van Oijen et al., 2005).
Fig. 8.3. N2O emissions from agricultural soils in Europe using the GIS coupled
DNDC model. For further details on databases and methodology see Butterbach-Bahl
et al. (2009).
This is a shortcoming, which needs to be properly addressed in
future work. Nevertheless, biogeochemical models offer a great
opportunity to improve our understanding of ecosystem processes
and GHG exchange and they will play an important role in identi-
fying and predicting consequences and feedbacks of global changes
(climate and land use change) for ecosystem functioning and
biosphere–atmosphere trace gas exchange.
8.6. Validation of models by landscape and regional
scale measurements
Developments in inverse modelling and direct large-scale
measurements provide very powerful tools to constrain and verify
our bottom up models and inventories. For example, Bergamaschi
et al. (2005) compared inverse models with national bottom–up
inventories for CH4. These developments are taken further within
the NitroEurope project (www.nitroeurope.eu).
The development of instruments sensitive enough to measure
very small concentration differences has made it possible to
directly measure CH4 and N2O concentrations from aircraft and
satellites. For example, in the UK aircraft based N2O and CH4
concentrations measurements downwind of the British coast have
delivered unique measurements of CH4 and N2O at the country
scale and provided independent top-down estimates of UK emis-
sions. Measurements were interpreted by using a simple boundary-
layer budget approach and the dispersion model NAME. This
approach suggests that the bottom up national emission inventory
underestimates CH4 emissions by a factor of two and N2O emissions
by a factor of three (Polson, submitted for publication). An under-
estimation of the UK national CH4 inventory was also reported by
Bergamaschi’s et al. (2005) comparison of bottom up and inverse
modelling approaches.
Satellite-borne instruments, such as SCIAMACHY, are able to
provide CH4 concentration measurements at the global scale.
SCIAMACHY can clearly detect spatial and temporal variations in
CH4 concentrations in the boundary layer, a considerable achieve-
ment given the small enhancements in a large background signal.
Using these methods emissions due to coalfields, rice cultivation,
ruminants and wetlands are visible for China and India and the Po
valley in Italy (Buchwitz et al., 2005, 2006). Comparisons between
SCIAMACHY observations of CH4 concentrations and those derived
from simple emission inventories revealed large regional and
seasonal differences, especially over tropical rainforests. To some
extent these differences were caused by overestimating CH4
concentrations when water vapour concentrations were large
(Frankenberg et al., 2008). With this correction, SCIAMACHY still
estimates a larger CH4 budget for the tropics than previously esti-
mated and is a clear priority for direct measurements at the surface
using chamber and micrometeorological methods. Validation of the
global N2O budget using satellites is currently not yet possible as
sufficiently accurate and precise N2O satellite data with high
sensitivity near the earth’s surface have not yet been obtained.
8.7. Conclusions
The key developments and gaps in knowledge are:
1. New molecular tools are now available to link soil microbial
biodiversity with soil function and can provide an overview of the
distribution of functional microbial groups in soils of different
landuses, and assign trace gas emissions to the active microbial
population.
2. Instrument development has facilitated CH4 and N2O flux
measurements at the field and landscape scale and provides
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
long-term measurements at large spatial scale and high temporal
resolution at key sites.
3. New methods to study denitrification rates to N2 and isotope
studies to elucidate the microbial pathway responsible for N2O
production and removal are being developed, but none of
these methods can currently be used at the field scale or high
frequency temporal scales.
4. There are insufficient data to scale up CH4 and N2O emissions to
the global scale or to include ‘new’ crops, i.e. bioenergy crops.
5. There is a gap in knowledge of the contribution and quantifi-
cation of plants, especially trees, in producing and transporting
N2O, CH4 from soil to atmosphere.
6. Biogeochemical models have been developed and synthesize
our understanding of ecosystem processes and GHG exchange.
They play an important role in identifying and predicting
consequences and feedbacks of global changes (climate and land
use change) for ecosystem functioning and biosphere–atmo-
sphere trace gas exchange. These models also provide mecha-
nistic tools to up-scale emissions to regional and global scales.
7. Inverse modelling, tower and aircraft based boundary layer
budget studies have been developed and now provide appro-
priate tools to challenge and validate bottom up inventories at
the regional and country scale.
9. Exchange of trace gases and aerosols over the oceans
In this section, considering recent developments in surface–
atmosphere exchange over the oceans, the focus has been narrowed
to organic trace gases and aerosols, in which there have been major
recent advances in understanding.
9.1. New trace gas interactions at the air–sea interface
Considering the size and potential importance of the air–ocean
interface, it is surprisingly poorly characterized for most organic
trace gases. These organic species are known to play important roles
in the Earth’s atmosphere, impacting ozone chemistry and aerosol
formation, thereby influencing the Earth’s overall oxidation capacity
and radiative budget (Williams, 2004 and references therein).
It should be noted that the net primary production (NPP) of the
ocean is comparable in size to that of the terrestrial biosphere
(ca 45 PgC yr1), even though there is approximately 100 times less
biomass in the ocean than on land. The relative paucity of ocean
based data compared to terrestrial sites is due partly to accessibility
and partly to the high spatial and temporal variation within the
limited oceanic biomass. Moreover, there has been a perception from
earlier studies of oceanic alkanes and alkenes that the global ocean
is a relatively minor source term. Over the period of the ACCENT
project, this view has changed remarkably and recent studies are
beginning to recognise the profound effects of the ocean–air inter-
face on global chemical budgets. For many important chemical
species in the atmosphere the role of the ocean remains the greatest
uncertainty in the budget.
The sunlit regions of the oceans are home to a myriad tiny
plant species and bacteria. These organisms photosynthesise
carbon dioxide (CO2) from the atmosphere into biomass, and
a fraction of the carbon ‘‘leaks’’ out into the surrounding seawater
in the form of organic compounds. Some small volatile species
with low Henry’s Law coefficients are known to escape directly to
the atmosphere (e.g. dimethyl sulphide, DMS) while larger species
will remain in the water phase. Subsequent photo-oxidation in
both air and seawater phases generates a multitude of photo-
chemical breakdown products. These compounds may affect the
hygroscopicity and reflectivity of the marine boundary layer
aerosol, either by condensing onto existing aerosol surfaces, or by
5245
Fig. 9.1. A schematic diagram of the processes affecting organic species at the air–sea
interface.
being ejected directly with primary aerosol from the sea surface
(Fig. 9.1).
Several important organic emissions from the ocean have
been identified previously. The best known is dimethyl sulphide
(DMS) which is produced biogenically in the ocean (e.g. Keller
et al., 1989; Liss et al., 1997, and references therein), and yields
the inorganic aerosol component sulphate upon complete
oxidation in the atmosphere (Kiene and Bates, 1990). It is also
well established that organohalogens are emitted in various
forms (e.g. methyl iodide, bromoform, methyl bromide) from
phytoplankton, bacteria, molluscs and worms (e.g. Gribble,
1992). Following atmospheric oxidation, these can affect either
tropospheric or stratospheric ozone, depending on the lifetime
of the species. However, over the period of the ACCENT project
(2003–2008), there has come a realisation that the surface ocean
can play an important role in the budgets of many more organic
trace gases. For example, the surface ocean has been shown
recently to be a large reservoir for oxygenated organic species
e.g. acetone (Singh et al., 2003; Williams et al., 2004). The
possible influence of oceanic isoprene on marine clouds has also
been hotly debated (Meskhidze and Nenes, 2006). Finally
a surface ocean source of methanol first speculated in mesocosm
studies has been implemented in a global model assessment of
methanol, thereby generating an improved fit between model
and measurement data (Millet et al., 2008). Therefore this article
has been focussed on the more recent discoveries related to
acetone (CH3COCH3), methanol (CH3OH), isoprene (C5H8),
monoterpenes (C10H16) and alkyl nitrates (RONO2) in order to
highlight the new developments in air/ocean interactions.
9.1.1. Case studies
9.1.1.1. Acetone (ocean uptake). Over the past 5–6 years our
understanding of the role of the ocean in the global acetone budget
has changed remarkably. Acetone is ubiquitous in the troposphere
and found at relatively high mixing ratios (ca 200 ppt) even in
the remote Pacific atmosphere. Since acetone is recognised as an
important precursor for PAN, ozone and HOx, especially in the cold,
dry, upper troposphere, there has been interest in determining the
sources and sinks worldwide. In 2002, Jacob et al. published
5246 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
a global budget of acetone (Jacob et al., 2002) which differed from
all previous budget attempts in that it considered the role of the
ocean for the first time. Through inverse modelling, they estimated
that the ocean was an important net source of acetone. Indeed,
from the total global source of 95 Tg, some 25 Tg was estimated to
originate from the ocean in order to balance the known sources and
sinks. This was pioneering work since at that time no seawater
acetone measurements, or air–sea fluxes were available. However,
in the space of just two years this view changed dramatically. In
2004 the model developed by Jacob et al., 2002 was tested against
measurements over the remote Pacific. It was found that the model
consistently overpredicted the measured acetone mixing ratios in
the marine boundary layer and the authors concluded that the
ocean was a net global sink for 15 Tg, and that the sources and sinks
were not balanced. In 2004, the first open ocean measurements of
acetone in air and seawater were made (Williams et al., 2004). The
interhemispheric gradients and depth profiles shown by Williams
et al., 2004 were consistent with uptake of acetone from the air to
the sea and a microbial sink in the seawater.
In 2004, two important new publications emerged concerning
acetone. The first was a laboratory-based study which re-deter-
mined the photolysis quantum yield of acetone as a function of
temperature and pressure (Blitz et al., 2004). It was found that
the accepted acetone photolysis rates were significantly over-
estimated by a factor ranging from 3 to 5, particularly for the
cold, low pressure conditions of the upper troposphere. In the
same year, a new shipborne measurement study was published in
which the authors directly measured the flux of acetone at the
ocean surface for the first time using an eddy correlation method
(Marandino et al., 2005). Interestingly, the authors consistently
found uptake fluxes (from the air to the ocean) for acetone over
the oligotrophic Pacific ocean which became stronger further
from the equator. For comparison Marandino et al., 2005 also
determined the flux of acetone by making separate measure-
ments in the seawater (5 m depth) and air (18 m height). Similar
to the results from the Tropical Atlantic (Williams et al., 2004),
these water and air measurements led to highly variable flux
results at the surface, whereas the direct flux measurement was
more consistent. This strongly suggested that for acetone, the
actual air/ocean flux is being driven by processes in the upper-
most layer (0–5 m).
Although these two new studies (Blitz et al., 2004; Marandino
et al., 2005) had a strong impact on the original budget of Jacob
Fig. 9.2. MODIS chlorophyll picture of the Southern Atlanic Ocean in January, inset the Research vessel Marion Dufresne.
et al. (2005), the overall the sources and and sinks for acetone were
still not balanced. To understand these processes better a new
approach to investigate acetone ocean fluxes was made using
so-called ‘‘mesocosms’’ (Sinha et al., 2007). The mesocosms are
light permeable Teflon tent-like structures which float on the
surface ocean enclosing a volume of air near the surface, and with
walls that extend some 20 m below the surface to restrict the
advection of the water mass below. The airspace in the top of the
mesocosm was continually flushed with ambient air to give a resi-
dence time of approximately 3 h in contact with the water surface.
By measuring at the inlet and outlet, the flux could be calculated
while phytoplankton in the water column were monitored. In the
case of methanol a clear uptake flux (from the air to the ocean) was
observed throughout the experiment, whereas for DMS the flux
was always from the ocean to the air. Interestingly, for acetone the
flux was found to be variable but systematic. In strong daylight and
in the presence of significant biological activity, acetone was
emitted from the ocean to the air. In low light or biologically poor
regimes, however, acetone was taken up by the water. These results
are consistent with the results of Marandino et al., 2005 and the
ocean being a net sink for acetone on a global scale, since most of
the ocean is oligotrophic. However, biologically active regions (e.g.
upwelling zones, ocean fronts, or large natural phytoplankton
blooms) can be strong sources in daylight and depending on their
size could to some extent offset the general sink. It is therefore
important to investigate these biological hotspots in future to
better constrain the global budget (Fig. 9.2).
9.1.1.2. Methanol (ocean uptake). In many respects the global
methanol budget is similar to that of acetone discussed above. Plant
growth accounts for most of the estimated global source (40–80%)
and again the role of the ocean is one of the largest uncertainties in the
budget. Studies of methanol have consistently indicated an ocean
uptake of methanol (Williams et al., 2004; Lewis et al., 2005; Sinha
et al., 2007; Carpenter et al., 2004 and references therein.) Recently,
a global 3-D chemical transport model (GEOS-Chem) was used to
integrate and interpret new aircraft, surface, and oceanic observations
of methanol in terms of the constraints that they place on the
atmospheric methanol budget (Millet et al., 2008). It was shown that
for methanol, although overall the ocean represents a net sink,
a separate light dependent oceanic source needs to be introduced in
order to correctly simulate regional distributions in the atmosphere.
This in-water source has the effect of tempering the uptake flux
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
particularly in the Tropics. It was deduced that that the ocean contains
a large primary source (85 Tg y1) of methanol to the atmosphere and
also a large sink (101 Tg y1), comparable in magnitude to atmo-
spheric oxidation by OH (88 Tg y1). Thus the ocean is a net sink
overall, but the in-water source term must be included to match with
available atmospheric measurements datasets.
9.1.1.3. Isoprene (ocean emission). Isoprene, the strongest terrestrial
biogenic emission, has also been observed as an oceanic emission
(Bonsang et al., 1992) and in laboratory-based studies of plankton
(Shaw et al., 2003 and references therein). It has been suggested
recently that marine isoprene emissions are the cause of cloud
droplet radius changes in marine clouds situated directly over
phytoplankton blooms (Meskhidze and Nenes, 2006). However, an
impact of the isoprene on cloud properties appears unlikely given
that concentrations of isoprene measured over the Southern Oceans
do not impact the organic carbon aerosol concentrations signifi-
cantly (Arnold et al., 2004). In the aforementioned paper an aerosol
production efficiency of 2% was assumed for isoprene, and the
modelled contribution of isoprene to organic carbon (OC) was found
to be less than a 1%. Moreover, since time is required to oxidise
isoprene to nucleating products, a superpositioning of a cloud effect
over a bloom in a region of high wind speeds again appears unlikely.
Typical mixing ratios of isoprene over phytoplankton rich areas are
200–300 ppt, approximately an order of magnitude less than over
the rain forest (Williams et al., 2001). However, since isoprene reacts
rapidly in air, terrestrial emissions will not impact the open ocean.
Marine isoprene emissions could influence the local ozone produc-
tion efficiency in regions where ship emissions of NOx occur. This
may be significant for fishing fleets, as the fish, and hence the fleet,
follow the isoprene producing phytoplankton.
9.1.1.4. Halogenated organics (ocean emission and uptake). The
ocean acts as a huge reservoir for chlorine, bromine and iodine and
volatile organic halogen species (e.g. halocarbons) provide a pathway to
transport halogens from the water phase to the atmosphere. Previous
studies revealed that halocarbons like CH3Cl, CH3Br, CH3I, CHBr3 and
CH2Br2 are emitted from various marine organisms, especially macro-
and microalgae, (Scarratt and Moore, 1999 and references therein). The
global sources of CH3I, CH2Br2 and CHBr3 are dominated by marine
contributions. Algal emissions of halogenated compounds vary
considerably, not only from species to species, but also as a function of
age, temperature, time of day, nutrition, partial desiccation, grazing,
light and tidal movement (Ekdahl et al., 1998). Polybrominated species
(e.g. bromoform) are primarily emitted by macroalgae which occur
only in coastal regions, whereas monohalgenated compounds can be
produced from various open ocean biomes.
9.1.1.5. Monoterpenes (ocean emission). Recent laboratory incuba-
tion experiments and shipboard measurements in the Southern
Atlantic Ocean have provided first evidence for marine production of
monoterpenes (Yassaa et al., 2008). Nine marine phytoplankton
monocultures were investigated using a GC–MS equipped with an
enantiomerically selective column and found to emit at rates,
expressed as nmol C10H16 (monoterpene). g [Chl_a]1 day1, from
0.3 nmol g [chl_a]1 day1 for Skeletonema costatum and Emiliania
huxleyi to 225.9 nmol g [chl_a]1 day1 for Dunaliella tertiolecta. Nine
monoterpenes were identified in the sample and not in the control,
namely; ()-/(þ)-pinene, myrcene, (þ)-camphene, ()-sabinene,
(þ)-3-carene, ()-pinene, ()-limonene and p-ocimene.
The laboratory measurements are also supported by shipboard
measurements of monoterpenes in air were made between January
and March 2007, while crossing the South Atlantic Ocean, see
Fig. 9.2. Monoterpenes were detected in air over high ocean chloro-
phyll regions sufficiently far from land as to exclude influence from
5247
terrestrial sources. Maximum levels of 100–200 pptv total mono-
terpenes were encountered when the ship crossed an active phyto-
plankton bloom, whereas over the oligotrophic ocean monoterpenes
were mostly below detection limit. The monoterpenes/isoprene
ratio reached 21% in laboratory experiments (the ratio between the
highest production rates of total monoterpenes and isoprene) and
ranged between 7 and 60% in the Southern Atlantic Ocean.
9.1.1.6. Alkyl nitrates (ocean emission). Alkyl nitrates were assumed
until recently to be exclusively of anthropogenic origin, being emitted
directly from combustion or chemical processes (Simpson et al., 2002),
or being produced at low yield in the photo-oxidation of organic
compounds in the presence of NOx via the reaction of an organic
peroxy radical (RO2) and NO (Roberts, 1990). However, measurements
of MeONO2 and EtONO2 both in equatorial air and seawater (Chuck
et al., 2002) have revealed positive saturation anomalies, and high
levels of RONO2 which correlate strongly with species of known
marine origin such as bromoform (Blake et al., 1999). The mechanism
of formation of marine alkyl nitrates still remains somewhat unclear.
Production in seawater through aqueous phase photochemistry (Dahl
et al., 2003) has been shown to occur via the reaction of ROO þ NO,
where photolysis of coloured dissolved organic matter (CDOM)
generates the peroxy radicals and nitrate (NO 2 ) photolysis generates
the NO. Interestingly, the yield of the reaction ROO þ NO in seawater
was found to be significantly higher than in the gas phase. Alterna-
tively, alkyl nitrates may be emitted directly from marine biota,
although direct evidence for enzymatically mediated production has
not yet been found. Using a chemical transport model Neu et al. (2008)
found the maximum impact of the oceanic alkyl nitrates to be over the
Western Pacific, where they were responsible for of increase of up to
20% of the ozone column.
9.2. Aerosols
9.2.1. Primary marine aerosol (PMA) source functions
Primary marine aerosol (PMA), or sea-spray aerosol is a major
source of global natural aerosol mass budgets and is important for
global climate. Mass is dominated by the super-micron size range
and traditionally source functions have been derived in this size
regime. The supermicon size range also contributes significantly to
aerosol scattering (Kleefeld et al., 2002) and optical depth (Mulcahy
et al., 2008) and thus the direct climate forcing effect. In terms of the
submicron size range, number concentration rather than mass
becomes important in terms of the indirect radiative forcing effect
through the production of cloud nuclei (O’Dowd et al., 1999). Only
quite recently it has become accepted that submicron sea-spray
aerosol exists, and as a result, submicron source functions are rela-
tively new in terms of development.
The PMA source function describes the flux of sea-spray aerosol,
i.e. the number of droplets produced per unit surface area and per
unit of time, evaluated typically at 10 m above the ocean surface.
Hence the function describes an effective flux, parameterised in
terms of ambient parameters such as wind speed and water
temperature. Measurements may provide total fluxes, i.e. the total
number of particles in a given size interval, or spectral fluxes.
The latter are expressed in number of droplets for a range of size
intervals, i.e. mm1 m2 s1. In this review, we focus on a selection of
recently developed or improved source functions which span both
submicron and super-micron sizes. Particular emphasis is focused
on the submicron spray flux and chemical characteristics. A
comprehensive historical review, focused primarily on sea-salt
aerosol production, is provided by Lewis and Schwartz (2005) with
some additions and description of specific source function formu-
lation in O’Dowd and de Leeuw (2007).
5248 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
It is often assumed that the dependences on droplet size and
environmental parameters can be separated, i.e. the source func-
tion is presented as the product of a size-dependent function, g(r),
and a function that describes the parameterisation as function of of
environmental parameters, f(a,b,.), where r is the droplet size
at a specified relative humidity (dry, RH ¼ 80%, or wet) and a, b, .
are, e.g. wind speed, water temperature, atmospheric stability, etc.
Scaling arguments show that droplet production varies approxi-
mately with the third power of the wind speed. However, other
types of paramterization have been proposed as well. Selected
source functions are shown in Fig. 9.3 for a wind speed of 8 m s1.
There are two main developments to report on: the first in terms of
the super-micron sizes where the data in Fig. 9.3 show that the
discrepancy between different formulations is much reduced with
respect to the review situation reported by Andreas (2002).
With respect to Lewis and Schwartz (2004), the uncertainty has
been reduced by a factor of 2. For small particles a clear size
dependence emerges varying roughly as r1.5 80 . The source functions
shown in Fig. 9.3 were obtained using different methods and
different physical principles but leading to consistent results.
The second main development is the extension of the source
function well into the submicron size range. The Mårtensson et al.
(2003) laboratory-based study extended the size-resolved source
function down to r80 ¼ 20 nm and found that the production as
a function of size was also dependent on temperature. Clarke et al.
(2006) provide a source function for particles down to 10 nm. These
studies combine experiments in the laboratory or over the surf
zone, to determine the spectral shape of the flux, with whitecap
coverage which in turn is paramterized as function of wind speed.
Direct and in situ measurements of sea spray total number fluxes
(D > 10 nm) are provided by the eddy covariance (EC) method that
was first attempted by Nilsson et al. (2001) in the Arctic Ocean. The
advantage of this method, as opposed to the whitecap method, is
that all particles within the detectable size range may be measured,
and hence there is no restriction to bubble-mediated production.
The technique was also used at a coastal station over the North East
Atlantic by Geever et al. (2005), who quantified total number
concentration over two size ranges covering the Aitken mode (10–
100 nm) and the Accumulation mode (100–500 nm).
Overall, the most recent schemes agree quite well (e.g. Clarke
et al. surf zone study compares very well to the Mårtensson et al.
laboratory-based parameterisation), providing an improved level of
confidence in PMA source functions over sizes from 0.01 mm to
w10 mm. In addition, the Mårtensson et al. (2003) parameterisation
108
107
106
-1
dF/dLog (r) m s
105
-2
104
Monahan et al 1986
Monahan Extrapol
103 Martensson et al., JGR, 2003
Vignati et al., JGR, 2001
102 Gong, JGR, 2003
Clarke et al., JGR, 2006
de Leeuw et al., JGR, 2000
101
de Leeuw et al., AMS, 2003
Reid et al., JGR, 2001,
100
10-2 10-1 100 101
Radius (microns)
Fig. 9.3. Compilation of sea-spray source functions. Flux values are for a wind speed of
8 m s1.
provides a water temperature dependence that compares favourably
with independent measurements (e.g. Clarke et al., 2006) for 25  C.
9.2.2. Chemical composition of primary sea spray
Although the dominant mass fraction of sea-spray aerosol is sea-
salt, organic matter also contributes to the overall mass and it has
long been known that marine aerosols contain organic material
(i.e. Blanchard, 1964). Field measurements suggested a significant
biogenic primary source of marine organic components (O’Dowd
et al., 2004; Cavalli et al., 2004). In particular a dominant water-
insoluble organic fraction in fine marine aerosol collected during
periods of phytoplankton bloom in the North Atlantic was observed
and it was hypothesized that these insoluble organic components
could have a mainly primary origin. Similar results supporting
a biologically driven oceanic OC source have been recently reported
by Spracklen et al. (2008).
The most comprehensive study to date on the organic fraction
of sea-spray aerosol has been conducted by O’Dowd et al. (2004).
They found a significant and dominating fraction of organic matter
in submicron sizes, while the super-micron size range was
predominately inorganic sea-salt. It should be noted, however,
that the absolute magnitudes of organic mass in the sub and
super-micron size ranges were equivalent (with one-third of the
total organic mass residing in the coarse mode), and that it was
their relative concentrations that differed significantly. Fig. 9.4
illustrates the chemical composition of clean marine aerosol over
the north east Atlantic during winter and summer periods,
corresponding to low and high biological activity periods (O’Dowd
et al., 2004). Also shown is the distribution of chlorophyll-
a derived from the SeaWifs satellite. During periods of high
biological activity, the organic fraction ranged from 40 to 60% of
the submicron mass, while during low biological activity periods,
the fraction reduced to about 10–15%. O’Dowd et al. (2004) argued
that the water-insoluble organic fraction, dominating the organic
composition in the fine size fraction, was likely to be derived from
bubble-mediated production.
Later experiments, using the gradient technique to determine
aerosol chemical fluxes at Mace Head (Ceburnis et al., 2008)
showed that the water-insoluble organic carbon (WIOC) mass
invariably had an upward mass flux associated with it and followed
similar trends to sea-salt gradients, while water-soluble organic
carbon (WSOC) mass possessed a downward flux profile identical
to nss-suphate. They concluded from the gradients that WSOC must
be formed from secondary aerosol formation processes while WIOC
must be formed from primary production. These conclusions were
further supported by Facchini et al. (2008) who conducted bubble-
bursting experiments amidst a plankton bloom over the NE Atlantic
during the MAP (Marine Aerosol Production) cruise in 2006
(Fig. 9.5). During these experiments, it was found that spray
particles exhibited a progressive increase in the organic matter
content from 3  0.4% up to 77  5% with decreasing particle
diameter from 8 to 0.125 microns (Fig. 9.5).
Submicron organic matter was almost entirely water insoluble
(WIOM) and consisted of colloids and aggregates exuded by
phytoplankton. Facchini et al. (2008) found that the WIOC to sea-
salt mass ratio fingerprint as a function of particle size in the bubble
tank experiments matched that observed in atmospheric samples
both at Mace Head (shown in Fig. 9.5) and on the MAP cruise over
the open ocean. These results conclusively confirmed that the
WIOC component observed in marine air samples relate to primary
aerosol production. Electron microscopy observations of individual
102
particles collected at the ocean surface in a number of sites sup-
port the hypothesis that complex exopolimers and the microgels
forming from these, produced by bacteria and algae, are involved in
bubble-bursting processes (Bigg and Leck, 2008).
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267 5249

Fig. 9.4. (Left) Chemical and mass size distributions for North Atlantic marine aerosol during periods of low biological activity and high biological activity. (Right) oceanic chlo-
rophyll-a concentrations over the North Atlantic for low and high biological activity periods.

These results indicate that a sea-spray source function should
not only consider size-resolved mass, but also chemical composi-
tion. The first attempt at a combined submicron organic-inorganic
sea-spray source function, implemented in a regional climate mode,
was produced by O’Dowd et al. (2008). They combined the Geever
et al. (2005) accumulation mode number flux, combined with
the Yoon et al. (2007) seasonal modal diameter (minus secondary
aerosol mass), and integrated with the seasonal trend in WIOM/sea-
salt ratios to produce a physico-chemical flux function driven by
wind speed and satellite-derived chlorophyll-a concentrations over

Fig. 9.5. (Left) Average chemical composition relative concentration from bubble-bursting tank samples. (Bottom) average ratio of WIOC to sea-salt from atmospheric samples at
Mace Head. Data for the 0.06–0.125 mm size range are not reported from the bubble tank because the total carbon analyses in this stage were below detection limit. The bars are the
standard deviation of the mean. (Right) Visible satellite image of plankton bloom off the west coast of Ireland during the MAP cruise June–July 2006. Bubble-bursting tank
experiments were conducted in and around the plankton bloom.
5250 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Fig. 9.6. (Top panel) Near surface sea-spray mass concentrations around the European regions and average wind vectors. (Bottom Panel) Percentage primary organic contribution to
sea-spray mass.
the North East Atlantic. The model predicted results compare well
to seasonal observations at Mace Head and are illustrated for winter
and summer seasons in Fig. 9.6.
9.2.3. Secondary aerosol production
In recent years, significant effort has been made into the study of
new particle formation in the coastal zone in the hope that it would
elucidate key processes associated with nucleation over the open
ocean. Most of these studies have focused on nucleation in coastal
zones (e.g. at Mace Head) and revealed regular particle bursts, with
burst concentrations often exceeding 106 cm3. These events have
been linked to release of biogenic iodine vapours from coastal algae
followed by the photochemical production of iodine oxide aerosols
(O’Dowd et al., 2002; McFiggans et al., 2004). A detailed review of
studies into these processes is found in O’Dowd and Hoffmann
(2005). Further studies revealed that the nucleation mode particles
could also contain some organic aerosol mass suggesting that
secondary organic aerosol production also occurs in marine air
and contributes to aerosol growth (Vaattovaara et al., 2006). The
findings of O’Dowd et al. (2004) and Ceburnis et al. (2008) also
point to significant contributions of secondary organic aerosol,
manifesting itself in the WSOC component. The most relevant
organic secondary component (SOA) is methanesulphonic acid
(MSA). Some dicarboxylic acids were associated with secondary
formation mechanisms in previous papers (i.e. Kawamura and
Sakaguchi, 1999) but a relevant fraction of the observed concen-
trations of oxidized organic matter in marine aerosol still remains
unaccounted. Modelling studies by Meskhidze and Nenes (2006),
proposed that isoprene emissions from plankton were sufficient
to produce enough water-soluble organic aerosol to significantly
enhance CCN concentrations and cloud albedo; however, it was
later revealed that the isoprene fluxes were inadvertently over-
estimated by a factor of 100. Nevertheless, Zorn et al. (2008) also
confirmed the dominance of organic aerosol mass in air overlying
plankton blooms over the southern ocean but no detail on speci-
ation was elucidated. Recently a new secondary organic aerosol
component, produced through the reaction of gaseous amines with
sulphuric acid has been found in marine aerosol over the North
Atlantic (Facchini et al., 2008). Dimethyl and diethyl ammonium
salts (DMAþ and DEAþ) are the most abundant organic species,
second only to MSA, detected in fine marine particles in North
Atlantic and represent on average 11% of SOA and a dominant part
(35% on average) of the aerosol water-soluble organic nitrogen
(WSON). Several evidences support the hypothesis that DMAþ and
DEAþ have a biogenic oceanic source even if the formation mech-
anism of these biogenic amines remains unclear.
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
In conclusion, apart from MSA and a few dicarboxylic acids and
amine salts, the vast majority of secondary organic marine aerosol
remains to be identified, suggesting that other formation mecha-
nisms and alternative SOA components should be studied.
10. The processes of wet scavenging of aerosols
and trace gases from the atmosphere
10.1. Introduction
Precipitation or wet scavenging is an efficient cleaning mecha-
nism of the atmosphere. It combines all the in and below cloud
processes that take up trace gases and particles into liquid drops or
crystals forming a cloud and deposits the material to terrestrial or
marine surfaces in rain or snow.
10.2. Nucleation scavenging of drops and ice crystals
Droplets form on a subset of the aerosol particles, the cloud
condensation nuclei (CCN), present in every air mass. This mech-
anism is probably the most important to incorporate pollutants
into the cloud phase. Depending on their size, chemical composi-
tion and the ambient relative humidity, aerosol particles take up
a certain amount of water (Pruppacher and Klett, 1997) and when
exceeding their critical size they activate to cloud droplets. In
the classical Köhler theory, only their composition with respect to
insoluble material and inorganic salts is considered. Recent studies
(e.g. Anttila and Kerminen, 2002; Sorjamaa et al., 2004; Romak-
kaniemi et al., 2005; Kokkola et al., 2006; Topping et al., 2007) have
highlighted the importance of soluble trace gases and partly soluble
organic substances which often coat the surface of the particles for
the activation properties.
Even though our knowledge of the formation of droplets is now
reasonably satisfactory, the nucleation of ice crystals as a subject is still
quite poorly understood. In the atmosphere, significant numbers of ice
particles start to form only below 5  C co-existing still with liquid
drops. Homogeneous freezing of liquid droplets depends on the size;
large droplets can freeze homogeneously at temperatures of around
33  C, whereas at 40  C even the smallest droplets freeze homo-
geneously. New insight into the homogeneous nucleation of ice crystals
under these conditions which correspond to cirrus clouds was
obtained in the AIDA chamber (Benz et al., 2005; Möhler et al., 2006). In
the temperature range between 5 and 40  C, the presence of
insoluble nuclei is necessary to initiate the formation of an ice crystal.
These ice nuclei (IN) are aerosol particles that can act in four main ways:
– Deposition mode: water is adsorbed directly from the vapour
phase onto the surface of an IN where it is transformed into ice
– Condensation–freezing mode: this is a hybrid process that
requires supersaturation with respect to water. Here, the CCN
that has formed the drop acts now as an IN. This process seems
far more effective than the deposition mode.
– Freezing mode: the IN, scavenged by the drop, initiates the ice
phase from within a supercooled water droplet
– Contact mode: the IN initiates the ice phase at the moment of
contact with the supercooled drop
The number of IN depends on the chemical properties of the
aerosol particles. It has been found that there exists a dependency
on supersaturation and also on temperature. In contrast to CCN,
a good IN should be insoluble and have a crystalline-type structure
to facilitate the formation of the ice lattice (e.g. silicate).
Recently, the role of primary biological aerosols for nucleation of
drops and ice crystals has been highlighted (Deguillaume et al., 2008).
These particles can be viable organisms capable of metabolic reactions
5251
which can involve atmospheric organic compounds and oxidants
(airborne microorganisms) (Ariya and Amyot, 2004; Sun and Ariya,
2006). They also comprise either biological particles including alive,
dead cells and cell fragments, capable of nucleating cloud droplets and
ice particles via physical processes (Möhler et al., 2007) or any kind of
organic substances deriving from biomolecules and contributing to
aerosol masses. Airborne microorganisms are incorporated into cloud
droplets and raindrops by nucleation scavenging as they have CCN or
IN potential (e.g. Bauer et al., 2003; Möhler et al., 2007) or by washout
processes. Some investigations clearly show that most of these
microorganisms are able to develop at low temperatures (between 5
and 5  C) encountered in clouds. Furthermore, measurements of
concentrations of adenosine triphosphate (ATP) in cloud water indi-
cate that most microorganisms are still metabolically active (Amato
et al., 2007a,b,c,d).
Despite the presence of ice in many cloud systems, interactions
between trace chemicals and ice are not well understood (Abbatt,
2003). Chemical solutes originally dissolved in a supercooled
drop may be retained or expelled from the drop as it freezes. Non-
volatile species, such as sulphate, are efficiently retained during
freezing but this retention process is not well characterized for
many soluble gases found in clouds (Voisin et al., 2000). Cloud
modelling studies have found that partitioning of solutes during
hydrometeor freezing may significantly affect chemical distribu-
tions in the troposphere and deposition to the ground (Audiffren
et al., 1999; Mari et al., 2000; Crutzen and Lawrence, 2000; Yin
et al., 2005; Kärcher and Basko, 2004). A better understanding of
the partitioning of volatile chemical solutes during freezing is
needed to quantify their effects on tropospheric gas-phase and
precipitation chemistry.
Bacteria which have entered the liquid phase find therein
a solution of organic compounds which may serve as nutrients.
Recent studies show that living and active microorganisms,
including bacteria, yeasts and fungi, are present in the atmospheric
water phase (Fuzzi et al., 1997; Bauer et al., 2003; Amato et al., 2005,
2007a). These microorganisms could play an active role in chemistry
and microphysics of clouds as discussed by a growing number of
scientists (Ariya and Amyot, 2004; Amato et al., 2005, 2007b; Möhler
et al., 2007; Deguillaume et al., 2008). Indeed, living microorganisms
are clearly biocatalysts which could transform organic compounds
as an alternative route to photochemistry. Many unresolved ques-
tions remain on this topic and long-term observations can be used
to evaluate the diurnal and seasonal variations of structure and
activity of microorganisms as a function of environmental conditions
(i.e. humidity, light, temperature, pH.).
10.3. Impaction scavenging of aerosol particles
Inside the cloud unactivated aerosol particles remain between
the nucleated drops as interstitial aerosol. These particles can
collide with the hydrometeors and become incorporated into the
cloud particles. However, due to the fact that already the main part
of the particle mass was scavenged by nucleation, inside cloud
this process does not contribute significantly to the pollution mass
in precipitation (Flossmann, 1998a,b; Flossmann and Wobrock,
1996). An importance can be attributed to this process in combi-
nation with the contact mode freezing of the previous section.
Once the hydrometeors fall and leave cloud base, on their way to
the earth’s surface they meet an unperturbed aerosol particles
population. Here, the collision with aerosol particles can contribute
a significant portion to the aerosol particle loading of the rain on
the ground, depending also on the height of cloud base.
During the cloud lifetime, chemical processes lead to the
formation of new chemical species with relatively low volatility
such as inorganic and organic acids, which can modify the physico-
5252 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
chemical properties of aerosol particles after the cloud dissipates
(Feingold and Kreidenweis, 2002; Yin et al., 2005) and lead to
secondary organic aerosols formation. For some chemical species,
aerosol particle dissolution is the only source in cloud droplets; for
instance, transition metal ions, and in particular iron, which is well
known to play a major role in the oxidizing capacity of clouds
(Deguillaume et al., 2005). Study of such complex interactions
needs process modelling efforts integrating in situ measurements.
10.4. Scavenging of gases
In addition to the particles, numerous trace gases are present
in the atmosphere. Gases are taken up into drops according to
their solubility. The maximum amount of a gas that can be taken
up into water is a function of the Henry’s law coefficient. A
comprehensive compilation of updated Henry’s law coefficients is
available at http://www2.mpch-mainz.mpg.de/~sander/res/henry.
html. Henry’s law describes the equilibrium between the
concentration in the air and the liquid, however, once in the liquid
phase most gases are destroyed by chemical reactions and, thus,
an equilibrium will never be achieved. Consequently, more and
more gas can be taken up into the cloud drops. Only the droplet
lifetime (max. 30 min) will limit the gas scavenging. Recently, our
knowledge of the uptake and reaction coefficients of the ambient
trace gases has significantly increased and quite complex aqueous
phase reaction schemes have become available (Herrmann et al.,
2005), including an extended reaction mechanism for atmo-
spherically important hydrocarbons containing more than two
and up to six carbon atoms.
The complexities of the cloud processes involved in pollutant
scavenging have discouraged investigators from simultaneously
treating all aspects of multiphase chemistry and microphysics with
equal rigor. However, efforts made to develop sophisticated cloud
models with complex multiphase chemistry allow more detailed
studies on the interaction between microphysical and chemical
multiphase processes (Leriche et al., 2007; Ervens et al., 2004a,b).
One important feature lies in a detailed representation of the
microphysical as well as multiphase chemical processes. These
developments really distance themselves from the other attempts
of coupling multiphase chemistry in 3D models, which are often
restricted to the study of inorganic species and basic organic species
wet deposition (Tost et al., 2007).
10.5. Clouds
Clouds form when air ascends and following expansion and
cooling the water vapour condenses. The droplets grow further by
condensation, then, collide and coalesce with each other, until they
become sufficiently heavy to fall against the updraft velocity that
has suspended them until now. Depending on the height of cloud
base and the temperature conditions they might reach the ground
as rain. If the temperature in the clouds reaches temperatures
sufficiently below zero, then ice crystals develop. They also grow by
water vapour deposition, and collide with each other. If they
become sufficiently heavy, they fall to the ground in solid or liquid
form, as a function of the below-cloud temperature. During their
entire lifetime, these cloud hydrometeors (¼drops or ice particles)
take up pollution in particulate and gaseous form and deposit it on
the ground together with precipitation. A schematic display for
liquid clouds is shown in Fig. 10.1.
Only few clouds form locally due to convection and, thus, have
only a limited geographical impact. Most clouds are embedded in
large-scale system and cover areas of several thousand km2. They
incorporate the local pollution when the droplets nucleate and
Fig. 10.1. Schematic of the microphysical and scavenging processes in liquid phase
clouds.
then transport them over larger distances, processing the material
during transport.
The problem of correctly describing this process is coupled to the
problem of scales. As shown below, the nucleation of hydrometeors
and all subsequent reactions take place on the scale of the individual
drop or ice crystal. The formation, transport and dissipation mech-
anisms of clouds, however, act over a much larger region and require
description on a synoptic or even hemispheric scale. In the past,
this fact imposed severe constraints in the accuracy of the modelling
of these processes and resulted either in highly parameterised
dynamical models with detailed treatments of the chemistry (Wolke
et al., 2005; Sander et al., 2005) or in highly simplified chemical
schemes in sophisticated meteorological models (Mari et al., 2000).
Only recently have 3-D dynamic codes with detailed microphysical
treatment and aerosol particles (Leroy et al., 2008) and chemistry
(Tost et al., 2007) become available due to developments in
computers. These models obviously are restricted to rather limited
modelling domains, however, they highlight e.g. the importance of
the background aerosol population for the development of the cloud
(Leroy et al., 2008).
Fig. 10.2 displays the results of a sensitivity test for the CRYSTAL-
FACE cloud (Leroy et al., 2008). The simulation shows a clean
boundary layer in which rain develops readily while precipitation
formation is suppressed in the polluted case by the large population
of aerosols derived from air pollutants. Not only has the precipita-
tion been suppressed but the horizontal and vertical structure of the
cloud is substantially modified.
By including as many as possible of these processes in larger
scale models parameterisations have been developed to yield the
first reliable maps on critical loads (e.g. Hoose et al., 2008; Pozzoli
et al., 2008). One emphasis of these models has been the aspect of
topography.
10.6. Orographic precipitation
At mid-latitudes, mountainous terrain is commonly associated
with high annual precipitation due to the forced ascent of air
resulting in cloud formation and precipitation. At a sub-grid scale,
however, there can be significant variations in pollutant deposition
due to local emissions and variation in topography and vegetation.
A need, therefore, arises for fine scale process models to investigate
pollutant deposition at the kilometer scale (Dore et al., 2006).
The aerosol population (size distribution and composition) has
a major influence on the dynamics and microphysics of orographic
cloud development. The cloud condensation nuclei (CCN) population
entering cloud base determines the extent and onset of warm rain
produced by collision coalescence. These, along with the presence of
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Fig. 10.2. Sensitivity study concerning the number concentration of boundary layer aerosol particles (Leroy et al., 2008) after 40 min of cloud development; the displayed domain is
a 2-D cross section of the 3-D domain restricted to 30 km in the horizontal and 15 km in the vertical; the envelopes of the different hydrometeors are specified for each panel.
heterogeneous ice nuclei affect the onset of the glaciation process and
the efficiency of secondary ice processes such as the Hallett–Mossop
process of ice splintering. These in turn determine the release of latent
heat of fusion in the cloud, which has a major influence on the vigour
and structure of the cloud dynamics. The initiation and development
of the ice phase is crucial to the precipitation formation and its loca-
tion within the cloud. More detailed process studies are needed to
understand such complex feedbacks. In the case of orographic clouds,
it is shown that aerosol–cloud interactions may cause a displacement
of precipitation from the upslope side of a hill towards the downslope
side when the number of aerosols is increased (Muhlbauer and Loh-
mann, 2008). Inverse relations between air pollution and orographic
precipitation could be of major interest for weather prediction and
hydrological budget evaluation.
The initial physical and chemical state of aerosol entering the
clouds is strongly influenced by the prevailing oxidant climate and
air mass history. The degree of in-particle oxidation and resultant
hygroscopic properties has been seen previously to be closely tied to
the degree of gas phase photochemical ageing (Cubison et al., 2006).
The specificity, in terms of time since surface emission and oxidative
exposure, which can be made from direct aerosol measurements, is
however relatively poor. This may be inferred much more accurately
however by making coincident measurements of gas phase volatile
organic tracers (VOCs).
10.7. Organic N in air and rain
Better understanding of the processes that link the chemical
and biological properties of aerosols with cloud formation and
droplet growth has indicated a need for better knowledge of the
organic components. Although transport or organic C, and depo-
sition to the earth’s surface, has not been regarded as quantita-
tively important for ecosystem health, organic N has the potential
to add to the known effects of inorganic N wet deposited from the
atmosphere especially in remote areas. Studies of precipitation
5253
chemistry have highlighted our lack of knowledge of the organic
nitrogen constituents (both gaseous and particulate) in the
atmosphere. Recent reviews (Cornell et al., 2003; Neff et al., 2002)
have indicated that the contribution of water soluble organic
nitrogen (WSON) in precipitation to wet deposition may be up to
one-third of the total, yet little is known about the chemical
composition, form or sources of this material. Initial scepticism
about the nature of WSON has to some extent been dispelled
(Cape et al., 2001), but the broad range of possible composition
and emission sources means that the transfer pathways are still
somewhat uncertain. It is known, for example, that biological
processes interconvert inorganic and organic nitrogen in forest
canopies (Fang et al., 2008), but it is not clear how much biological
activity may occur in the atmosphere or on the surfaces of
sampling equipment. The presence of both gaseous and particulate
WSON in the atmosphere implies that dry deposition is an
important but unquantified pathway for transfer of organic
nitrogen to the earth’s surface.
10.8. Conclusions and some priority areas of future research
The processing of atmospheric contaminants as gases and
particles by clouds and precipitation form part of the biogeo-
chemical cycling within the atmosphere. The gases and particles
are taken up into cloud hydrometeors during the lifetime of a cloud,
processed and either released during evaporation or deposited onto
the ground with the liquid or solid precipitation. Knowledge of the
underlying processes has greatly advanced concerning the liquid
phase. Here, the gap concerning the role of the organic material is
now almost closed. The greatest uncertainty nowadays lies with the
ice phase. Generally, the ice phase is chemically less active than
the liquid phase. Thus, the uptake and processing is reduced.
Furthermore, the role of the ice phase in the precipitation forma-
tion and deposition is not completely known and these weaknesses
5254 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
in understanding give rise to large uncertainty in values are
obtained by current models.
The second challenge in the modelling of wet deposition is
linked to role that bacteria and other living organic matter (bio-
aerosols) can play in the microphysics of a cloud and in atmospheric
aqueous phase chemistry, which is largely unknown.
11. Ecosystem–atmosphere exchange – concluding remarks
This paper has reviewed the state of knowledge of atmosphere–
surface interactions of a broad range of trace gases and particles.
Given the wide range of chemical species reviewed and the
reasonably self contained sections within the paper, this concluding
section does not attempt to provide a summary of the sections. The
following commentary reflects on the overall direction of the
science which, like the subject material, is becoming ever more
global and searching for integrating mechanisms. There has been
substantial progress over the last decade in process understanding,
field measurement and in modelling. Models have been developed
incorporating the process understanding to generalize the
ecosystem–atmosphere exchange over regions and are currently
able to describe the fluxes with uncertainties of the order of 30% in
wet deposition and 50% in dry deposition for the main chemical
species. However, there is a lack of measurements to evaluate the
models. For the future, extensive measuring campaigns and long-
term monitoring of fluxes are necessary to further develop this
important field. The development of super sites in the European
EMEP network with a full spectrum of gas and aerosol phase trace
atmospheric constituents and continuous measurements of
surface–atmospheric fluxes represents an important development
in this direction. The development of long-term micrometeorolog-
ical CO2 flux monitoring sites, initially within CarboEurope and
followed by AmeriFlux, but now extending to a global network
provides much of the infrastructure for extension to trace gases.
Such long-term flux measurements of reactive pollutants to test,
develop and validate models represent an important development,
which, in turn will be expanded regionally.
11.1. Policy needs
In the policy development there is a need to address environ-
mental priority issues, among which none are currently greater than
climate change. However, human health, ecosystem quality and the
sustainable use of natural resources is growing in importance.
There is a current tendency to group the environmental impacts
because they are linked through the pollutants and the receptor
which follows historical tradition. New, much broader and more
integrated directions include global change, reactive nitrogen,
air quality and climate change, bringing together a range of related
issues in the search for more sustainable solutions to the under-
lying problems. This is however far from being implemented in
policies because it involves a larger scale and therewith global
political developments. However, the process has begun within
initiatives such as those described in the Millenium Ecosystem
Assessment (2005). Ultimately, political developments will be
required to allow such integrated environmental policies to be
developed, but evidence of the time it is taking to develop appro-
priate controls to limit greenhouse gas emissions suggest that
it will be a slow process.
11.2. Current understanding
It is questionable whether our current understanding of the
atmosphere–surface exchange is keeping pace with these more
integrated needs. The processes are very variable and the
interactions of the different components are not yet studied mainly
because of instrument and resource limitations. In the 1950s the
work started with single component fluxes to a few ecosystems.
Currently, as presented in this section, the state of knowledge is
grouped into families of components (VOC, reactive nitrogen, GHG,
particles), in which our understanding provides regional budgets
as well as deposition fluxes of chemical species of interest for
effects assessment and forms a part of continental scale integrated
assessment. Clearly, progress has been rapid in some areas, moti-
vated by pressure for control measures. The next steps in the wider
integration will require similar pressure to deliver the necessary
information to support policy development.
Within the area of reactive nitrogen it has been shown that there is
a dynamic exchange between the atmosphere and surface, regulated
by stomatal and chemical interactions; deposition, re-emission and
re-deposition processes and by the exchange of different forms of
nitrogen in interaction with the status of the system (saturation,
carbon, phosphorus, water-filled pore space, etc) (Sutton et al., 2008a;
Pilegaard et al., 1995). Sulphur has a large impact on the uptake and
release of ammonia at the surface. This is all is part of the nitrogen
cascade, where one molecule of reactive nitrogen that enters a system
in oxidized or reduced state is used and transformed in that system,
can be leached to the groundwater as nitrate, entering the river and in
the estuaries where it can be emitted as N2O contributing to climate
change and into the stratosphere, where eventually it is broken down
depleting the ozone layer (Galloway et al., 2003). There is evidence
that increased nitrogen deposition leads to NO emissions from the soil.
This links nitrogen deposition with the oxidant surface–atmosphere
exchange. Oxidants in their turn affect the ecosystem health and
therewith the nitrogen uptake and use efficiency. These are examples
of the strong interaction between the components in the surface–
atmosphere exchange.
11.3. Future developments
Agriculture is a major source of emissions to the atmosphere,
which relative to industry has been regulated substantially less (Aneja
et al., 2008). Until now the policy requirements for food security from
agriculture has moderated the willingness to limit emissions of trace
gases from this sector. More and more, however, it is recognised that
the production should be within the limits of sustainability, limiting
pollutant emissions to surface or groundwater and to the atmosphere
of reactive nitrogen compounds, greenhouse gases, persistent organic
pollutants, phosphorus and odour. Agriculture is a collection of diffuse
sources with many uncertainties in the emissions. Greenhouse gas
emissions and ammonia are uncertain because the emissions depend
on farm management practices, soil type, fertilizer use, type of crop
or animal breeding, size and location of the farm, etc. This makes
quantification of the sources and successful targeted measures and
policies for control very difficult.
The next step will include quantifying the strong interactions
between land use, food supply, biodiversity and biogeochemical
cycling of key nutrients. Studying these landscape interactions is
a new topic, where just a few exercises have been attempted. The
landscape scale, such as agricultural areas, complex terrain, urban
areas, etc. have their own dynamic and interactions which differ
from the normally studied stationary conditions. It is necessary to
study this scale because of the need to determine the contribution
of the individual sources which need to be controlled. In rural,
agriculture dominated areas there is a large contribution of
different reactive nitrogen sources, such as animals in- or outside
housing systems, application of fertilizers or manure, storage of
manure, traffic and small industries. Within such an area deposi-
tion and re-emission takes place with a high spatial and temporal
dynamic. Especially for nitrogen the efficiency of use can be
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
improved if the individual contribution of the different sources and
resulting losses can be quantified.
The majority of surface–atmosphere exchange measurements
have been made in rural landscapes, yet a large fraction of emissions
occur in urban areas, where most of the global human population
now resides. In urban areas there is a concentration of sources
of gases and pollutants from industry, traffic and households. The
emissions to the atmosphere and the resulting exposure in these
areas are therefore a growing concern globally and our knowledge
base for many of the processes in these areas is very limited. This
paper reports some of the first measurements of fluxes of aerosols
and trace gases by micrometeorological methods over urban areas.
The limitations until recently have been partly instrument avail-
ability, but there has also been a reluctance to work in urban areas
simply due to the complexity of the surface and inertia within
the measurement community. It is necessary to understand the
dynamics in emissions and deposition of primary and secondary
particles. Trees or treated surfaces might act as depositing surfaces
improving air quality in cities (McDonald et al., 2007) or decreasing
the net ammonia emissions around farms. In many cases the
scientific challenge is clear and the measurement and modelling
needs are well within the capability of the community. There are
therefore many opportunities to advance the science which will find
rapid application in the policy arena.
The emerging subject of bioaerosols has been very briefly
mentioned in this review, and this represents a developing field
with application in cloud physics, air quality and human health as
well as the advance of basic understanding. A diverse range of
natural and anthropogenic particles are capable of initiating the ice
phase, but some of the most active naturally occurring ice nuclei (IN)
are biological in origin and have the capacity to catalyze freezing at
temperatures near to 2  C. Based on the ubiquitous distribution of
biological IN in snow and rain from global locations, they are likely
to encounter the appropriate conditions to affect atmospheric
processes leading to precipitation. The subject of organic aerosols
and cloud formation has been recently reviewed by Sun and Ariya
(2006). The cloud nucleation processes are currently among the
most uncertain in the global climate change modelling and
predictions. Surface fluxes of bioaerosols are a rapidly developing
field, and have wide application within current priority areas in
atmospheric composition, air quality and climate.
Acknowledgements
We gratefully acknowledge financial support from the European
Commission for the ACCENT, NitroEurope and GRAMINAE projects,
from COST for ACTION 729 and the European Science Foundation for
the Nitrogen in Europe (NinE) program. This work was also supported
by the UK Department for Environment Food and Rural Affairs.
References
Abbatt, J.P.D., 2003. Interactions of atmospheric trace gases with ice surfaces:
adsorption and reaction. Chemical Reviews, ACS Publications 103, 4783.
Abbot, D.S., Palmer, P.I., Martin, R.V., Chance, K.V., Jacob, D.J., Guenther, A., 2003.
Seasonal and interannual variability of isoprene emissions as determined by
formaldehyde column measurements from space. Geophysical Research Letters.
doi:10.1029/2003GL017336.
Allen, A.G., Harrison, R.M., Nicholson, K.W., 1991. Dry deposition of fine aerosol to
a short grass surface. Atmospheric Environment 25A, 2671–2676.
Altimir, N., Kolari, P., Tuovinen, J.-P., Vesala, T., Bäck, J., Suni, T., Kulmala, M., Hari, P.,
2006. Foliage surface ozone deposition: a role for surface moisture? Bio-
geosciences 3, 209–228.
Amato, P., Ménager, M., Sancelme, M., Laj, P., Mailhot, G., Delort A-, M., 2005.
Microbial population in cloud water the Puy de Dôme: implications for the
chemistry of clouds. Atmospheric Environment 39, 4143–4153.
Amato, P., Parazols, M., Sancelme, M., Laj, P., Mailhot, G., Delort, A.-M., 2007a. Micro-
organisms isolated from the water phase of tropospheric clouds at the Puy de
5255
Dôme: major groups and growth abilities at low temperatures. FEMS Micro-
biology Ecology 59 (2), 242–254.
Amato, P., Hennebelle, R., Magand, O., Sancelme, M., Delort, A.-M., Barbante, C.,
Boutron, C., Ferrari, C., 2007b. Bacterial characterization of the snow cover at
Spitzberg, Svalbard. FEMS Microbiology Ecology 59 (2), 255–264.
Amato, P., Demeer, F., Melaouhi, A., Martin-Biesse, A.-S., Sancelme, M., Laj, P.,
Delort, A.-M., 2007c. A fate for organic acids, formaldehyde and methanol in
cloud water: their biotransformation by micro-organisms. Atmospheric
Chemistry and Physics 7, 4159–4169.
Amato, P., Parazols, M., Sancelme, M., Mailhot, G., Laj, P., Delort, A.-M., 2007d. An
important oceanic source of micro-organisms for cloud water at the puy de
D̂ome (France). Atmospheric Environment 41, 8253–8263.
Ammann, C., Brunner, A., Spirig, C., Neftel, A., 2006. Technical note: water vapour
concentration and flux measurements with PTR-MS. Atmospheric Chemistry
and Physics 6, 4643–4651.
Andreas, E.L., 2002. A review of the sea spray generation function for the open
ocean. In: Perrie, W.A. (Ed.), Atmosphere–Ocean Interactions, vol. 1. WIT Press,
Southampton, UK, pp. 1–46.
Aneja, V.P., Schlesinger, W.H., Erisman, J.W., 2008. Farming pollution. Nature
Geoscience 1, 409–411.
Anttila, T., Kerminen, V.-M., 2002. Influence of organic compounds on the cloud
droplet activation: a model investigation considering the volatility, water solu-
bility, and surface activity of organic matter. Journal of Geophysical Research D
107 (D22), 4662. doi:10.1029/2001JD001482.
Ariya, P.A., Amyot, M., 2004. New directions: the role of bioaerosols in atmospheric
chemistry and physics. Atmospheric Environment 38, 1231–1232.
Arneth, A., Monson, R., Schurgers, G., Niinemets, Ü., Palmer, P.I. Why are estimates of
global isoprene emissions so similar (and why is this not so for monoterpenes)?
Atmospheric Chemistry and Physics, in press.
Arnold, S.R., Chipperfield, M.P., Blitz, M.A., Heard, D.E., Pilling, M.J., 2004. Photodisso-
ciation of acetone: atmospheric implications of temperature-dependent quantum
yields. Geophysical Research Letters 31, L07110. doi:10.1029/2003GL019099.
Ashmore, M., Fuhrer, J., 2000. Use and abuse of the AOT40 concept. Atmospheric
Environment 34, 1157–1158.
Ashmore, M.R., 2005. Assessing the future global impacts of ozone vegetation. Plant
Cell and Environment 28, 949–964.
Asman, W.A.H., Sutton, M.A., Schjoerring, J.K., 1998. Ammonia: emission, atmo-
spheric transport and deposition. New Phytologist 139, 27–48.
Audiffren, N., Cautenet, S., Chaumerliac, N., 1999. A modeling study of the influence of
ice scavenging on the chemical composition of liquid-phase precipitation of
a cumulonimbus cloud. Journal of Applied Meteorology 38 (8), 1148–1160 (AMS).
Bach, L.H., Frostegård, Å., Ohlson, M., 2008. Variation in soil microbial communities
across a boreal spruce forest landscape. Canadian Journal of Forest Research 38,
1504–1516.
Baker, B., Guenther, A., Greenberg, J., Goldstein, A., Fall, R., 1999. Canopy fluxes of
2-methyl-3-buten-2-ol over a ponderosa pine forest by relaxed eddy accumu-
lation: field data and model comparison. Journal of Geophysical Research 104,
26107–26114.
Balderston, W.L., Sherr, B., Payne, W.J., 1976. Blockage by acetylene of nitrous oxide
reduction in Pseudomonas perfectomarinus. Applied and Environmental Micro-
biology 31, 504–508.
Baldocchi, D., Falge, E., Gu, L., Olson, R., Hollinger, D., Running, S., Anthoni, P.,
Bernhofer, C., Davis, K., Evans, R., Fuentes, J., Goldstein, A., Katul, G., Law, B.,
Lee, X., Malhi, Y., Meyers, T., Munger, W., Oechel, W., Paw, U.K.T., Pilegaard, K.,
Schmid, H.P., Valentini, R., Verma, S., Vesala, T., Wilson, K., Wofsy, S., 2001.
FLUXNET: a new tool to study the temporal and spatial variability of ecosystem-
scale carbon dioxide, water vapour, and energy flux densities. Bulletin of the
American Meteorological Society 82, 2415–2434.
Barkley, M.P., Palmer, P.I., De Smedt, I., Karl, T., Guenther, A., Van Roozendael, M., 2009.
Regulated large-scale annual shutdown of Amazonian isoprene emissions?
Geophysical Research Letters 36, L04803. doi:10.1029/2008GL036843. 2009.
Bassin, S., Calanca, P., Weidinger, T., Gerosa, G., Fuhrer, J., 2004. Modelling seasonal
ozone fluxes to grassland and wheat: model improvement, testing and appli-
cation. Atmospheric Environment 38, 2349–2359.
Bauer, H., Giebl, H., Hitzenberger, R., Kasper-Giebl, A., Reischl, G., Zibuschka, F.,
Puxbaum, H., 2003. Airborne bacteria as cloud condensation nuclei. Journal of
Geophysical Research 108 (D21), 4658. doi:10.1029/2003JD003545.
Beauchamp, J., Wisthaler, A., Hansel, A., Kleist, E., Miebach, M., Niinemets, Ü.,
Schurr, U., Wildt, J., 2005. Ozone induced emissions of biogenic VOC from
tobacco: relations between ozone uptake and emission of LOX products. Plant
Cell and Environment 28, 1334–1343.
Benz, S., Megahed, K., Möhler, O., Saathoff, H., Wagner, R., Schurath, U., 2005.
T-dependent rate measurements of homogeneous ice nucleation in cloud
droplets using a large atmospheric simulation chamber. Journal of Photo-
chemistry and Photobiology A: Chemistry 176, 1–3 (special issue, 208–217).
Bergamaschi, P., Krol, M., Dentener, F., Vermeulen, A., Meinhardt, F., Graul, R.,
Ramonet, M., Peters, W., Dlugokencky, E.J., 2005. Onverse modelling of national
and European CH4 emissions using the atmospheric zoom model TM5. Atmo-
spheric Chemistry and Physics 5, 2431–2460.
Beswick, K.M., Hargreaves, K.J., Gallagher, M.W., Choularton, T.W., Fowler, D., 1991.
Size-resolved measurements of cloud droplet deposition velocity to a forest
canopy using an eddy-correlation technique. Quarterly Journal of the Royal
Meteorological Society 117 (499), 623–645.
Bigg, E.K., Leck, C., 2008. The composition of fragments of bubble bursting at ocean
surface. Journal of Geophysical Research 113, D11209. doi:10.1029/2007JD009078.
5256 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Blake, N.J., Blake, D.R., Wingenter, O.W., Sive, B.C., Thornton, D.C., Bandy, A.R.,
Atlas, E., Flocke, F., Rowland, F.S., 1999. Aircraft measurements of latitudinal,
vertical, and seasonal variations of NMHC, methyl nitrate, and selected halo-
carbons during the first aerosol characterization experiment (ACE-1). Journal of
Geophysical Research 104, 21803–21817.
Blanchard, D.C., 1964. Sea to air transport of surface active material. Science 146,
396–397.
Blande, J.D., Tiiva, P., Freiwald, V., Oksanen, E., Holopainen, J.K., 2005. The effects of
herbivore damage and elevated ozone concentration on the volatile terpenoids
produced by two hybrid aspen (Populus tremula x tremuloides) clones. In:
Abstracts. XVII International Botanical Congress, Vienna, Austria, 17–23 July
2005, Vienna, 544 pp.
Blatter, A., Neftel, A., Dasgupta, P.K., Simon, P.K., 1993. A combined wet effluent
denuder and mist chamber system for deposition measurements of NH3, NHþ 4,
HNO3 and NO 3 , 6th European Symposium of Physico-Chemical behavior of
atmospheric Pollutants, Varese, Italy.
Bleeker, A., Reinds, G.J., Vermeulen, A.T., de Vries, W., Erisman, J.W., 2004. Critical
loads and present deposition thresholds of nitrogen and acidity and their
exceedances at the level II and level I monitoring plots in Europe. ECN report
ECN-C-04–117, December 2004.
Bleeker, A., Sutton, M.A., Acherman, B., Alebic-Juretic, A., Aneja, V.P., Ellermann, T.,
Erisman, J.W., Fowler, D., Fagerli, H., Gauger, T., Harlen, K.S., Hole, L.R., Horváth, L.,
Mitosinkova, M., Smith, R.I., Tang, Y.S., van Pul, A., 2006. Linking ammonia
emission trends to measured concentrations and deposition of reduced nitrogen
at different scales. In: Proceedings of the UNECE NH3 Worshop, Edinburgh.
Blitz, M.A., Heard, D.E., Pilling, M.J., Arnold, S.R., Chipperfield, M.P., 2004. Pressure
and temperature-dependent quantum yields for the photodissociation of
acetone between 279 and 327.5 nm. Geophysical Research Letters 31, L06111.
doi:10.1029/2003GL018793.
Bollmann, A., Conrad, R., 1997. Enhancement by acetylene of the decomposition of
nitric oxide in soil. Soil Biology and Biochemistry 29, 1057–1066.
Bonn, B., Hirsikko, A., Hakola, H., Kurtén, T., Laakso, L., Boy, M., Dal Maso, M.,
Mäkelä, J.M., Kulmala, M., 2007. Ambient sesquiterpene concentration and its link
to air ion measurements. Atmospheric Chemistry and Physics 7, 2893–2916.
Bonsang, B., Polle, C., Lambert, G., 1992. Evidence for marine production of isoprene.
Geophysical Research Letters 19, 1129–1132.
Braaten, D.A., Paw, U.K.T., 1992. A stochastic particle resuspension and deposition
model. In: Fifth International Conference on Precipitation Scavenging and
Atmosphere–Surface Exchange Processes, Richland, Washington, 15–19 July
1991, pp. 1143–1152.
Brilli, F., Barta, C., Fortunati, A., Lerdau, M., Loreto, F., Centritto, M., 2007. Response of
isoprene emission and carbon metabolism to drought in white poplar (Populus
alba) saplings. New Phytologist 175, 244–254.
Brost, R.A., Delany, A.C., Huebert, B.J., 1988. Numerical modeling of concentrations
and fluxes of HNO3, NH3, and NH4NO3 near the surface. Journal of Geophysical
Research 93, 7137–7152.
Brunner, A., Ammann, C., Neftel, A., Spirig, C., 2007. Methanol exchange between
grassland and the atmosphere. Biogeosciences 4, 395–410.
Buchwitz, M., de Beek, R., Burrows, J.P., Bovensmann, H., Warneke, T., Notholt, J.,
Meirink, J.F., Goede, A.P.H., Bergamaschi, P., Körner, S., Heimann, M., Schulz, A.,
2005. Atmospheric methane and carbon dioxide from SCIAMACHY satellite
data: initial comparison with chemistry and transport models. Atmospheric
Chemistry and Physics 5, 941–962.
Buchwitz, M., de Beek, R., Noel, S., 2006. Atmospheric carbon gases retrieved
from SCIAMACHY by WFM-DOAS: version 0.5 CO and CH4 and impact of
calibration improvements on CO2 retrieval. Atmoshperic Chemistry and
Physics 6, 2727–2751.
Burkhard, R., Eugster, W., Wrzesinski, T., Klemm, O., 2002. Vertical divergence of
fogwater fluxes above a spruce forest. Atmospheric Research 64, 133–145.
Burkhardt, J., Flechard, C.R., Gresens, F., Mattsson, M.E., Jongejan, P.A.C., Erisman, J.W.,
Weidinger, T., Meszaros, R., Nemitz, E., Sutton, M.A., 2008. Modelling the chemical
interactions of atmospheric ammonia and other trace gases fluxes with measured
leaf surface wetness in a managed grassland canopy. Biogeosciences Discussions
5, 2505–2539.
Businger, J.A., Wyngaard, J., Izumi, Y., Bradley, E.F., 1971. Flux–profile relationships
in the atmospheric surface layer. Journal of the Atmospheric Sciences 28,
181–189.
Butterbach-Bahl, K., Gasche, R., Breuer, L., Papen, H., 1997. Fluxes of NO and N2O
from temperate forest soils: impact of forest type, N deposition and of liming on
the NO and N2O emissions. Nutrient Cycling in Agroecosystems 48, 1314–1385.
Butterbach-Bahl, K., Willibald, G., Papen, H., 2002. Soil core method for direct
simultaneous determination of N2 and N2O emissions from forest soils. Plant
and Soil 240, 105–116.
Butterbach-Bahl, K., Kesik, M., Miehle, P., Papen, H., Li, C., 2004. Quantifying the
regional source strength of N-trace gases across agricultural and forest
ecosystems with process based models. Plant and Soil 260, 311–329.
Butterbach-Bahl, K., Mykhayliv, L., Werner, C., Kiese, R., Li, C., 2009. A European
wide inventory of soil NO emissions using the biogeochemical models DNDC/
Forest DNDC. Atm. Environm 43, 1392–1402.
Buzorius, G., Rannik, U., Makela, J.M., Vesala, T., Kulmala, M., 1998. Vertical aerosol
particle fluxes measured by eddy covariance technique using condensational
particle counter. Journal of Aerosol Science 29, 157–171.
Buzorius, G., Rannik, U., Nilsson, D., Kulmala, M., 2001. Vertical fluxes and micro-
meteorology during aerosol particle formation events. Tellus Series B-Chemical
and Physical Meteorology 53, 394–405.
Buzorius, G., Kalogiros, J., Varutbangkul, V., 2006. Airborne aerosol flux measure-
ments with eddy correlation above the ocean in a coastal environment. Journal
of Aerosol Science 37, 1267–1286.
Cape, J.N., Sheppard, L.J., Binnie, J., Dickinson, A.L., Dollard, G.F., Fowler, D., 1998.
Enhancement of the dry deposition of sulphur dioxide to a forest in the
presence of ammonia. Atmospheric Environment 32, 519–524.
Cape, J.N., Kirika, A., Rowland, A.P., Wilson, D.R., Jickells, T.D., Cornell, S., 2001.
Organic nitrogen in precipitation: real problem or sampling artefact? The
Scientific World 1, 230–237.
Cape, J.N., 2008. Surface ozone concentrations and ecosystem health: past trends and
a guide to future projections. Science of the Total Environment 400, 257–269.
Cape, J.N., Hamilton, R., Heal, M.R., 2009. Reactive uptake of ozone at simulated leaf
surfaces: implications for ‘non-stomatal’ ozone deposition. Atmospheric Envi-
ronment 43, 1116–1123.
Carpenter, L.J., Lewis, A.C., Hopkins, J.R., Read, K.A., Longley, I.A., Gallagher, M.W.,
2004. Uptake of methanol to the North Atlantic Ocean surface. Global Biogeo-
chemical Cycles 18 (4), GB4027.
Casciotti, K.L., Böhlke, J.K., McIlvin, M.R., Mroczkowski, S.J., Hannon, J.E., 2007.
Oxygen isotopes in nitrite: analysis, calibration, and equilibration. Analytical
Chemistry 79, 2427–2436.
Cavalli, F., Facchini, M.C., Decesari, S., Mircea, M., Emblico, L., Fuzzi, S., Ceburnis, D.,
Yoon, Y.J., O’Dowd, C.D., Putaud, J.-P., Dell’Acqua, A., 2004. Advances in char-
acterization of size resolved organic matter in marine aerosol over the North
Atlantic. Journal of Geophysical Research. doi:10.1029/2004JD0051377.
Ceburnis, D., O’Dowd, C.D., Jennings, S.G., Facchini, M.C., Emblico, L., Decesari, S.,
Fuzzi, S., Sakalys, J., 2008. Elucidation of production mechanisms of water
soluble and insoluble organic carbon in marine air and associated gradient
fluxes over the Northeast Atlantic. Geophysical Research Letters 35, L07804.
doi:10.1029/2008GL033462.
Chameides, W.L., Lindsay, R.W., Richardson, J., Kiang, C.S., 1988. The role of biogenic
hydrocarbons in urban photochemical smog: Atlanta as a case study. Science
241, 1473–1475.
Chance, K., Palmer, P.I., Martin, R.V., Spurr, R.J.D., Kurosu, T.P., Jacob, D.J., 2000.
Satellite observations of formaldehyde over North America from GOME.
Geophysical Research Letters 27, 3461–3464.
Chang, C., Janzen, H.H., Cho, C.M., Nakonechny, E.M., 1998. Nitrous oxide emission
through plants. Soil Science Society of America Journal 62, 35–38.
Chang, W., Heikes, B.G., Lee, M., 2004. Ozone deposition to the sea surface: chemical
enhancement and wind speed dependence. Atmospheric Environment 38,
1053–1059.
Chapuis-Lardy, L.E., Wrage, N., Metay, A., Chotte, J.L., Bernoux, M., 2007. Soils, a sink
for N2O? A review. Global Change Biology 13, 1–17.
Chen, X., Boeckx, P., Shen, S., Van Cleemput, O., 1999. Emission of N2O from rye grass
(Lolium perenne L.). Biology and Fertility of Soils 8, 393–396.
Christensen, S., Ambus, P., Arah, J.R.M., Clayton, H., Galle, B., Griffith, D.W.T.,
Hargreaves, K.J., Klemedtsson, L., Lind, A.-M., Maag, M., Scott, A., Skiba, U.,
Smith, K.A., Welling, M., Wienhold, F.G., 1996. Nitrous oxide emission from an
agricultural field: comparison between measurements by flux chamber and
micrometerological techniques. Atmospheric Environment 30, 4183–4190.
Christensen, C.S., Hummelshøj, P., Jensen, N.O., Larsen, B., Lohse, C., Pilegaard, K.,
Skov, H., 2000. Determination of the terpene flux from orange species and
Norway spruce by relaxed eddy accumulation. Atmospheric Environment 34,
3057–3067.
Chuck, A.L., Turner, S.M., Liss, P.S., 2002. Direct evidence of a marine source of C1
and C2 alkyl nitrates. Science 297, 1151–1154.
Ciccioli, P., Fabozzi, C., Brancaleoni, E., Cecinato, A., Frattoni, M., Cieslik, S.,
Kotzias, D., Seufert, G., Foster, P., Steinbrecher, R., 1997. Biogenic emission from
the Mediterranean pseudosteppe ecosystem present in Castelporziano. Atmo-
spheric Environment 31, 167–175.
Ciccioli, P., Brancaleoni, E., Frattoni, M., Di Palo, V., Valentini, R., Tirone, G.,
Seufert, G., Bertin, N., Hansen, U., Csiky, O., Lenz, R., Sharma, M., 1999.
Emission of reactive terpene compounds from orange orchards and their
removal by within-canopy processes. Journal of Geophysical Research 104,
8077–8094.
Cicerone, R., 1989. Analysis of sources and sinks of atmospheric nitrous oxide (N2O).
Journal of Geophysical Research 94, 18265–18271.
Cieslik, S.A., 2004. Ozone uptake by various surface types: a comparison between
dose and exposure. Atmospheric Environment 38, 2409–2420.
Cieslik, S. 2009. Ozone fluxes over various plant ecosystems in Italy: a review.
Ozone and Mediterranean Ecology: Plants, People, Problems. Environmental
Pollution, 157, 1487–1496 (Special Issue Section)
Clarke, A.D., Owens, S.R., Zhou, J., 2006. An ultrafine sea-salt flux from breaking
waves: implications for cloud condensation nuclei in the remote marine
atmosphere. Journal of Geophysical Research 111, D06202. doi:10.1029/
2005JD006565. 14.
Clifford, D., Donaldson, D.J., Brigante, M., D’Anna, B., George, D., 2008. Reactive
uptake of ozone by chlorophyll at aqueous surfaces. Environmental Science &
Technology 42, 1138–1143.
Colbeck, I., Harrison, R.M., 1985. The photochemical pollution episode of 5–16 July
1983 in North-West England. Atmospheric Environment 19, 1921–1929.
Conen, F., Smith, K.A., 1998. A re-examination of closed flux chamber methods for
the measurement of trace gas emissions from soils to the atmosphere. Euro-
pean Journal of Soil Science 49, 701–707.
Conen, F., Neftel, A., 2007. Do increasingly depleted d15N values of atmospheric N2O
indicate a decline in soil N2O reduction? Biogeochemistry 82, 321–326.
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Conrad, R., 1995. Soil microbial processes and the cyclig of atmospheric trace gases.
Philosophical Transactions of the Royal Society of London 351, 219–230.
Cornell, S.E., Jickells, T.D., Cape, J.N., Rowland, A.P., Duce, R.A., 2003. Organic
nitrogen deposition on land and coastal environments: a review of methods
and data. Atmospheric Environment 37, 2173–2191.
Coyle, M., Smith, R., Fowler, D., 2003. An ozone budget for the UK: using
measurements from the national ozone monitoring network; measured and
modelled meteorological data, and a ‘big-leaf’ resistance analogy model for dry
deposition. Environmental Pollution 123, 115–123.
Coyle, M., 2005. The Gaseous Exchange of Ozone at Terrestrial Surfaces: Non-
stomatal Deposition to Grassland, School of Geosciences, Faculty of Science and
Engineering. PHD thesis. The University of Edinburgh, Edinburgh, 270 pp.
Coyle, M., Fowler, D., Nemitz, E., Philips, G., Storeton-West, R., Thomas, R., 2006.
Field measurements of the ozone flux to vegetation. In: Ozone Umbrella: Effects
of Ground-level Ozone on (Upland) Vegetation in the UK. Centre of Ecology and
Hydrology, UK, pp. 68–104. CEH C02158 Report No. AS 06/02.
Coyle, M., Altimir, N., Grunhage, L., Gerosa, G., Tuovinen, J.P., Loubet, B., Ammann, C.,
Cieslik, S., Paoletti, E., Fowler, D., Mikkleson, T., Ro-Poulsen, H., Cellier, P., 2008a.
Non-stomatal Ozone Deposition to Vegetation: New Insights and Models. EGU
General Assembly 2008. European Geophysical Union, Vienna, Austria.
Coyle, M., Nemitz, E., Storeton-West, R., Fowler, D., Cape, J.N. 2009. Measurements of
ozone deposition to a potato canopy. Agricultural and Forest Meteorology, 149,
656–666.
Crutzen, P.J., Lawrence, M.G., 2000. The impact of precipitation scavenging on the
transport of race gases: a 3-D dimensional model sensitivity study. Journal of
Atmospheric Chemistry 37, 81–112.
Crutzen, P.J., Mosier, A.R., Smith, K.A., Winiwarter, W., 2008. N2O release from agro-
biofuel production negates global warming reduction by replacing fossil fuels.
Atmospheric Chemistry and Physics 8, 389–395.
Cubison, M.J., Alfarra, M.R., Allan, J., Bower, K.N., Coe, H., McFiggans, G.B.,
Whitehead, J.D., Williams, P.I., Zhang, Q., Jimenez, J.L., Hopkins, J., Lee, J., 2006. The
characterisation of pollution aerosol in a changing photochemical environment.
ACP 6, 1–15.
Dahl, E.E., Saltzman, E.S., de Bruyn, W.J., 2003. The aqueous phase yield of alkyl
nitrates from ROO þ NO: implications for photochemical production in
seawater. Geophysical Research Letters 30 (6), 1271. doi:10.1029/2002GL016811.
Darmais, S., Dutaur, L., Larsen, B., Cieslick, S., Luchetta, L., Simon, V., Torres, L., 2000.
Emission flux of VOC by orange trees determined by both eddy accumulation
and vertical gradient approaches. Chemosphere 2, 47–56.
Davidson, C.I., Miller, J.M., Pleskow, M.A., 1982. The influence of surface structure on
predicted particle dry deposition to natural grass canopies. Water, Air and Soil
Pollution 18, 25–43.
Davidson, E.A., 1991. Fluxes of nitrous oxide and nitric oxide from terrestrial
ecosystems. In: Rogers, J.E., Whitman, W.B. (Eds.), Microbial Production and
Consumption of Greenhouse Gases: Methane, Nitrogen Oxides, and Halo-
methanes. American Society for Microbiology, Washington, pp. 219–235.
Davison, B., Brunner, A., Ammann, C., Spirig, C., Jocher, M., Neftel, A., 2008.
Cut-induced VOC emissions from agricultural grasslands. Plant Biology 10,
76–85.
Davison, B., Taipale, R., Langford, B., Misztal, P., Fares, S., Matteucci, G., Loreto, F.,
Cape, J.N., Rinne, J., Hewitt, C.N., 2009. Concentrations and fluxes of biogenic
volatile organic compounds above a Mediterranean macchia ecosystem in
Western Italy. Biogeosciences Discussions 6, 2183–2216.
De Arellano, J., Duynkerke, P., 1992. Influence of chemistry on flux–gradient rela-
tionships in the NO–O3–NO2 system. Boundary-Layer Meteorology 28, 181–189.
De Carlo, P.F., Kimmel, J.R., Trimborn, A., Northway, M.J., Jayne, J.T., Aiken, A.C.,
Gonin, M., Fuhrer, K., Horvath, T., Docherty, K., Worsnop, D.R., Jimenez, J.L.,
2006. Field-deployable, high-resolution, time-of-flight aerosol mass spec-
trometer. Analytical Chemistry 78, 8281–8289.
Deguillaume, L., Leriche, M., Desboeufs, K., Mailhot, G., George, C., Chaumerliac, N.,
2005. Transition metals in atmospheric liquid phases: sources, reactivity, and
sensitive parameters. Chemical Reviews 105 (9), 3388–3431.
Deguillaume, L., Leriche, M., Amato, P., Ariya, P.A., Delort, A.-M., Pöschl, U.,
Chaumerliac, N., Bauer, H., Flossmann, A.I., Morris, C.E., 2008. Microbiology and
atmospheric processes: chemical interactions of primary biological aerosols.
Biogeosciences 5, 1073–1084.
Denmead, O.T., Freney, J.R., Simpson, J.R., 1976. A closed ammonia cycle within
a plant canopy. Soil Biology and Biochemistry 8, 161–164.
Denmead, O.T., 2008. Approaches to measuring fluxes of methane and nitrous oxide
between landscapes and the atmosphere. Plant and Soil 309, 5–24.
Dentener, F.J., Crutzen, P.J., 1994. Atmospheric ammonia from undisturbed land.
Journal of Geophysics Research 82, 3125–3133.
Dentener, F., Drevet, J., Lamarque, J.F., Bey, I., Eickhaut, B., Fiore, A.M.,
Hauglustaine, D., Horowitz, L.W., Krok, M., Kulshrestha, U.C., Lawrence, M.,
Galy-Lacaux, C., Rast, S., Shindell, D., Stevenson, D., van Noije, T., Atherton, C.,
Bell, N., Bergman, D., Butler, T., Cofala, J., Collins, B., Docherty, R., Ellingsen, K.,
Galloway, J., Gauss, M., Montanaro, V., Müller, J.F., Pitari, G., Rodriguez, J.,
Sanderson, M., Solmon, F., Strahan, S., Schulz, M., Sudo, K., Szopa, S., Wild, O.,
2006. Nitrogen and sulfur deposition on regional and global scales: a multi-
model evaluation. Global Biogeochemistry Cycles 20 (4), GB4003.
Derome, J., Nieminen, T., Saarsalmi, A., 2004. Sulphur dioxide adsorption in Scots
pine canopies exposed to high ammonia emissions near a Cu–Ni smelter in SW
Finland. Environmental Pollution 129, 79–88.
Di Carlo, P., Brune, W.H., Martinez, M., Harder, H., Lesher, R., Ren, X., Thornberry, T.,
Carroll, M.A., Young, V., Shepson, P.B., Riemer, D., Apel, E., Campbell, C., 2004.
5257
Missing OH reactivity in a forest: evidence for unknown reactive biogenic VOCs.
Science 304, 722–724.
Di Marco, C., Skiba, U., Weston, K., Hargreaves, K., 2004. Field scale N2O flux
measurements from grassland using eddy covariance. Water, Air and Soil
Pollution: Focus 4, 143–149.
Dollard, G.J., Unsworth, M.H., 1983. Field measurements of turbulent fluxes of wind-
driven fog drops to a grass surface. Atmospheric Environment 17, 775–780.
Donateo, A., Contini, D., Belosi, F., 2006. Real time measurements of PM2.5
concentrations and vertical turbulent fluxes using an optical detector. Atmo-
spheric Environment 40, 1346–1360.
Dore, A.J., Mousavi-Baygi, M., Smith, R.I., Hall, J., Fowler, D., Choularton, T.W., 2006.
A model of annual orographic precipitation and acid deposition and its appli-
cation to Snowdonia. Atmospheric Environment 40, 3316–3326.
Dorsey, J.R., Nemitz, E., Gallagher, M.W., Fowler, D., Williams, P.I., Bower, K.N.,
Beswick, K.M., 2002. Direct measurements and parameterisation of aerosol flux,
concentration and emission velocity above a city. Atmospheric Environment 36,
791–800.
Dorsey, J.R., Duyzer, J.H., Gallagher, M.W., Coe, H., Pilegaard, K., Weststrate, J.H.,
Jensen, N.O., Walton, S., 2004. Oxidized nitrogen and ozone interaction with
forest. I: experimental observations and analysis of exchange with Douglas fir.
Quarterly Journal of the Royal Meteorological Society 130, 1941–1955.
Duan, B., Fairall, C.W., Thomson, D.W.,1988. Eddy-covariance measurements of the dry
deposition of particles in wintertime. Journal of Applied Meteorology 28, 642–652.
Dueck, T.A., de Visser, R., Poorter, H., Persijn, S., Gorissen, A., de Visser, W.,
Schapendonk, A., Verhagen, J., Snel, J., Harren, F.J.M., Ngai, A.K.Y., Verstappen, F.,
Bouwmeester, H., Voesenek, L.A.C.J., van der Werf, A., 2007. No evidence for
substantial aerobic methane emission by terrestrial plants: a 13C-labelling
approach. New Phytologist 175, 29–35.
Duyzer, J.H., Meyer, G.M., van Aalst, R.M., 1983. Measurement of dry deposition
velocities of NO, N and O3 and the influence of chemical reactions. Atmospheric
Environment 17 (10), 2117–2120 (1967).
Duyzer, J., 1994. Dry deposition of ammonia and ammonium aerosols over heath-
land. Journal of Geophysical Research – Atmospheres 99, 18757–18763.
Duyzer, J., Weststrate, H., Walton, S., 1995. Exchange of ozone and nitrogen oxides
between the atmosphere and coniferous forest. Journal Water, Air, & Soil
Pollution 85 (4), 2065–2070. Springer, Netherlands.
Duyzer, J.H., Dorsey, J.R., Gallagher, M.W., Pilegaard, K., Walton, S., 2004. Oxidized
nitrogen and ozone interaction with forests. II: multi-layer process-oriented
modelling results and a sensitivity study for Douglas fir. Quarterly Journal of the
Royal Meteorological Society 130 (600 PART A), 1957–1971.
Duyzer, J., 2005a. Interactive comment on ‘‘A simple model to estimate exchange
rates of nitrogen dioxide between the atmosphere and forests’’. Biogeosciences
Discussions 2 (Suppl.), S905–S911.
Duyzer, J., 2005b. A simple model to estimate exchange rates of nitrogen dioxide between
the atmosphere and forests. Biogeosciences Discussions 2, 1033–1065. 2005.
Eastman, J.A., Stedman, D.H., 1977. A fast sensor for ozone eddy-correlation flux
measurements. Atmospheric Environment 11, 1209–1211.
Ekdahl, A., Pedersén, M., Abrahamsson, K., 1998. A study of the diurnal variation of
biogenic volatile halocarbons. Marine Chemistry 63, 1–8.
Emberson, L.D., Ashmore, M.R., Cambridge, H.M., Simpson, D., Tuovinen, J.-P., 2000.
Modelling stomatal ozone flux across Europe. Environmental Pollution 109,
403–413.
Emberson, L.D., Büker, P., Ashmore, M.R., 2007. Assessing the risk caused by ground
level ozone to European forest trees: a case study in pine, beech and oak across
different climate regions. Environmental Pollution 147, 454–466.
Erisman, J.W., 1993. Acid deposition onto nature areas in The Netherlands. Part II:
throughfall measurements compared to deposition estimates. Water Air Soil
Pollut. 71, 81–99.
Erisman, J.W., Wyers, G.P., 1993. Continuous measurements of surface exchange of
SO2 and NH3: implications for their possible interaction in the deposition
process. Atmospheric Environment 27A, 1937–1949.
Erisman, J.W., 1994. Evaluation of a surface resistance parametrization of sulphur
dioxide. Atmospheric Environment 28, 2583–2594.
Erisman, J.W., Draaijers, G., Duyzer, J., Hofschreuder, P., Van Leeuwen, N., Roemer, F.,
Ruijgrok, W., Wyers, P., Gallagher, M., 1996. Particle deposition to forests –
summary of results and application. Atmospheric Environment 31, 321–332.
Erisman, J.W., Hensen, A., Fowler, D., Flechard, C., Grüner, A., Spindler, G., Duyzer, J.,
Weststrate, H., Römer, F., Vonk, A., van Jaarsveld, H., 2001. Dry deposition
monitoring in Europe. WASP Focus 1, 17–27.
Erisman, J.W., Sutton, M.A., Galloway, J., Klimont, Z., Winiwarter, W., 2008. How
a century of ammonia synthesis changed the world. Nature Geoscience 1, 636–
639. doi:10.1038/ngeo325.
Ervens, B., George, C., Williams, J.E., Boxton, G.V., Salmon, G.A., Bydder, M.,
Wilkinsons, F., Dentener, F., Mirabel, P., Wolke, R., Herrmann, H., 2004a. CAP-
RAM 2.4 (MODAC mechanism): an extended and condensed tropospheric
aqueous phase mechanism and its application. Journal of Geophysical Research
108. doi:10.1029/2002JD002202.
Ervens, B., Feingold, G., Frost, G.J., Kreidenweis, S.M., 2004b. A modeling study of
aqueous production of dicarboxylic acids: 1. Chemical pathways and speciated
organic mass production. Journal of Geophysical Research 109, D15205.
doi:10.1029/2003JD004387.
Facchini, M.C., Decesari, S., Rinaldi, M., Carbone, C., Finessi, E., Mircea, M., Fuzzi, S.,
Moretti, F., Tagliavini, E., Ceburnis, D., O’Dowd, C.D., 2008. An important source
of marine secondary organic aerosol from biogenic amines. Environmental
Science & Technology. doi:10.1021/es8018385.
5258 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Fairall, C.W., 1984. Interpretation of eddy-correlation measurements of particulate
deposition and aerosol flux. Atmospheric Environment 18, 1329–1337.
Fairall, C.W., Helmig, D., Ganzeveld, L., Hare, J., 2007. Water-side turbulence
enhancement of ozone deposition to the ocean. Atmospheric Chemistry and
Physics 7, 443–451.
Fall, R., 2003. Abundant oxygenates in the atmosphere: a biochemical perspective.
Chemical Reviews 103, 4941–4951.
Fall, R., Karl, T., Hansel, A., Jordan, A., Lindinger, W., 1999. Volatile organic
compounds emitted after leaf wounding: online analysis by proton transfer-
reaction mass spectrometry. Journal of Geophysical Research 104, 15963–15974.
Famulari, D., Fowler, D., Hargreaves, K., Milford, C., Nemitz, E., Sutton, M.,
Weston, K., 2004. Measuring eddy covariance fluxes of ammonia using tunable
diode laser absorption spectroscopy. WASP Focus 4 (6), 151–158.
Famulari, D., Fowler, D., Storeton-West, R.L., Nemitz, E., Hargreave, K., Rutherford, G.,
Tang, Y.S, Sutton, M.A., Weston, K.J. Development of a low-cost system for
measuring conditional time-averaged gradients of SO2 and NH3. Environmental
Monitoring and Assessment, in press, doi:10.1007/s10661-008-0723-6.
Fang, Y.T., Gundersen, P., Mo, J.M., Zhu, W.X., 2008. Input and output of dissolved
organic and inorganic nitrogen in subtropical forests of South China under high
air pollution. Biogeosciences 5, 339–352.
Farmer, D.K., Woolridge, P.J., Cohen, R.C., 2006. Application of thermal-dissociation
laser induced fluorescence (TD-LIF) to measurement of HNO3, aklyl nitrates,
peroxy nitrates and NO2 fluxes using eddy covariance. Atmospheric Chemistry
and Physics 6, 3471–3486.
Farquhar, G.D., Firth, P.M., Wetselaar, R., Wier, B., 1980. On the gaseous exchange of
ammonia between leaves and the environment: determination of the ammonia
compensation point. Plant Physiology 66, 710–714.
Feingold, G., Kreidenweis, S.M., 2002. Cloud processing of aerosol as modeled by
a large eddy simulation with coupled microphysics and aqueous chemistry.
Journal of Geophysical Research 107, 4687. doi:10.1029/2002JD002054.
Feliciano, M.S., Pio, C.A., Vermeulen, A.T., 2001. Evaluation of SO2 dry deposition
over short vegetation in Portugal. Atmospheric Environment 35, 3633–3643.
Felzer, B., Reilly, J., Melillo, J., Kicklighter, D., Sarofim, M., Wang, C., Prinn, R., Zhuang, Q.,
2005. Future effects of ozone on carbon sequestration and climate change policy
using a global biogeochemical model. Climatic Change 73, 345–373.
Finkelstein, P.L., Ellestad, T.G., Clarke, J.F., Meyers, T.P., Schwede, D., Hebert, E.O.,
Neal, J.F., 2000. Ozone and sulfur dioxide dry deposition to forests: observations
and model evaluation. Journal of Geophysical Research 105, 15365–15377.
Fiore, A.M., Horowitz, L.W., Purves, D.W., Levy II, H., Evans, M.J., Wang, Y., Li, Q.,
Yantosca, R.M., 2005. Evaluating the contribution of changes in isoprene
emissions to surface ozone trends over the eastern United States. Journal of
Geophysical Research 110, D12303. doi:10.1029/2004JD005485.
Fischbach, R.J., Staudt, M., Zimmer, I., Rambal, S., Schnitzler, J.P., 2002. Seasonal
pattern of monoterpene synthase activities in leaves of the evergreen tree
Quercus ilex. Physiologia Plantarum 114, 354–360.
Fisher, B.E.A., 1978. The calculation of long term sulphur deposition in Europe.
Atmospheric Environment 12, 489–501.
Flechard, C.R., Fowler, D., 1998. Atmospheric ammonia at a moorland site. II: long-
term surface–atmosphere micrometeorological flux measurements. Quarterly
Journal of the Royal Meteorological Society 124, 759–791.
Flechard, C., Fowler, D., Sutton, M.A., Cape, J.N., 1999. A dynamic chemical model
of bi-directional ammonia exchange between semi-natural vegetation and
the atmosphere. Quarterly Journal of the Royal Meteorological Society 125,
2611–2641.
Flechard, C.R., Neftel, A., Jocher, M., Ammann, C., Leifeld, J., 2007. Temporal changes
in soil pore space CO2 concentration and storage under permanent grassland.
Agricultural and Forest Meteorology 142, 66–84.
Flossmann, A.I., Wobrock, W., 1996. Venting of gases by convective clouds. Journal
of Geophysical Research 101, 18639–18649.
Flossmann, A., 1998a. Clouds and pollution. Pure & Applied Chemistry 70, 1345–1352.
Flossmann, A.I., 1998b. Interaction of aerosol particles and clouds. Journal of
Atmospheric Science 55, 879–887.
Fontan, J., Lopez, A., Lamaud, E., Druilhet, A., 1997. Vertical flux measurements of the
submicronic aerosol particles and parameterization of the dry deposition
velocity. In: Slanina, J. (Ed.), Biosphere–Atmosphere Exchange of Pollutants and
Trace Substances. Springer Verlag, Heidelberg, Germany, pp. 381–390.
Fowler, D., Unsworth, M.H., 1974. Dry deposition of sulphur dioxide on wheat.
Nature, London 249, 389–390.
Fowler, D., Unsworth, M.H., 1979. Turbulent transfer of sulphur dioxide to a wheat
crop. Quarterly Journal of the Royal Meteorological Society 105, 767–783.
Fowler, D., Duyzer, J.H., 1989. Micrometeorological techniques for the measurement
of trace gas exchange. In: Andreae, M.O., Schimel, D.S. (Eds.), Exchange of Trace
Gases Between Terrestrial Ecosystems and the Atmosphere. Wiley, Chichester,
UK, pp. 189–207.
Fowler, D., Flechard, C.R., Sutton, M.A., Storeton-West, R.L., 1998. Long term
measurements of land–atmosphere exchange of ammonia over moorland.
Atmospheric Environment (Ammonia Special Issue) 32, 453–459.
Fowler, D., Cape, J.N., Coyle, M., Flechard, C., Kuylenstierna, J., Hicks, K.,
Derwent, R.G., Johnson, C., Stevenson, D., 1999. The global exposure of forests to
air pollutants. Water, Air and Soil Pollution 116, 5–32.
Fowler, D., Flechard, C., Cape, J.N., Storeton-West, R.L., Coyle, M., 2001a. Measure-
ments of ozone deposition to vegetation quantifying the flux, the stomatal and
non-stomatal components. Water, Air and Soil Pollution 130, 63–74.
Fowler, D., Coyle, M., Flechard, C., Hargreaves, K.J., Nemitz, E., Storeton-West, R.,
Sutton, M.A., Erisman, J.W., 2001b. Advances in micrometeorological methods
for the measurement and interpretation of gas and particle nitrogen fluxes.
Plant and Soil 228, 117–129.
Fowler, D., Sutton, M.A., Flechard, C., Cape, J.N., Storeton-West, R., Coyle, M.,
Smith, R.I., 2001c. The control of SO2 dry deposition on to natural surfaces and
its effects on regional deposition. Water, Air and Soil Pollution: Focus 1, 39–48.
Fowler, D., Smith, R.I., Muller, J.B.A., Hayman, G., Vincent, K.J., 2005. Changes in the
atmospheric deposition of acidifying compounds in the UK between 1986 and
2001. Environmental Pollution 137, 15–25.
Fowler, D., Smith, R.I., Muller, J., Cape, J.N., Sutton, M., Erisman, J.W., Fagerli, H., 2007.
Long term trends in sulphur and nitrogen deposition in Europe and the cause of
non-linearities. Water, Soil and Air Pollution: Focus 7, 41–47.
Frankenberg, C., Bergamaschi, P., Butz, A., Houweling, S., Meirink, J.F., Notholt, J.,
Petersen, A.K., Schrijver, H., Warneke, T., Aben, I., 2008. Tropical methane
emissions: a revised view from SCIAMACHY onboard ENVISAT. Geophysical
Research Letters 35, LI15811.
Fratini, G., Ciccioli, P., Febo, A., Forgione, A., Valentini, R., 2007. Size-segregated
fluxes of mineral dust from a desert area of northern China by eddy covariance.
Atmospheric Chemistry and Physics 7, 2839–2854.
Fuentes, J.D., 1992. Effect of Foliage Surface Wetness on the Deposition of Ozone.
Ph.D. thesis. University of Guelph, Guelph, Ontario, Canada.
Fuhrer, J., Skärby, L., Ashmore, M.R., 1997. Critical levels for ozone effects on vege-
tation in Europe. Environmental Pollution 97, 91–106.
Fuzzi, S., Mandrioli, P., Perfetto, A., 1997. Fog droplets – an atmospheric source of
secondary biological aerosol particles. Atmospheric Environment 31, 287–290.
Galbally, I.E., 1971. Ozone profiles and fluxes in the atmospheric surface layer.
Quarterly Journal of the Royal Meteorological Society 97, 18–29.
Galbally, I.E., Roy, C.R., 1980. Destruction of ozone at the earth’s surface. Quarterly
Journal of the Royal Meteorological Society 106, 599–620.
Galbally, I.E., Kirstine, W., 2002. The production of methanol by flowering plants
and the global cycle of methanol. Journal of Atmospheric Chemistry 43,
195–229.
Gallagher, M.W., Beswick, K.M., Duyzer, J., Westrate, H., Choularton, T.W.,
Hummelshoj, P., 1997. Measurements of aerosol fluxes to Speulder forest using
a micrometeorological technique. Atmospheric Environment 31, 359–373.
Gallagher, M.W., Beswick, K.M., Coe, H., 2001. Ozone dry deposition to coastal
waters. Quarterly Journal of the Royal Meteorological Society 127, 539–558.
Galloway, J.N., Aber, J.D., Erisman, J.W., Seitzinger, S.P., Howarth, R.W., Cowling, E.B.,
Cosby, B.J., 2003. The nitrogen cascade. BioScience 53, 341–356.
Galloway, J.N., Dentener, F.J., Capone, D.G., Boyer, E.W., Howarth, R.W.,
Seitzinger, S.P., Asner, G.P., Cleveland, C.C., Green, P.A., Holland, E.A., Karl, D.M.,
Michaels, A.F., Porter, J.H., Townsend, A.R., Vorosmarty, C.J., 2004. Nitrogen
cycles: past, present, and future. Biogeochemistry 70, 153–226.
Gaman, A., Rannik, U., Aalto, P., Pohja, T., Siivola, E., Kumala, M., Vesala, T., 2004.
Relaxed eddy accumulation system for size resolved aerosol particle flux
measurements. Journal of Atmospheric and Oceanic Technology 21, 933–943.
Gao, W., Shaw, R.H., Paw, U.K.T., 1989. Observation of organized structures in
turbulent flow within and above a forest canopy. Boundary-Layer Meteorology
47, 349–377.
Garland, J.A., Derwent, R.G., 1979. Destruction at the ground and the diurnal cycle of
concentration of ozone and other gases. Quarterly Journal of the Royal Mete-
orological Society 105, 169–183.
Gasche, R., Papen, H., 1999. A 3-year continuous record of nitrogen trace gas fluxes
from untreated and limed soil of a N-saturated spruce and beech forest
ecosystem in Germany. Part 2: NO and NO2 fluxes. Journal of Geophysical
Research D, Atmospheres 104 (15), 18505–18520.
Geever, M., O’Dowd, C., van Ekeren, S., Flanagan, R., Nilsson, D., de Leeuw, G.,
Rannik, U., 2005. Sub-micron sea-spray fluxes. GRL 32 (2005), L15810.
Gerosa, G., Cieslik, S., Ballarin-Denti, A., 2003. Micrometeorological determination
of time-integrated stomatal ozone fluxes over wheat: a case study in Northern
Italy. Atmospheric Environment 37, 777–788.
Gerosa, G., Marzuoli, R., Cieslik, S., Ballarin-Denti, A., 2004. Stomatal ozone
uptake by barley in Italy. ‘‘Effective exposure’’ as a possible link between
concentration- and flux-based approaches. Atmospheric Environment 38,
2421–2432.
Gerosa, G., Vitale, M., Finco, A., Manes, F., Ballarin Denti, A., Cieslik, S., 2005. Ozone
uptake by an evergreen Mediterranean forest (Quercus ilex) in Italy. Part I:
micrometeorological flux measurements and flux partitioning. Atmospheric
Environment 39, 3255–3266.
Gerosa, G., Finco, A., Mereu, S., Vitale, M., Manes, F., Ballarin Denti, A., 2008. Comparison
of seasonal variations of ozone exposure and fluxes in a Mediterranean Holm oak
forest between the exceptionally dry 2003 and the following year. Environmental
Pollution 157 (15), 1737–1744. doi:10.1016/j.envpol.2007.11.025.
Gershenzon, J., Dudareva, N., 2007. The function of terpene natural products in the
natural world. Nature Chemical Biology 3, 408–414.
Gillette, D.A., Chen, W., 2001. Particle production and aeolian transport from
a ‘‘supply-limited’’ source area in the Chihuahuan desert, New Mexico, United
States. Journal of Geophysical Research – Atmospheres 106, 5267–5278.
Gödde, M., Conrad, R., 1998. Simultaneous measurement of nitric oxide production
and consumption in soil using a simple static incubation system, and the effect
of soil water content on the contribution of nitrification. Soil Biology and
Biochemistry 30, 433–442.
Goldstein, A.H., McKay, M., Kurpius, M.R., Schade, G.W., Lee, A., Holzinger, R.,
Rasmussen, R.A., 2004. Forest thinning experiment confirms ozone deposition
to forest canopy is dominated by reaction with biogenic VOCs. Geophysical
Research Letters 31, L22106. doi:10.1029/2004GL021259.
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Gribble, G.W., 1992. Sources of halogenated alkanes. Chemical & Engineering News
70 3–3.
Grivicke, R., Pressley, S., Allwine, G., Jobson, T., Westberg, H., Lamb, B., Jimenez, J.L.,
Nemitz, E., Alexander, L., Velasco, E., Molina, L., Ramos, R., 2007. Eddy covari-
ance flux measurements of urban aerosols and related urban gaseous pollutants
during the MILAGRO Mexico City Field Campaign. In: American Association for
Aerosol Research Annual Meeting 2007, Reno, 24–28 Sept 2007. American
Association for Aerosol Research.
Groffman, P.M., Altabet, M.A., Böhlke, J.K., Butterbach-Bahl, K., David, M.B.,
Firestone, M.K., Giblin, A.E., Kana, T.M., Nielsen, L.P., Voytek, M.A., 2006.
Methods for measuring denitrification: diverse approaches to a difficult
problem. Ecological Applications 16, 2091–2122.
Grulke, N.E., Alonso, R., Nguyen, T., Cascio, C., Dobrowolski, W., 2004. Stomata open
at night in pole sized and mature ponderosa pine: implications for O3 exposure
metrics. Tree Physiology 24, 1001–1010.
Grönholm, T., Aalto, P.P., Hiltunen, V., Rannik, U., Rinne, J., Laakso, L., Hyvonen, S.,
Vesala, T., Kulmala, M., 2007. Measurement of aerosol particle dry deposition
velocities using relaxed eddy accumulation technique. Tellus 59B, 381–386.
Grünhage, L., Jäger, H.J., 1994. Influence of the atmospheric conductivity on the
ozone exposure of plants under ambient conditions: considerations for
establishing ozone standards to protect vegetation. Environmental Pollution
85, 125–131.
Grünhage, L., Haenel, H.-D., 2008. Detailed documentation of the PLATIN (PLant–
ATmosphere INteraction) model. vTI Agriculture and Forestry Reseach 319, 85
(Special Issue).
Guenther, A.B., Zimmerman, P.R., Harley, P.C., Monson, R.K., Fall, R., 1993. Isoprene
and monoterpene emission rate variability: model evaluations and sensitivity
analyses. Journal of Geophysical Research 98, 12609–12617.
Guenther, A., Hewitt, C., Erickson, D., Fall, R., Geron, C., Graedel, T., Harley, P.,
Klinger, L., Lerdau, M., Mckay, W., Pierce, T., Scholes, R., Steinbrecher, R.,
Tallamraju, R., Taylor, J., Zimmerman, P., 1995. A global model of natural volatile
organic compound emissions. Journal of Geophysical Research 100, 8873–8892.
Guenther, A., 1999. Modeling biogenic volatile organic compound emissions to the
atmosphere. In: Hewitt, C.N. (Ed.), Reactive Hydrocarbons in the Atmosphere.
Academic Press, San Diego, pp. 41–94.
Guenther, A.B., Hills, A.J., 1998. Eddy covariance measurement of isoprene fluxes.
Journal of Geophysical Research 103, 13145–13152.
Guenther, A., Geron, C., Pierce, T., Lamb, B., Harley, P., Fall, R., 2000. Natural
emissions of non-methane volatile organic compounds, carbon monoxide,
and oxides of nitrogen from North America. Atmospheric Environment 34,
2205–2230.
Güsten, H., Heinrich, G., Schmidt, R.W.H., Schurath, U., 1992. A novel sensor for
direct eddy flux measurements. Journal of Atmospheric Chemistry 14, 73–84.
Guenther, A., Karl, T., Harley, P., Wiedinmyer, C., Palmer, P.I., Geron, C., 2006.
Estimates of global terrestrial isoprene emissions using MEGAN (Model of
Emissions of Gases and Aerosols from Nature). Atmospheric Chemistry and
Physics 6, 107–173.
Haapanala, S., Rinne, J., Pystynen, H.-K., Hellén, H., Hakola, H., Riutta, T., 2006.
Measurements of biogenic hydrocarbon emissions from a boreal fen in the
southern Finland with a REA system. Biogeosciences 3, 103–112.
Hakata, M., Takahashi, M., Zumft, W., Sakamoto, A., Morikawa, H., 2003. Conversion
of the nitrate nitrogen and nitrogen dioxide to nitrous oxides in plants. Acta
Biotechnologica 23, 249–257.
Hakola, H., Laurila, T., Rinne, J., Puhto, K., 2000. The ambient concentrations of
biogenic hydrocarbons at a North-European site. Atmospheric Environment 34,
4971–4982.
Hakola, H., Tarvainen, V., Bäck, J., Ranta, H., Bonn, B., Rinne, J., Kulmala, M., 2006.
Seasonal variation of mono- and sesquiterpene emission rates of Scots pine.
Biogeosciences 3, 93–101.
Hari, P., Raivonen, M., Vesala, T., Munger, J.W., Pilegaard, K., Kulmala, M., 2003.
Ultraviolet light and leaf emission of NOx. Nature 422, 134.
Harley, P., Greenberg, J., Niinemets, Ü., Guenther, A., 2007. Environmental controls
over methanol emission from leaves. Biogeosciences 4, 1083–1099.
Harmens, H., Mills, G., Emberson, L.D., Ashmore, M.R., 2007. Implications of climate
change for the stomatal flux of ozone: a case study for winter wheat. Envi-
ronmental Pollution 146, 763–770.
Harrison, R.M., Yin, J.X., Mark, D., Stedman, J., Appleby, R.S., Booker, J., Moorcroft, S.,
2001. Studies of the coarse particle (2.5–10 mm) component in UK urban
atmospheres. Atmospheric Environment 35, 3667–3679.
Hatanaka, A., 1993. The biogeneration of green odour by green leaves. Phyto-
chemistry 34, 1201–1218.
Hayes, F., Mills, G., Harmens, H., Norris, D., 2007. Evidence of Widespread Ozone
Damage to Vegetation in Europe (1990–2006). Programme Coordinating Centre
for the ICP Vegetation, Centre for Ecology and Hydrology, Bangor, UK. Available
from: <icpvegetation.ceh.ac.uk>.
Heiden, A.C., Kobel, K., Wildt, J., 1999. Einfluß verschiedener Streßfaktoren auf die
Emission pflanzlicher flüchtiger organischer Verbindungen. Institut für Chemie
und Dynamik der Geosphäre 2: Chemie der Belasteten Atmosphäre, For-
schungszentrum Jülich, Jülich.
Heiden, A.C., Kobel, K., Langebartels, C., Schuh-Thomas, G., Wildt, J., 2003. Emissions
of oxygenated volatile organic compounds from plants. Part I: emissions from
lipoxygenase activity. Journal of Atmospheric Chemistry 45, 143–172.
Held, A., Hinz, K.-P., Trimborn, A., Spengler, B., Klemm, O., 2003. Towards direct
measurement of turbulent vertical fluxes of compounds in atmospheric aerosol
particles. Geophysical Research Letters 30. doi:10.1029/2003GL017854.
5259
Held, A., Nowak, A., Wiedensohler, A., Klemm, O., 2006. Field measurements and
size-resolved model simulations of turbulent particle transport to a forest
canopy. Journal of Aerosol Science 37, 786–798.
Hellén, H., Hakola, H., Pystynen, K.-H., Rinne, J., Haapanala, S., 2006. C2–C10
hydrocarbon emissions from a boreal wetland and forest floor. Biogeosciences
3, 167–174.
Helmig, D., Ganzeveld, L., Butler, T., Oltmans, S.J., 2007. The role of ozone
atmosphere–snow gas exchange on polar, boundary-layer tropospheric
ozone – a review and sensitivity analysis. Atmospheric Chemistry and
Physics 7, 15–30.
Hensen, A., Groot, T.T., van den Bulk, W.C.M., Vermeulen, A.T., Olesen, J.E.,
Schelde, K., 2006. Dairy farm CH4 and N2O emissions, from one square metre to
the full farm scale. Agriculture, Ecosystem & Environment 112, 146–152.
Hensen, A., Nemitz, E., Flynn, M.J., Blatter, A., Jones, S.K., Sørensen, L.L., Hensen, B.,
Pryor, S., Jensen, B., Otjes, R.P., Cobussen, J., Loubet, B., Erisman, J.W.,
Gallagher, M.W., Neftel, A., Sutton, M.A., 2008. Inter-comparison of ammonia
fluxes obtained using the Relaxed Eddy Accumulation Technique. Biogeosciences
Discussions 5, 3965–4000.
Herrmann, B., Mattsson, M., Jones, S.K., Cellier, P., Milford, C., Sutton, M.A.,
Schjoerring, J.K., Neftel, A., 2008. Vertical structure and diurnal variability of
ammonia emission potential within an intensively managed grass canopy.
Biogeosciences Discussions 5, 2897–2921.
Herrmann, H., Tilgner, A., Barzaghi, P., Majdik, Z., Gligorovski, S., Poulain, L.,
Monod, A., 2005. Towards a more detailed description of tropospheric
aqueous phase organic chemistry: CAPRAM 3.0. Atmospheric Environment 39,
4351–4363.
Hertel, O., Skjøth, C.A., Lofstrøm, P., Geels, C., Frohn, L.M., Ellermann, T., Madsen, P.V.,
2006. Modelling nitrogen deposition on a local scale – a review of the current
state of the art. Environmental Chemistry 3, 317–337.
Hirsch, A.I., Michalak, A.M., Bruhwiler, L.M., Peters, W., Dlugokencky, E.J., Tans, P.P.,
2006. Inverse modelling estimates of the global nitrous oxide surface flux from
1998–2001. Global Biogeochemistry Cycles 20, GB1008.
Hogg, A., Uddling, J., Ellsworth, D., Carroll, M.A., Pressley, S., Lamb, B., Vogel, C., 2007.
Stomatal and non-stomatal fluxes of ozone to a northern mixed hardwood
forest. Tellus B 59, 514–525.
Hole, L.R., Brunner, S.H., Hanssen, J.E., Zhang, L., 2008. Low cost measurements of
nitrogen and sulphur dry deposition velocities at a semi-alpine site: gradient
measurements and a comparison with deposition model estimates. Environ-
mental Pollution 154, 473–481.
Holtslag, A.A.M., Moeng, C.H., 1991. Eddy diffusivity and countergradient transport
in the convective atmospheric boundary-layer. Journal of the Atmospheric
Sciences 48, 1690–1698.
Holzke, C., Dindorf, T., Kesselmeier, J., Kuhn, U., Koppmann, R., 2006. Terpene
emissions from European beech (Fagus sylvatica L.): pattern and emission
behaviour over two vegetation periods. Journal of Atmospheric Chemistry 55,
81–102.
Hong, J., Kim, J., Lee, D., Lim, J.H. 2008. Estimation of the storage and advection
effects on H2O and CO2 exchanges in a hill KoFlux forest catchment. Water
Resources Research 44, 1.
Hoose, C., Lohmann, U., Stier, P., Verheggen, B., Weingartner, E., 2008. Aerosol
processing in mixed-phase clouds in ECHAM5-HAM: model description and
comparison to observations. Journal of Geophysical Research D: Atmospheres
113 (7), D07210.
Horii, C.V., Munger, J.W., Wofsky, S.C., Zahniser, M., Nelson, D., McManus, J.B., 2005.
Atmospheric reactive nitrogen concentration and flux budgets at a North-
eastern U.S. forest site. Agricultural Forest Meteorology 133, 210–225.
Horvath, H., Pesava, P., Toprak, S., Aksu, R., 1996. Technique for measuring the
deposition velocity of particulate matter to building surfaces. Science of the
Total Environment 189–190, 255–258.
Horváth, L., 1983. Concentration and near surface vertical flux of ammonia in the
air in Hungary. Idöjárás. Journal of the Hungarian Meteorological Service 87,
65–70.
Horváth, L., Asztalos, M., Führer, E., Mészáros, R., Weidinger, T., 2005. Measurement
of ammonia exchange over grassland in the Hungarian Great Plain. Agricultural
and Forest Meteorology 130, 282–298.
Huebert, B., Robert, C., 1985. The dry deposition of nitric acid to grass. Journal of
Geophysical Research 90, 2085–2090.
Hummelshoj, P., 1994. Dry Deposition of Particles and Gases. Riso, R-658(EN). RISO
National Laboratory, Roskilde, ISBN 87-550-1864-5.
Husar, R.B., Lodge, J.P., Moore, D.J. (Eds.), 1978. Sulfur in the Atmosphere. Pergamon
Press, New York.
Husted, S., Hebbern, C.A., Mattsson, M., Schjoerring, J.K., 2000. A critical experi-
mental evaluation of methods for determination of NHþ 4 in plant tissue, xylem
sap and apoplastic fluid. Physiologia Plantarum 109 (2), 167–179.
Hüve, K., Christ, M.M., Kleist, E., Uerlings, R., Niinemets, Ü., Walter, A., Wildt, J., 2007.
Simultaneous growth and emission measurements demonstrate an interactive
control of methanol release by leaf expansion and stomata. Journal of Experi-
mental Botany 58, 1783–1793.
IPCC, 2006. IPCC Guidelines for National Greenhouse Gas Inventories, Prepared by
the National Greenhouse Gas Inventories Programme. In: Eggleston, H.S.,
Buendia, L., Miwa, K., Ngara, T., Tanabe, K. (Eds.), Agriculture, Forestry and Other
Land Use, vol. 4. IGES, Japan.
IPCC, 2007. Climate Change 2007 – the Physical Science Basis; Working Group I
Contribution to the Fourth Assessment Report of the IPCC, Intergovernmental
Panel on Climate Change.
5260 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Jacob, D.J., Field, B.D., Jin, E.M., Bey, I., Li, Q.B., Logan, J.A., Yantosca, R.M., Singh, H.B.,
2002. Atmospheric budget of acetone. Journal of Geophysical Research –
Atmospheres 107, D10. 10.1029.
Jitto, P., Vinitnantarat, S., Khummongkol, P., 2007. Dry deposition velocity of sulfur
dioxide over rice paddy in the tropical region. Atmospheric Research 85, 140–147.
Jones, A.E., Weller, R., Wolff, E.W., Jacobi, H.-W., 2000. Speciation and rate of
photochemical NO and NO2 production in Antarctic snow. Geophysical
Research Letters 27, 345–348.
Jones, A.E., Weller, R., Anderson, P.S., Jacobi, H.W., Wolff, E.W., Schrems, O., Miller, H.,
2001. Measurements of NOx emissions from the Antarctic snowpack.
Geophysical Research Letters 28, 1499–1502.
Jones, M.R., Leith, I.D., Fowler, D., Raven, J.A., Sutton, M.A., Nemitz, E., Cape, J.N.,
Sheppard, L.J., Smith, R.I., Theobald, M.R., 2007. Concentration-dependent NH3
deposition processes for mixed moorland semi-natural vegetation. Atmospheric
Environment 41, 2049–2060. doi:10.1016/j.atmosenv.2006.11.003.
Junge, C.E., 1963. Air Chemistry and Radioactivity. Academic Press, New York,
London.
Kanemasu, E.T., Flitcroft, I.D., Shah, T.D.H., Kidd, G., Nie, D., Simpson, I., Lin, M.,
Neue, H.-U., Bronson, K., 1995. Comparison of micrometeorological and
chamber measurements of methane emisisns from rice fields. In: Peng, S.,
Ingram, K.J., Lampe, K.J., Neue, H.-U. (Eds.), Climate Change and Rice. IRRI,
pp. 91–101.
Kärcher, B., Basko, M.M., 2004. Trapping of trace gases in growing ice crystals.
Journal of Geophysical Research 109, D22204. doi:10.1029/2004JD005254.
Karl, T., Fall, R., Jordan, A., Lindinger, W., 2001a. On-line analysis of reactive VOCs
from urban lawn mowing. Environmental Science & Technology 35, 2926–2931.
Karl, T., Guenther, A., Jordan, A., Fall, R., Lindinger, W., 2001b. Eddy covariance
measurement of biogenic oxygenated VOC emissions from hay harvesting.
Atmospheric Environment 35, 491–495.
Karl, T., Guenther, A., Lindinger, C., Jordan, A., Fall, R., Lindinger, W., 2001c. Eddy
covariance measurements of oxygenated volatile organic compound fluxes
from crop harvesting using a redesigned proton-transfer-reaction mass spec-
trometer. Journal of Geophysical Research 106, 24157–24167.
Karl, T., Fall, R., Rosenstiel, T.N., Prazeller, P., Larsen, B., Seufert, G., Lindinger, W.,
2002a. On-line analysis of the 13CO2 labeling of leaf isoprene suggests multiple
subcellular origins of isoprene precursors. Planta 215, 894–905.
Karl, T., Curtis, A.J., Rosenstiel, T.N., Monson, R.K., Fall, R., 2002b. Transient releases
of acetaldehyde from tree leaves – products of a pyruvate overflow mecha-
nism? Plant Cell and Environment 25, 1121–1131.
Karlsson, P.E., Tang, L., Sundberg, J., Chen, D., Lindskog, A., Pleijel, H., 2007.
Increasing risk for negative ozone impacts on vegetation in northern Sweden.
Environmental Pollution 150, 96–106.
Karlsson, P.G., Karlsson, P.E., Soja, G., Vandermeiren, K., Pleijel, H., 2004. Test of the
short-term critical levels for acute ozone injury on plants – improvements by
ozone uptake modelling and the use of an effect threshold. Atmospheric
Environment 38, 2237–2245.
Karnosky, D.F., Skelly, J.M., Percy, K.E., Chappelka, A.H., 2007. Perspectives regarding
50 years of research on effects of tropospheric ozone air pollution on US forests.
Environmental Pollution 147, 489–506.
Kawamura, K., Sakaguchi, F., 1999. Molecular distributions of water-soluble dicar-
boxylic acids in marine aerosols over the Pacific Ocean including tropics.
Journal of Geophysical Research 104, 3501–3509.
Keller, M.D., Bellows, W.K., Guillard, R.R.L., 1989. Dimethyl sulfide production in
marine-phytoplankton. In: Saltzmann, E.S., Cooper, W.J. (Eds.), Biogenic Sulfur
in the Environment. American Chemical Society, pp. 167–182.
Keller, F., Bassin, S., Ammann, C., Fuhrer, J., 2007. High-resolution modelling of
AOT40 and stomatal ozone uptake in wheat and grassland: a comparison
between 2000 and the hot summer of 2003 in Switzerland. Environmental
Pollution 146, 671–677.
Keppler, F., Hamilton, J.T.G., Braß, M., Röckmann, T., 2006. Methane emissions from
terrestrial plants under aerobic conditions. Nature 439, 187–191.
Keppler, F., Hamilton, J.T.G., McRoberts, W.C., Vigano, I., Brass, M., Röckmann, T.,
2008. Methoxyl groups of plant pectin as a precursor of atmospheric methane:
evidence from deuterium labelling studies. New Phytologist 178, 808–814.
Kerkeweg, A., Buchholz, J., Ganzeveld, L., Pozzer, A., Tost, H., Jöckel, P., 2006. Tech-
nical note: an implementation of the dry removal processes DRY DEPosition
and SEDImentation in the Modular Earth Submodel System (MESSy). Atmo-
spheric Chemistry and Physics 6, 4617–4632.
Keronen, P., Reissell, A., Rannik, Ü., Pohja, T., Siivola, E., Hiltunen, V., Hari, P.,
Kulmala, M., Vesala, T., 2003. Ozone flux measurements over a Scots pine forest
using eddy covariance method: performance evaluation and comparison with
flux–profile method. Boreal Environmental Research 8, 425–443.
Kesik, M., Brüggemann, N., Forkel, R., Knoche, R., Li, C., Seufert, G., Simpson, D.,
Butterbach-Bahl, K., 2006. Future scenarios of N2O and NO emissions from
European forest soils. Journal of Geophysical Research 111, G02018. doi:10.1029/
2005JG000115.
Kiene, R.P., Bates, T.S., 1990. Biological removal of dimethyl sulphide from seawater.
Nature 345, 702–705.
King, J.S., Kubiske, M.E., Pregitzer, K.S., Hendry, G.R., Giardina, C.P., Quinn, V.S.,
Karnosky, D.F., 2005. Tropospheric O3 compromises net primary production in
young stands of trembling aspen, paper birch and sugar maple in response to
elated CO2. New Phytologist 168, 623–636.
Kitzler, B., Zechmeister Boltenstern, S., Holtermann, C., Skiba, U., Butterbach-
Bahl, K., 2006. Controls over N2O, NOx and CO2 fluxes in a calcareous mountain
forest soil. Biogeosciences 3, 383–395.
Kleefeld, Ch., O’Dowd, C.D., O’Riely, S., Jennings, S.G., Aalto, P., Becker, E., Kunz, G., de
Leeuw, G., 2002. The relative scattering of sub and super micron particles to
aerosol light scattering in the marine boundary layer (MBL). Journal of
Geophysical Research 107. doi:10.1029/2000JD000262.
Kleffmann, J., Kurtenbach, R., Loerzer, J., Wiesen, P., Kalthoff, N., Vogel, B., Vogel, H.,
2003. Measured and simulated vertical profiles of nitrous acid – Part I: field
measurements. Atmospheric Environment 37, 2949–2955.
Kleffmann, J., Gavriloaiei, T., Hofzumahaus, A., Holland, F., Koppmann, R., Rupp, L.,
Schlosser, E., Siese, M., Wahner, A., 2005. Daytime formation of nitrous acid:
a major source of OH radicals in a forest. Geophysical Research Letters 32,
L05818. doi: 05810.01029/02005GL022524.
Klemm, O., Wrzesinski, T., 2007. Fog deposition fluxes of water and ions to
a mountainous site in Central Europe. Tellus B 59B, 705.
Kokkola, H., Sorjamaa, R., Peräniemi, A., Raatikainen, T., Laaksonen, A., 2006. Cloud
formation of particles containing humic-like substances. Geophysical Research
Letters 33, 10.
Kool, D.M., Wrage, N., Oenema, O., Harris, D., Van Groenigen, J.W., 2009. The 18O
signature of biogenic nitrous oxide is determined by O exchange with water.
Rapid communications in Mass Spectrometry 23, 104–108.
Kowalski, A.S., Vong, R.J., 1999. Near-surface fluxes of cloud water evolve vertically.
Quarterly Journal of the Royal Meteorological Society 125, 2663–2684.
Kowalski, A.S., 2001. Deliquescence induces eddy covariance and estimable dry
deposition errors. Atmospheric Environment 35, 4843–4851.
Kreuzwieser, J., Schnitzler, J.P., Steinbrecher, R., 1999. Biosynthesis of organic
compounds emitted by plants. Plant Biology 1, 149–159.
Kreuzwieser, J., Graus, M., Wisthaler, A., Hansel, A., Rennenberg, H., Schnitzler, J.P.,
2002. Xylem-transported glucose as additional carbon source for leaf isoprene
formation in Quercus robur. New Phytologist 156, 171–178.
Kroon, P.S., Hensen, A., van den Bulk, W.C.M., Jongejan, P.A.C., Vermeulen, A.T., 2008.
The importance of reducing the systematic error due to non-linearity in N2O
flux measurements by static chambers. Nutrient Cycling in Agroecosystems 82,
175–186.
Lagzi, I., Mészáros, R., Horváth, L., Tomlin, A., Weidinger, T., Turányi, T., Ács, F.,
Haszpra, L., 2004. Modelling ozone fluxes over Hungary. Atmospheric Envi-
ronment 38, 6211–6222.
Lamaud, E., Carrara, A., Brunet, Y., Lopez, A., Druilhet, A., 2002. Ozone fluxes above
and within a pine forest canopy in dry and wet conditions. Atmospheric
Environment 36, 77–88.
Lathiere, J., Hauglustaine, D.A., Friend, A.D., De Noblet-Ducoudre’, N., Viovy, N.,
Folberth, G.A., 2006. Impact of climate variability and land use changes on
global biogenic volatile organic compound emissions. Atmospheric Chemistry
and Physics 6, 2129–2146.
Lee, A., Goldstein, A.H., Kroll, J.H., Ng, N.L., Varutbangkul, V., Flagan, R.C.,
Seinfeld, J.H., 2006. Gas-phase products and secondary aerosol yields from the
photooxidation of 16 different terpenes. Journal of Geophysical Research 111,
D17305. doi:10.1029/2006JD007050.
Lehning, A., Zimmer, W., Zimmer, I., Schnitzler, J.P., 2001. Modelling of annual
variations of oak (Quercus robur L.) isoprene synthase activity to predict
isoprene emission rates. Journal of Geophysical Research 106, 3157–3166.
Lemon, E., Van Houtte, R., 1980. Ammonia exchange at the land surface. Agronomy
Journal 72, 876–883.
Lerdau, M., 2007. A positive feedback with negative consequences. Science 316,
212–213.
Leriche, M., Curier, R.L., Deguillaume, L., Caro, D., Sellegri, K., Chaumerliac, N., 2007.
Numerical quantification of sources and phase partitioning of chemical species
in cloud: application to wintertime anthropogenic air masses at the Puy de
Dôme station. Journal of Atmospheric Chemistry 57-3, 281–297.
Leroy, D., Wobrock, W., Flossmann, A.I., 2008. The role of boundary layer aerosol
particles for the development of deep convective clouds: a high-resolution 3D
model with detailed (bin) microphysics applied to CRYSTAL-FACE. Atmospheric
Research. doi:10.1016/j.atmosres.2008.06.001.
Lewis, A.C., Hopkins, J.R., Carpenter, L.J., Stanton, J., Read, K.A., Pilling, M., 2005.
Sources and sinks of acetone, methanol, and acetaldehyde in North Atlantic
marine air. Atmospheric Chemistry and Physics 5, 1963–1974.
Lewis, E.R., Schwartz, S.E., 2004. Sea Salt Aerosol Production: Mechanisms,
Methods, Measurements, and Models: A Critical Review. American Geophysical
Union, Washington, DC.
Lewis, E.R., Schwartz, S.E., 2005. Sea Salt Aerosol Production. Mechanisms, Methods,
Measurements, and Models. American Geophysical Union, Washington, D.C. USA.
Li, C., Aber, J., Stange, F., Butterbach-Bahl, K., Papen, H., 2000. A process oriented
model of N2O and NO emissions from forest soils: 1, model development.
Journal of Geophysical Research 105, 4369–4384.
Li, C., Salas, W., DeAngelo, B., Rose, S., 2006. Assessing alternatives for mitigating net
greenhouse gas emissions and increasing yields from rice production in China
over the next twenty years. Journal of Environmental Quality 35, 1554–1565.
Li, D., Wang, X., 2008. Nitrogen isotopic signature of soil-released nitric oxide (NO)
after fertilizer application. Atmospheric Environment 42, 4747–4754.
Lichtenthaler, H.K., 1999. The 1-deoxy-D-xylulose-5-phosphate pathway of iso-
prenoid biosynthesis in plants. Annual Review of Plant Physiology and Plant
Molecular Biology 50, 47–65.
Lindinger, W., Hansel, A., Jordan, A., 1998. Review: on-line monitoring of volatile
organic compounds at pptv levels by means of Proton-Transfer-Reaction Mass
Spectrometry (PTR-MS), Medical applications, food control and environmental
research. International Journal of Mass Spectrometry and Ion Processes 173,
191–241.
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Liss, P.S., Balls, P.W., Martinelli, F.N., Coantic, M., 1981. The effect of evaporation and
condensation on gas transfer across an air–water interface. Oceanologica Acta 4,129.
Liss, P.S., Hatton, A.D., Malin, G., Nightingale, P.D., Turner, S.M., 1997. Marine
sulphur emissions. Philosophical Transactions of the Royal Society of London
Series B – Biological Sciences 352, 159–168.
Loreto, F., Ciccioli, P., Brancaleoni, E., Valentini, R., De Lillis, M., Csiky, O., Seufert, G., 1998.
A hypothesis on the evolution of isoprenoid emission by oaks based on the corre-
lation between emission type and Quercus taxonomy. Oecologia 115, 302–305.
Loreto, F., Ciccioli, P., Brancaleoni, E., Frattoni, M., Delfine, S., 2000. Incomplete 13C
labeling of alpha-pinene content in Quercus ilex leaves and appearance of unlabeled
C in alpha-pinene emission in the dark. Plant Cell and Environment 23, 229–234.
Loreto, F., Fischbach, R.J., Schnitzler, J.-P., Ciccioli, P., Brancaleoni, E., Calfapietra, C.,
Seufert, G., 2001. Monoterpene emission and monoterpene synthase activities
in the Mediterranean evergreen oak Quercus ilex L. grown at elevated CO2
concentrations. Global Change Biology 7, 709–717.
Loreto, F., Pinelli, P., Brancaleoni, E., Ciccioli, P., 2004. 13C labelling reveals chloro-
plastic and extra-chloroplastic pools of dimethylallyl pyrophosphate and their
contribution to isoprene formation. Plant Physiology 135, 1903–1907.
Loreto, F., Barta, C., Brilli, F., Nogues, I., 2006. On the induction of volatile organic
compound emissions by plants as consequence of wounding or fluctuations of
light and temperature. Plant Cell and Environment 29, 1820–1828.
Loubet, B., Milford, C., Sutton, M.A., Cellier, P., 2001. Investigation of the interaction
between sources and sinks of atmospheric ammonia in an upland landscape
using a simplified dispersion-exchange model. Journal of Geophysical Research
106 (D20), 24183–24196.
Loubet, B., Cellier, P., Milford, C., Sutton, M.A., 2006. A coupled dispersion and
exchange model for short-range dry deposition of atmospheric ammonia.
Quarterly Journal of the Royal Meteorological Society 132, 1733–1763.
Loubet, B., Asman, W.A.H., Theobald, M.R., Hertel, O., Tang, Y.S., Robin, P.,
Hassouna, M., Daemmgen, U., Genermont, S., Cellier, P., Sutton, M.A., 2008.
Ammonia deposition near hot spots: processes, models and monitoring
methods. In: Sutton, M.A., Baker, S., Reis, S. (Eds.), Atmospheric Ammonia:
Detecting Emission Changes and Environmental Impacts. Springer.
Loubet, B., Milford, C., Hensen, A., Dämmgen, U., Cellier, P., Sutton, M.A., 2009.
Advection of ammonia over a pasture field, and its effect on gradient flux
measurements. Biogeosciences Discussions 6, 163–196.
Lovett, G.M., 1994. Atmospheric deposition of nutrients and pollutants to North
America: an ecological perspective. Ecological Applications 4, 629–650.
Loya, W.M., Pregitzer, K.S., Karberg, N.J., King, J.S., Giardina, C.P., 2003. Reduction of
soil carbon formation by tropospheric ozone under increased carbon dioxide
levels. Nature 425, 705–707.
Marandino, C.A., De Bruyn, W.J., Miller, S.D., Prather, M.J., Saltzman, E.S., 2005.
Oceanic uptake and the global atmospheric acetone budget. Geophysical
Research Letters 32 (15), L15806.
Mari, C., Jacob, D.J., Bechtold, P., 2000. Transport and scavenging of soluble gases in
a deep convective cloud. Journal of Geophysical Research 105, 22255–22267.
Martensson, E.M., Nilsson, E.D., Johansson, C., 2002. Emissions of aerosol particles in
the urban environment measured by eddy correlation. In: Proceedings of the
6th International Aerosol Conference, Taiwan, 9–13 September 2002.
Mårtensson, M., Nilsson, E.D., de Leeuw, G., Cohen, L.H., Hansson, H.-C., 2003.
Laboratory simulations of the primary marine aerosol generated by bubble
bursting. JGR-Atmospheres 108 (D9). doi:10.1029/2002JD002263.
Martensson, E.M., Nilsson, E.D., Buzorius, G., Johansson, C., 2006. Eddy covariance
measurements and parameterisaton of traffic related emissions in an urban
environment. Atmospheric Chemistry and Physics 6, 769–785.
Martin, C.L., Longley, I.D., Dorsey, J.R., Thomas, R.M., Gallagher, M.W., Nemitz, E.
Ultrafine particle fluxes above four major European cities. Atmospheric Envi-
ronment, in press.
Massad, R.S., Loubet, B., Tuzet, A., Cellier, P., 2008. Relationship between ammonia
stomatal compensation point and nitrogen metabolism in arable crops: current
status of knowledge and potential modelling approaches. Environmental
Pollution 154, 390–403.
Massman, W.J., 2004. Toward an ozone standard to protect vegetation based on
effective dose: a review of deposition resistances and a possible metric.
Atmospheric Environment 38, 2323–2337.
Matsuda, K., Aoki, M., Zhang, S., Kominami, T., Fukuyama, T., Fukuzaki, N., Totsuka, T.,
2002. Dry deposition velocity of sulfur dioxide on a red pine forest in Nagano,
Japan. Journal of Japan Society for Atmospheric Environment 37 (6), 387–392.
Matsuda, K., Watanabe, I., Wingpud, V., Theramongkol, P., Ohizumi, T., 2006.
Deposition velocity of O3 and SO2 in the dry and wet season above a tropical
forest in Northern Thailand. Atmospheric Environment 40, 7557–7564.
Mattsson, M., Herrmann, B., David, M., Loubet, B., Riedo, M., Theobald, M.R.,
Sutton, M.A., Bruhn, D., Neftel, A., Schjoerring, J.K., 2008a. Temporal variability in
bioassays of ammonia emission potential in relation to plant and soil N parame-
ters in intensively managed grassland. Biogeosciences Discussions 5, 2749–2772.
Mattsson, M., Herrmann, B., Jones, S.K., Neftel, A., Sutton, M.A., Schjoerring, J.K., 2008b.
Contribution of different grass species to plant–atmosphere ammonia exchange
in intensively managed grassland. Biogeosciences Discussions 5, 2583–2605.
Matyssek, R., Sandermann, H., Wieser, G., Booker, F., Cieslik, S., Musselman, R.,
Ernst, D., 2008. The challenge of making ozone risk assessment for forest trees
more mechanistic. Environmental Pollution 156 (3), 567–582. doi:10.1016/
j.envpol.2008.04.017.
McBain, M.C., Warland, J.S., McBride, R.A., Wagner-Riddle, C., 2004. Laboratory-scale
measurements of N2O and CH4 emissions from hybrid poplars (Populus deltoides
x Populus nigra). Waste Management Research 22, 454–465.
5261
McDonald, A.G., Bealey, W.J., Fowler, D., Dragosits, U., Skiba, U., Smith, R.I.,
Donovan, R.G., Brett, H.E., Hewitt, C.N., Nemitz, E., 2007. Quantifying the effect
of urban tree planting on concentrations and depositions of PM10 in two UK
conurbations. Atmospheric Environment 41 (38), 8455–8467.
McFiggans, G., Coe, H., Burgess, R., Allan, J., Cubison, M., Alfarra, M.R., Saunders, R.,
Saiz-Lopez, A., Plane, J.M.C., Wevill, D.J., Carpenter, L.J., Rickard, A.R., Monks, P.S.,
2004. Atmospheric Chemistry and Physics 4, 701–713.
McLaughlin, S.B., Wullschleger, S.D., Sun, G., Nosal, M., 2007. Interactive effects of
ozone and climate on water use, soil moisture content and streamflow in
a southern Appalachian forest in the USA. New Phytologist 174, 125–136.
McLeod, A.R., Fry, S.C., Loake, G.J., Messenger, D.J., Reay, D.S., Smith, K.A., Yun, B.-W.,
2008. Ultraviolet radiation drives methane emissions from terrestrial plant
pectins. New Phytologist 9999 (9999).
Meixner, F.X., Ammann, C., Arenz, R., Nathaus, F.J., Neftel, A., Blatter, A., Gut, A.,
Hoegger, D., Wyers, G.P., Jongejan, P., Loesch, R., Busch, J., Guesten, H., Sprung, D.,
Baumann, M., 1996. The Bellheim ’95 experiment: bi-directional fluxes of
ammonia. Annales Geophysicae 14 (Suppl. II), C467.
Meskhidze, N., Nenes, A., 2006. Phytoplankton and cloudiness in the Southern
Ocean Science. 314 (5804), 1419–1423.
Meyers, T.P., Finkelstein, P.L., Clarke, J., Ellestad, T.G., Sims, P., 1998. A multilayer
model for inferring dry deposition using standard meteorological measure-
ments. Journal of Geophysical Research 103, 22645–22661.
Meyers, T.P., Luke, W.T., Meisinger, J.J., 2006. Fluxes of ammonia and sulfate over
maize using relaxed eddy accummulation. Agricultural Forest Meteorology 136,
203–213.
Michou, M., Laville, P., Serça, D., Fotiadi, A., Bouchou, P., Peuch, V.-H., 2005.
Measured and modeled dry deposition velocities over the ESCOMPTE area.
Atmospheric Research 74, 89–116.
Mikkelsen, T.N., Ro-Poulsen, H., Hovmand, M.F., Jensen, N.O., Pilegaard, K.,
Egeløv, A.H., 2004. Five-year measurements of ozone fluxes to a Danish Norway
spruce canopy. Atmospheric Environment 38, 2361–2371.
Milford, C., Theobald, M.R., Nemitz, E., Sutton, M.A., 2001a. Dynamics of ammonia
exchange in response to cutting and fertilizing in an intensively-managed
grassland. Water, Air and Soil Pollution: Focus 1, 167–176.
Milford, C., Hargreaves, K.J., Sutton, M.A., Loubet, B., Cellier, P., 2001b. Fluxes of NH3
and CO2 over upland moorland in the vicinity of agricultural land. Journal of
Geophysical Research (Atmospheres) 106, 24169–24181.
Milford, C., Theobald, M.R., Nemitz, E., Hargreaves, K.J., Horvath, L., Raso, J.,
Dämmgen, U., Neftel, A., Jones, S.K., Hensen, A., Loubet, B., Sutton, M.A., 2009.
Ammonia fluxes in relation to cutting and fertilization of an intensively
managed grassland derived from an inter-comparison of gradient measure-
ments. Biogeosciences Discussions, 6, 819–834.
Millenium Ecosystem Assessment, 2005. Ecosystems and Human Well-being:
Current State and Trends. Island Press.
Millet, D.B., Jacob, D.J., Turquety, S., Hudman, R.C., Wu, S., Fried, A., Walega, J.,
Heikes, B.G., Blake, D.R., Singh, H.B., Anderson, B.E., Clarke, A.D., 2006. Form-
aldehyde distribution over North America: implications for satellite retrievals of
formaldehyde columns and isoprene emission. Journal of Geophysical Research
111, D24S02. doi:10.1029/2005JD006853.
Millet, D.B., Jacob, D.J., Custer, T.G., de Gouw, J.A., Goldstein, A.H., Karl, T., Singh, H.B.,
Sive, B.C., Talbot, R.W., Warneke, C., Williams, J., 2008. New constraints on
terrestrial and oceanic sources of atmospheric methanol. Atmospheric Chem-
istry and Physics Discussions 8, 7609–7655.
Möhler, O., Bunz, H., Stetzer, O., 2006. Homogeneous nucleation rates of nitric acid
dihydrate (NAD) at simulated stratospheric conditions – Part II: modelling.
Atmospheric Chemistry and Physics 6 (10), 3035–3047.
Möhler, O., DeMott, P.J., Vali, G., Levin, Z., 2007. Microbiology and atmospheric
processes: the role of biological particles in cloud physics. Biogeosciences
Discuss. 4, 2559–2591. Available at: http://www.biogeosciences-discuss.net/4/
2559/2007/.
Monin, A.S., Obukhov, A.M., 1954. ‘Basic laws of turbulent mixing in the ground
layer of the atmosphere. Transactions of the Geophysical Institute. Akademy
Nauk USSR 151, 163–187.
Monin, A.S., Zilitinkevich, S., 1974. Similarity theory and resistance laws for the
planetary layer. Boundary-Layer Meteorology 7, 391–397.
Monks, P.S., Granier, C., Fuzzi, S., Stohl, A., Williams, M., Akimoto, H., Amman, M.,
Baklanov, A., Baltensperger, U., Bey, I., Blake, N., Blake, R.S., Carslaw, K., Cooper,
O.R., Dentener, F., Fowler, D., Fragkou, E., Frost, G., Generoso, S., Ginoux, P.,
Grewe, V., Guenther, A., Hansson, H.C., Henne, S., Hjorth, J., Hofzumahaus, A.,
Huntrieser, H., Isaksen, I.S.A., Jenkin, M.E., Kaiser, J., Kanakidou, M., Klimont, Z.,
Kulmala, M., Laj, P., Lawrence, M.G., Lee, J.D., Liousse, C., Maione, M., McFiggans,
G., Metzger, A., Mieville, A., Moussiopoulos, N., Orlando, J.J., O’Dowd, C., Palmer,
P.I., Parrish, D.D., Petzold, A., Platt, U., Poeschl, U., Prévôt, A.S.H., Reeves, C.E.,
Reimann, S., Rudich, Y., Sellegri, K., Steinbrecher, R., Simpson, D., ten Brink, H.,
Theloke, J., van der Werf, G.R., Vautard, R., Vestreng, V, Vlachokostas, Ch.,
vonGlasow, R. Atmospheric composition change – global and regional air
quality (Accent Special Issue) 43 (33), 5264–5344.
Monson, R.K., Harley, P.C., Litvak, M.E., Wildermuth, M., Guenther, A.B., Zimmerman, P.R.,
Fall, R., 1994. Environmental and developmental controls over the seasonal pattern
of isoprene emission from aspen leaves. Oecologia 99, 260–270.
Monteith, J.L., Unsworth, M.H., 2007. Principles of Environmental Physics. Academic
Press.
Mosier, A.R., Duxbury, J.M., Freney, J.R., Heinemyer, O., Minami, K., 1998. Assessing
and mitigating N2O emissions from agricultural soils. Climate Change 40,
1573–1580.
5262 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Mosquera, J., Hensen, A., van den Bulk, W.C.M., Vermeulen, A.T., Erisman, J.W., 2001.
Long term NH3 flux measurements at two locations in The Netherlands. Water,
Air and Soil Pollution: Focus 1, 203–212.
Moukhtar, S., Bessagnet, B., Rouil, L., Simon, V., 2005. Monoterpene emissions from
beech (Fagus sylvatica) in a French forest and impact on secondary pollutants
formation at regional scale. Atmospheric Environment 39, 3535–3547.
Muhlbauer, A., Lohmann, U., 2008. Sensitivity studies of the role of aerosols in
warm-phase orographic precipitation in different dynamical flow regimes.
Journal of Atmospheric Science 65, 2522–2542.
Mukammal, E.I., 1965. Ozone as a cause of tobacco injury. Agricultural Meteorology
2, 145–165.
Mulcahy, J.P., O’Dowd, C.D., Jennings, S.G., Ceburnis, D., 2008. Significant enhance-
ment of aerosol optical depth in marine air under high wind conditions.
Geophysical Research Letters 35, L16810. doi:10.1029/2008GL034303.
Müller, C., 2003. Plants affect the in situ N2O emissions of a temperate grassland
ecosystem. Journal of Plant Nutrition and Soil Science – Zeitschrift Für Pflan-
zenernährung Und Bodenkunde 166, 771–773.
Neff, J.C., Holland, E.A., Dentener, F.J., McDowell, W.H., Russell, K.M., 2002. The
origin, composition and rates of organic nitrogen deposition: a missing piece of
the nitrogen cycle? Biogeochemistry 57, 99–136.
Neftel, A., Blatter, A., Gut, A., Hoegger, D., Meixner, F.X., Ammann, C., Nathaus, F.J.,
1998. NH3 soil and soil surface gas measurements in a triticale wheat field.
Atmospheric Environment (Ammonia Special Issue) 32 (3), 499–506.
Neftel, A., Blatter, A., Otjes, R., Erisman, J.W., Hansen, A., 1999. State of the art REA
NH3 flux measurements. In: Proc. 10th Nitrogen Workshop, Copenhagen,
August 1999. II.49. Royal Veterinary and Agricultural University, Copenhagen.
Neftel, A., Ammann, C., Brunner, A., Jocher, M., Spirig, M., Davidson, B., Rinne, J.,
Dommen, J., 2007. Comparison of different approaches to measure VOC exchange
over grassland by PTR-MS. In: Hansel, A., Märk, T. (Eds.), 3rd International
Conference on Proton Transfer Reaction Mass Spectrometry and Its Applications –
Contributions. January 27th–February 1st, 2007, Obergurgl, Austria. Conference
Series, Innsbruck University Press, pp. 80–84.
Neinhuis, C., Barthlott, W., 1997. Characterization and distribution of water-repel-
lent, self-cleaning plant surfaces. Annals of Botany 79, 667–677.
Neirynck, J., Kowalski, A.S., Carrara, A., Ceulemans, R., 2005. Driving forces for
ammonia fluxes over mixed forest subjected to high deposition loads. Atmo-
spheric Environment 39, 5013–5024.
Neirynck, J., Ceulemans, R. 2008. Bidirectional ammonia exchange above a mixed
coniferous forest. Reduced Nitrogen in Ecology and the Environment 154, 424–438.
Nemecek-Marshall, M., MacDonald, M.C., Franzen, J.J., Wojciechowski, C.L., Fall, R.,
1995. Methanol emission from leaves: enzymatic detection of gas-phase
methanol and relation of methanol fluxes to stomatal conductance and leaf
development. Plant Physiology 108, 1359–1368.
Nemitz, E., Sutton, M.A., Fowler, D., Choularton, T., 1996. Application of a NH3 gas-to-
particle conversion model to measurement data. In: Sutton, M.A., Lee, D.S.,
Dollard, G.J., Fowler, D. (Eds.), Poster Proceedings of Atmospheric Ammonia:
Emission, Deposition and Environmental Impacts. Institute of Terrestrial Ecology,
Edinburgh, pp. 98–103.
Nemitz, E., Sutton, M.A., Gut, A., San José, R., Husted, S., Schjoerring, J.K., 2000a.
Sources and sinks of ammonia within an oilseed rape canopy. Agricultural and
Forest Meteorology (Ammonia Special Issue) 105 (4), 385–404.
Nemitz, E., Theobald, M.R., McDonald, A.G., Fowler, D., Dorsey, J.R., Bower, K.N.,
Gallagher, M.W., 2000b. Direct micrometeorological eddy-correlation measure-
ments of size-dependent particle emission above a city. In: Midgley, P.M., Reu-
ther, M., Williams, M. (Eds.), EUROTRAC Symposium 2000. Springer Verlag,
Heidelberg, Garmisch-Parenkirchen.
Nemitz, E., Sutton, M.A., Schjoerring, J.K., Husted, S., Wyers, G.P., 2000c. Resistance
modelling of ammonia exchange over oilseed rape. Agriculture and Forest
Meteorology (Ammonia Special Issue) 105 (4), 405–425.
Nemitz, E., Williams, P.I., Theobald, M.R., McDonald, A.G., Fowler, D., Gallagher, M.W.,
2000d. Application of two micrometeorological techniques to derive fluxes of
aerosol components above a city. In: Midgley, P.M., Reuther, M., Williams, M.
(Eds.), EUROTRAC-2 Symposium 2000. Springer Verlag, Berlin, Garmisch-
Partenkirchen, Germany.
Nemitz, E., Sutton, M.A., Wyers, G.P., Otjes, R.P., Schjoerring, J.K., Gallagher, M.W.,
Parrington, J., Fowler, D., Choularton, T.W., 2000e. Surface/atmosphere
exchange and chemical interaction of gases and aerosols over oilseed rape.
Agricultural and Forest Meteorology 105, 427–445.
Nemitz, E., Fowler, D., Dorsey, J.R., Theobald, M.R., McDonald, A.D., Bower, K.N.,
Beswick, K.M., Williams, P.I., Gallagher, M.W., 2000f. Direct measurements of
size-segregated particle fluxes above a city. Journal of Aerosol Science 31,
116–117.
Nemitz, E., Flynn, M., Williams, P.I., Milford, C., Theobald, M.R., Blatter, A.,
Gallagher, M.W., Sutton, M.A., 2001a. A relaxed eddy accumulation system for
the automated measurement of atmospheric ammonia fluxes. Water, Air and
Soil Pollution: Focus 1, 189–202.
Nemitz, E., Milford, C., Sutton, M.A., 2001b. A two-layer canopy compensation point
model for describing bi-directional biosphere–atmosphere exchange of
ammonia. Quarterly Journal of the Royal Meteorological Society 127, 815–833.
Nemitz, E., Gallagher, M.W., Duyzer, J.H., Fowler, D., 2002a. Micrometeorological
measurements of particle deposition velocities to moorland vegetation. Quar-
terly Journal of the Royal Meteorological Society 128, 2281–2300.
Nemitz, E., Hargreaves, K.J., McDonald, A.G., Dorsey, J.R., Fowler, D., 2002b. Micro-
meteorological measurements of the urban heat budget and CO2 emissions on
a city scale. Environmental Science & Technology 36, 3139–3146.
Nemitz, E., Sutton, M.A., 2004. Gas-particle conversions above a Dutch heathland:
III. Modelling of size-dependent NHþ 4 fluxes as modified by the NH3–HNO3–
NH4NO3 equilibrium. Atmospheric Chemistry and Physics 4, 1025–1045.
Nemitz, E., Sutton, M.A., Wyers, G.P., Jongejan, P.A.C., 2004a. Gas-particle conver-
sions above a Dutch heathland: I. Surface exchange fluxes of NH3, SO2, HNO3
and HCl. Atmospheric Chemistry and Physics 4, 989–1005.
Nemitz, E., Sutton, M.A., Wyers, G.P., Otjes, R.P., Mennen, M.G., van Putten, E.M.,
Gallagher, M.W., 2004b. Gas-particle interactions above a Dutch heathland: II.
Concentrations and surface exchange fluxes of atmospheric particles. Atmo-
spheric Chemistry and Physics 4, 1007–1024.
Nemitz, E., Jimenez, J.L., Huffman, A., Canagaratna, M., Worsnop, D.R., Guenther, A.B.,
2008. An eddy covariance system for the measurement of surface/atmosphere
exchange fluxes of submicron aerosol chemical species – first application above an
urban area. Aerosol Science Technology 42 (8), 636–657.
Nemitz, E., Dorsey, J.R., Flynn, M., Gallagher, M.W., Hensen, A., Erisman, J.W.,
Owen, S., Daemmgen, U., Sutton, M.A., 2009b. Aerosol fluxes and particle
growth above grassland following the application of NH4NO3 fertilizers. Bio-
geosciences Discussions 6 (1), 341–389.
Neu, J.L., Lawler, M.J., Prather, M.J., Saltzman, E.S., 2008. Oceanic alkyl nitrates as
a natural source of tropospheric ozone. Geophysical Research Letters 35,
L13814. doi:10.1029/2008GL034189.
Neumann, H.H., den Hartog, G., 1985. Eddy correlation measurements of atmo-
spheric fluxes of ozone, sulphur, and particulates during the champaign inter-
comparison study. Journal of Geophysical Research 90, 2097–2110.
Nicholson, K.W., Davies, T.D., 1987. Field measurements of the dry deposition of
particulate sulphate. Atmospheric Environment 21, 1561–1571.
Nicholson, K.W., 1988. A review of particle resuspension. Atmospheric Environment
22, 2639–2651.
Nicholson, K.W., Branson, J.R., Giess, P., Cannell, R.J., 1989. The effect of vehicle
activity on particle resuspension. Journal of Aerosol Science 20, 1425–1428.
Nicholson, K.W., 1993. Wind-tunnel experiments on the resuspension of particulate
material. Atmospheric Environment Part A – General Topics 27, 181–188.
Niinemets, Ü., Tenhunen, J.D., Harley, P.C., Steinbrecher, R., 1999. A model of
isoprene emission based on energetic requirements for isoprene synthesis and
leaf photosynthetic properties for Liquidambar and Quercus. Plant Cell and
Environment 22, 1319–1336.
Niinemets, Ü., Reichstein, M., 2002. A model analysis of the effects of nonspecific
monoterpenoid storage in leaf tissues on emission kinetics and composition in
Mediterranean sclerophyllous Quercus species. Global Biogeochemical Cycles 16
(1110) DOI: 1110.1029/2002GB001927.
Niinemets, Ü., Seufert, G., Steinbrecher, R., Tenhunen, J.D., 2002a. A model coupling
foliar monoterpene emissions to leaf photosynthetic characteristics in Medi-
terranean evergreen Quercus species. New Phytologist 153, 257–276.
Niinemets, Ü., Reichstein, M., Staudt, M., Seufert, G., Tenhunen, J.D., 2002b. Stomatal
constraints may affect emission of oxygenated monoterpenoids from the foliage
of Pinus pinea. Plant Physiology 130, 1371–1385.
Niinemets, Ü., Peñuelas, J., 2008. Gardening and urban landscaping: significant
players in global change. Trends in Plant Science 13, 60–65.
Niinemets, Ü, 2008. Getting hold of terpene emissions from vegetation. ILEAPS
Newsletter 5, 40–42.
Nilsson, E.D., Rannik, U., 2001. Turbulent aerosol fluxes over the Arctic Ocean 1. Dry
deposition over sea and pack ice. Journal of Geophysical Research – Atmo-
spheres 106 (D23), 32125–32137.
Nilsson, E.D., Rannik, U., Swietlicki, E., Leck, C., Aalto, P.P., Zhou, J., Norman, M., 2001.
Journal of Geophysical Research 106 (D23), 32139–32154.
Noe, S.M., Ciccioli, P., Brancaleoni, E., Loreto, F., Niinemets, Ü., 2006. Emissions of
monoterpenes linalool and ocimene respond differently to environmental
changes due to differences in physico-chemical characteristics. Atmospheric
Environment 40, 4649–4662.
Noe, S.M., Copolovici, L., Niinemets, Ü., Vaino, E., 2008a. Foliar limonene uptake
scales positively with leaf lipid content: ‘‘non-emitting’’ species absorb and
release monoterpenes. Plant Biology 10, 129–137.
Noe, S.M., Peñuelas, J., Niinemets, Ü, 2008b. Monoterpene emissions from orna-
mental trees in urban areas: a case study of Barcelona, Spain. Plant Biology 10,
163–169.
Norris, S., Brooks, I., de Leeuw, G., Smith, M.H., Moeman, M., Lingard, J., 2007. Eddy
covariance measurements of sea spray particles over the Atlantic Ocean.
Atmospheric Chemistry and Physics Discussion 7, 13243–13269.
Novak, J., Pierce, T., 1993. Natural emissions of oxidant precursors, Water. Air, and
Soil Pollution 67, 57–77.
O’Dowd, C.D., Lowe, J., Smith, M.H., Kaye, A.D., 1999. The relative importance of sea-
salt and nss-sulphate aerosol to the marine CCN population: an improved
multi-component aerosol-droplet parameterisation. Quarterly Journal of the
Royal Meteorological Society 125, 1295–1313.
O’Dowd, C.D., Jimenez, J.L., Bahreini, R., Flagan, R.C., Seinfeld, J.H., Pirjola, L.,
Kulmala, M., Jennings, S.F.G., Hoffmann, T., 2002. Marine particle formation
from biogenic iodine emissions. Nature 417, 632–636.
O’Dowd, C.D., Facchini, M.C., Cavalli, F., Ceburnis, D., Mircea, M., Decesari, S.,
Fuzzi, S., Yoon, Y.J., Putaud, J.P., 2004. Biogenically-driven organic contribution
to marine aerosol. Nature. doi:10.1038/nature02959.
O’Dowd, C.D., Hoffmann, T., 2005. Coastal new particle formation: a review of the current
state-of-the-art. Environmental Chemistry 2, 245–255. doi:10.1071/EN05077.
O’Dowd, C.D., de Leeuw, G., 2007. Marine aerosol production: a review of the
current knowledge. Philosophical Transactions of the Royal Society.
doi:10.1098/rsta.2007.2043.
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
O’Dowd, C.D., Langmann, B., Varghese, S., Scannell, C., Ceburnis, D., Facchini, M.C.,
2008. A combined organic-inorganic sea-spray source function. Geophysical
Research Letters 35, L01801. doi:10.1029/2007GL030331.
Okin, G.S., 2005. Dependence of wind erosion and dust emission on surface
heterogeneity: stochastic modelling. Journal of Geophysical Research – Atmo-
spheres 110. doi:10.1029/2004JD005288.
Ould-Dada, Z., 2002. Dry deposition profile of small particle within a model spruce
canopy. Science of the Total Environment 286, 83–96.
Owen, S., Boissard, S., Street, R.A., Duckham, S.C., Csiky, O., Hewitt, N., 1997.
Screening of 18 Mediterranean plant species for volatile organic compound
emission. Atmospheric Environment 31, 101–117.
Owen, S.M., MacKenzie, A.R., Stewart, H., Donovan, R., Hewitt, C.N., 2003. Biogenic
volatile organic compound (VOC) emission estimates from an urban tree
canopy. Ecological Applications 13, 927–938.
Palmer, P.I., Jacob, D.J., Fiore, A.M., Martin, R.V., Chance, K., Kurosu, T.P., 2003. Mapping
isoprene emissions over North America using formaldehyde column observations
from space. Journal of Geophysical Research. doi:10.1029/2002JD002153.
Palmer, P.I., Abbot, D.S., Fu, T.-M., Jacob, D.J., Chance, K., Kurosu, T., Guenther, A.,
Wiedinmyer, C., Stanton, J., Pilling, M., Pressley, S., Lamb, B., Sumner, A.L., 2006.
Quantifying the seasonal and interannual variability of North American
isoprene emissions using satellite observations of formaldehyde column. Jour-
nal of Geophysical Research. doi:10.1029/2005JD006689.
Palmer, P.I., Barkley, M.P., Kurosu, T.P., Lewis, A.C., Saxton, J.E., Chance, K., Gatti, L.V.,
2007. Interpreting satellite column observations of formaldehyde over tropical
South America. Philosophical Transactions of the Royal Society. A. 365, 1741–1751.
Palmer, P.I., 2008. Quantifying sources and sinks of trace gases using space-borne
measurements: current and future science. Philosophical Transaction of the
Royal Society A – 2008 Triennial Issues, 366, 4509–4528.
Parton, W.J., Morgan, J.A., Wang, G.M., Del Grosso, S., 2007. Projected ecosystem
impact of the Prairie Heating and CO2 enrichment experiment. New Phytologist
174, 823–834.
Pesava, P., Aksu, R., Toprak, S., Horvath, H., Seidl, S., 1999. Dry deposition of particles
to building surfaces and soiling. Science of the Total Environment 235, 25–35.
Petroff, A., Mailliat, A., Amielh, M., Anselmet, F., 2007a. Aerosol dry deposition
on vegetative canopies. Part I: review of present knowledge. Atmospheric
Environment 42, 3625–3653.
Petroff, A., Mailliat, A., Amielh, M., Anselmet, F., 2007b. Aerosol dry deposition on
vegetative canopies. Part II: a new modelling approach and applications.
Atmospheric Environment 42, 3654–3683.
Pérez, T., Trumbore, S.E., Tyler, S.C., Matson, P.A., Ortiz-Monasterio, I., Rahn, T.,
Griffith, D.W.T., 2001. Identifying the agricultural imprint on the global
N2O budget using stable isotopes. Journal of Geophysical Research 106,
9869–9878.
Personne, E., Loubet, B., Herrmann, B., Mattsson, M., Schjoerring, J.K., Nemitz, E.,
Sutton, M.A., Cellier, P., 2009. SURFATM-NH3: a model combining the surface
energy balance and bi-directional exchanges of ammonia applied at the field
scale. Biogeosciences Discussions 6, 71–114.
Philippot, L., Hallin, S., Börjesson, G., Baggs, E.M., 2009 Biochemical cycling in the
rhizosphere having an impact on global change. Plant and Soil Special Issue
S28-RHIZO-BOOK, 321, 1–2.
Phillips, G.J., Thomas, R., Famulari, D., Williams, P.I., Crosier, J., Allan, J., Coe, H.,
Gallagher, M.W., Flynn, M., Nemitz, E., 2007. Fluxes of submicron organic
particles above three UK cities. In: Measurement of Speciated Aerosol Fluxes.
Ph.D. thesis. Thomas, R. (Ed.). University of Manchester, Manchester.
Phillips, G., Thomas, R., Famulari, D., Williams, P.I., Bower, K.N., Allan, J.D., Gallagher,
M.W., Flynn, M., Nemitz, E. Fluxes of submicron aerosol above three UK cities.
Atmospheric Chemistry and Physics, in preparation.
Pihlatie, M., Ambus, P., Rinne, J., Pilegaard, K., Vesala, T., 2005. Plant-mediated
nitrous oxide emissions from beech (Fagus sylvatica) leaves. New Phytologist
168, 93–98.
Pilegaard, K., Jensen, N.O., Hummelshøj, P., 1995. Seasonal and diurnal variation in
the deposition velocity of ozone over a spruce forest in Denmark. Water, Air and
Soil Pollution 85, 2223–2228.
Pilegaard, K., 2001. Air–Soil exchange of NO, NO2 and O3 in forests. Water, Air and
Soil Pollution: Focus 1 (5–6), 79–88 (10).
Pilegaard, K., Skiba, U., Ambus, P., Beier, C., Brüggemann, N., Butterbach-Bahl, K.,
Dick, J., Dorsey, J., Duyzer, J., Gallagher, M., Gasche, R., Horvath, L., Kitzler, B.,
Leip, A., Pihlatie, M.K., Rosenkranz, P., Seufert, G., Vesala, T., Westrate, H., Zech-
meister-Boltenstern, S., 2006. Factors controlling regional differences in forest
soil emission of nitrogen oxides (NO and N2O). Biogeosciences 3, 651–661.
Pio, C.A., Feliciano, M.S., Vermeulen, A.T., 2000. Seasonal variability of ozone
dry deposition under southern European climate conditions. Atmospheric
Environment 34 (2), 195.
Pio, C.A., Silva, P.A., Cerqueira, M.A., Nuñes, T.V., 2005. Diurnal and seasonal emis-
sions of volatile organic compounds from cork oak (Quercus suber) trees.
Atmospheric Environment 39, 1817–1827.
Pleijel, H., Pihl, G., Karlsson, G., Danielsson, H., Selldén, G., 1995. Surface wetness
enhances ozone deposition to a pasture canopy. Atmospheric Environment 29
(22), 3391–3393.
Pleijel, H., Danielsson, H., Ojanperä, K., De Temmerman, L., Högy, P., Badiani, M.,
Karlsson, P.E., 2004. Relationship between ozone exposure and yield loss in
European wheat and potato – a comparison of concentration- and flux-based
exposure indices. Atmospheric Environment 38, 2259–2269.
Pleijel, H., Danielsson, H., Emberson, L., Ashmore, M.R., Mills, G., 2007. Ozone risk
assessment for agricultural crops in Europe: further development of stomatal
5263
flux and flux–response relationships for European wheat and potato. Atmo-
spheric Environment 41, 3022–3040.
Polson, D. Boundary-layer-budget measurements of greenhouse gas emissions at
the country scale indicate national inventories underestimate nitrous oxide and
methane. Quarterly Journal of Royal Meteorological Society, submitted for
publication.
Pozzoli, L., Bey, I., Rast, S., Schultz, M.G., Stier, P., Feichter, J., 2008. Trace gas and
aerosol interactions in the fully coupled model of aerosol-chemistry-climate
ECHAM5-HAMMOZ: 2. Impact of heterogeneous chemistry on the global
aerosol distributions. 113 (7), D07309.
Pruppacher, H.R., Klett, J.D., 1997. Microphysics of Clouds and Precipitation, Second
Revised and Enlarged Edition. Kluwer Academic Publisher, 953 pp.
Pryor, S.C., Soerensen, L.L., 2000. Nitric acid–sea salt reactions: implication for
nitrogen deposition to wate surfaces. Journal of Applied Meteorology 39,
725–731.
Pryor, S.C., Binkowski, F.S., 2004. An analysis of the time scales assocaited with
aerosol processes during dry deposition. Aerosol Science Technology 38,
1091–1098.
Pryor, S.C., Klemm, O., 2004. Experimentally derived estimates of nitric acid dry
deposition velocity and viscous sub-layer resistance at a conifer forest. Atmo-
spheric Environment 38, 2769–2777.
Pryor, S.C., 2006. Size resolved particle deposition velocities of sub-100 nm diam-
eter particles over a forest. Atmospheric Environment 40, 6192–6200.
Pryor, S.C., Larsen, S.E., Sorensen, L.L., Barthelmie, R.J., Gronholm, T., Kulmala, M.,
Lauiainen, S., Rannik, Ü, Vesala, T., 2007. Particle fluxes over forests: analyses of
flux methods and functional dependencies. Journal of Geophysical Research 112
(D07205). doi:10.1029/2006JD008066.
Pryor, S.C., Barthelmie, R.J., Larsen, S.E., Sorensen, L.L., Sempreviva, A.M.,
Groenholm, T., Kulmala, M., Rannik, Ü, Vesala, T., 2008a. Upward particle
number fluxes over forest: where, when, why? Tellus B 60, 372–380.
Pryor, S.C., Gallagher, M.W., Sievering, H., Larsen, S.E., Barthelmie, R.J., Birsan, F.,
Nemitz, E., Rinne, J., Kulmala, M., Groenholm, T., Taipale, R., Vesala, T., 2008b. A
review of measurement and modelling results of particle atmosphere–surface
exchange. Tellus B 60, 42–75.
Pumpanen, J., Kolari, P., Ilvesniemi, H., Minkkinen, K., Vesala, T., Niinistö, S.,
Lohila, A., Larmola, T., Morero, M., Pihlatie, M., Janssens, I., Curiel Yuste, J.,
Grünzweig, J.M., Reth, S., Subke, J.-A., Savage, K., Kutsch, W., Østreng, G.,
Ziegler, W., Anthoni, P., Lindroth, A., Hari, P., 2004. Comparison of different
chamber techniques for measuring soil CO2 efflux. Agricultural and Forest
Meteorology 123, 159–176.
Raivonen, M., Bonn, M., Sanz, M.J., Vesala, T., Kulmala, M., Hari, P., 2006. UV-induced
NOy emissions from Scots pine: could they originate from photolysis of
deposited HNO3? Atmospheric Environment 40, 6201–6213.
Rannik, U., Petaja, T., Buzorius, G., Aalto, P., Vesala, T., Kulmala, M., 2000. Deposition
velocities of nucleation mode particles into a Scots pine forest. Environmental
and Chemical Physics 22, 97–102.
Rattray, G., Sievering, H., 2001. Dry deposition of ammonia, nitric acid, ammonium,
and nitrate to alpine tundra at Niwot Ridge, Colorado. Atmospheric Environ-
ment 35, 1105–1109.
Regener, V.H., 1957. The vertical flux of atmospheric ozone. Journal of Geophysical
Research 62, 221–228.
Reid, J.S., Jonsson, H.H., Smith, M.H., Smirnov, A., 2001. Evolution of the vertical
profile and flux of large sea-salt particles in the coastal zone. Journal of
Geophysical Research 106, 12039–12053.
Ren, L.-Q., Wang, S.-J., Tian, X.-M., Han, Z.-W., Yan, L.-N., Qui, Z.-M., 2007. Non-
smooth morphologies of typical plant leaf surfaces and their anti-adhesion
effects. Journal of Bionic Engineering 4, 33–40.
Rich, S., Waggoner, P.E., Tomlinson, H., 1970. Ozone uptake by bean leaves. Science
169, 79–80.
Riedo, M., Milford, C., Schmid, M., Sutton, M.A., 2002. Coupling soil–plant–atmo-
sphere exchange of ammonia with ecosystem functioning in grasslands.
Ecological Modelling 158, 83–110.
Rinne, J., Hakola, H., Laurila, T., 1999. Vertical fluxes of monoterpenes above a Scots
pine stand in the boreal vegetation zone. Physics and Chemistry of Earth 24,
711–715.
Rinne, J., Hakola, H., Laurila, T., Rannik, U., 2000. Canopy scale monoterpene emissions
of Pinus sylvestris dominated forests. Atmospheric Environment 34, 1099–1107.
Rinne, H.J.I., Guenther, A.B., Warneke, C., de Gouw, J.A., Luxembourg, S.L., 2001.
Disjunct eddy covariance technique for trace gas flux measurements.
Geophysical Research Letters 28, 3139–3142.
Rinne, H.J.I., Guenther, A.B., Greenberg, J.P., Harley, P.C., 2002. Isoprene and
monoterpene fluxes measured above Amazonian rainforest and their depen-
dence on light and temperature. Atmospheric Environment 36, 2421–2426.
Rinne, J., Ruuskanen, T.M., Reissell, A., Taipale, R., Hakola, H., Kulmala, M., 2005. On-
line PTR-MS measurements of atmospheric concentrations of volatile organic
compounds in a European boreal forest ecosystem. Boreal Environmental
Research 10, 425–436.
Rinne, J., Taipale, R., Markkanen, T., Ruuskanen, T.M., Hellén, H., Kajos, M.K., Vesala, T.,
Kulmala, M., 2007. Hydrocarbon fluxes above a Scots pine forest canopy:
measurements and modelling. Atmospheric Chemistry and Physics 7, 3361–3372.
Rinne, J., Douffet, T., Prigent, Y., Durand, P., 2008. Field comparison of disjunct and
conventional eddy covariance techniques for trace gas flux measurements.
Environmental Pollution 152, 630–635.
Roberts, J.M., 1990. The atmospheric chemistry of organic nitrates. Atmospheric
Environment 24A (2), 243–287.
5264 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Robinson, A.L., Donahue, N.M., Shrivastava, M.K., Weitkamp, E.A., Sage, A.M.,
Grieshop, A.P., Lane, T.E., Pierce, J.R., Pandis, S.N., 2007. Rethinking organic
aerosols: semivolatile emissions and photochemical aging. Science 2, 1259–1262.
Romakkaniemi, S., Kokkola, H., Laaksonen, A., 2005. Soluble trace gas effect on
cloud condensation nuclei activation: influence of initial equilibration on
cloud model results. Journal of Geophysical Research D 110, 15. doi:10.1029/
2004JD005364.
Rosenstiel, T.N., Potosnak, M.J., Griffin, K.L., Fall, R., Monson, R.K., 2003. Increased
CO2 uncouples growth from isoprene emission in an agriforest ecosystem.
Nature 421, 256–259.
Ruijgrok, W., Tieben, H., Eisinga, P., 1997. The dry deposition of particles to a forest
canopy: a comparison of model and experimental results. Atmospheric Envi-
ronment 31, 399–415.
Rummel, U., Ammann, C., Kirkman, G.A., 2007. Seasonal variation of ozone depo-
sition to a tropical rain forest in southwest Amazonia. Atmospheric Chemistry
and Physics 7, 7399–7450.
Russow, R., Sich, I., Neue, H.-U., 2000. The formation of the trace gases NO and N2O in
soils by the coupled processes of nitrification and denitrification: results of kinetic
15
N tracer investigations. Chemosphere – Global Change Science 2, 359–366.
Sakamoto, K., Takada, H., Sekiguchi, K., 2004. Influence of ozone, relative humidity
and flow rate on the deposition and oxidation of sulfur dioxide on yellow sand.
Atmospheric Environment 38, 6961–6967.
Sander, R., Kerkweg, A., Jöckel, P., Lelieveld, J., 2005. Technical note: the new
comprehensive atmospheric chemistry module MECCA. Atmospheric Chem-
istry and Physics 5, 445–450. http://www.atmos-chem-phys.net/5/445/2005/.
Sanderson, M.G., Collins, W.J., Hemming, D.L., Betts, R.A., 2007. Stomatal conduc-
tance changes due to increasing carbon dioxide levels: projeced impact on
surface ozone levels. B. Tellus 59, 404–411.
Scarratt, M.G., Moore, R.M., 1999. Production of chlorinated hydrocarbons and
methyl iodide by the red microalga Porphyridium purpureum. Limnology and
Oceanography 44, 703–707.
Schade, G.W., Goldstein, A.H., Gray, D.W., Lerdau, M.T., 2000. Canopy and leaf level
2-methyl-3-buten-2-ol fluxes from a ponderosa pine plantation. Atmospheric
Environment 34, 3535–3544.
Schade, G.W., Goldstein, A.H., 2001. Fluxes of oxygenated volatile organic
compounds from a ponderosa pine plantation. Journal of Geophysical Research
106, 3111–3123.
Schindlbacher, A., Zechmeister-Boltenstern, S., Butterbach-Bahl, K., 2004. Effects of
soil moisture and temperature on NO, NO2, and N2O emissions from European
forest soils. Journal of Geophysical Research 109, D17302.
Schjoerring, J.K., Husted, S., Mattsson, M., 1998. Physiological parameters control-
ling plant–atmosophere ammonia exchange. Atmospheric Environment
(Ammonia Special Issue) 32 (3), 491–498. 1998.
Schmidt, A., Klemm, O., 2008. Direct determination of highly size-resolved turbu-
lent particle fluxes with the disjunct eddy covariance method and a 12-stage
electrical low pressure impactor. Atmospheric Chemistry and Physics Discus-
sions 8, 8997–9034.
Schnitzler, J.P., Graus, M., Kruezwieser, J., Heizmann, U., Renneberg, H., Wisthaler, A.,
Hansel, A., 2004. Contribution of different carbon sources to isoprene biosyn-
thesis in poplar leaves. Plant Physiology 135, 152–160.
Scholefield, D., Hawkins, J.M.B., Jackson, S.M., 1997. Development of a helium
atmosphere soil incubation technique for direct measurement of nitrous oxide
and dinitrogen fluxes during denitrification. Soil Biology and Biochemistry 29,
1345–1352.
Schween, J.H., Dlugi, R., Hewitt, C.N., Foster, P., 1997. Determination and accuracy of
VOC-fluxes above the pine/oak forest at Castelporziano. Atmospheric Envi-
ronment 31, 199–215.
Seco, R., Peñuelas, J., Filella, I., 2007. Short-chain oxygenated VOCs: emission and
uptake by plants and atmospheric sources, sinks, and concentrations. Atmo-
spheric Environment 41, 2477–2499.
Sempreviva, A.M., Gryning, S.-E., 2000. Mixing height over water and its role on the
correlation between temperature and humidity fluctuations in the unstable
surface layer. Boundary-Layer Meteorology 97, 273–291.
Seufert, G., Bartzis, J., Bomboi, T., Ciccioli, P., Cieslik, S., Dlugi, R., Foster, P.,
Hewitt, C.N., Kesselmeier, J., Kotzias, D., Lenz, R., Manes, F., Perez Pastor, R.,
Steinbrecher, R., Torres, L., Valentini, R., Versino, B., 1997. An overview of the
Castelporziano experiments. Atmospheric Environment 31, 5–17.
Sharkey, T.D., Singsaas, E.L., Lerdau, M.T., Geron, C.D., 1999. Weather effects on
isoprene emission capacity and applications in emissions algorithms. Ecological
Applications 9, 1132–1137.
Sharkey, T.D., Yeh, S.S., 2001. Isoprene emission from plants. Annual Review Plant
Physiology and Molecular Biology 52, 407–436.
Shaw, W.J., Spicer, C.W., Kenny, D.V., 1998. Eddy correlation fluxes of trace gases
using a tandem mass spectrometer. Atmospheric Environment 32, 2887–2898.
Shaw, S.L., Chisholm, S.W., Prinn, R.G., 2003. Isoprene production by Pro-
chlorococcus, a marine cyanobacterium, and other phytoplankton. Marine
Chemistry 80, 227–245.
Sievering, H., 1983. Eddy flux and profile measurements of small particle dry-
deposition velocity at the Boulder Atmospheric Observatory (BAO). In:
Pruppacher, H.R., Semonin, R.G., Slinn, W.G.N. (Eds.), Precipitation Scavenging,
Dry Deposition and Resuspension. Elsevier, Amsterdam, NL, pp. 963–977.
Simon, E., Meixner, F.X., Ganzeveld, L., Kesselmeir, J., 2005a. Coupled carbon–water
exchange of the Amazon rain forest, II. Comparison of predicted and observed
seasonal exchange of energy, CO2, isoprene and ozone at a remote site in
Rondônia. Biogeosciences 2, 255–275.
Simon, V., Dumergues, L., Bouchou, P., Torres, L., Lopez, A., 2005b. Isoprene emission
rates and fluxes measured above a Mediterranean oak (Quercus pubescens)
forest. Atmospheric Research 74, 49–63.
Simpson, D., Winiwarter, W., Börjesson, G., Cinderby, S., Ferreiro, A., Guenther, A.,
Hewitt, C.N., Janson, R., Khalil, M.A.K., Owen, S., Pierce, T.E., Puxbaum, H.,
Shearer, M., Skiba, U., Steinbrecher, R., Tarrason, L., Öquist, M.G., 1999. Inventorying
emissions from nature in Europe. Journal of Geophysical Research 104, 8113–8152.
Simpson, D., Fagerli, H., Jonson, J.E., Tsyro, S., Wind, P., Tuovinen J.-, P., 2003.
Transboundary Acidification, Eutrophication and Ground Level Ozone in
Europe. Part I: Unified EMEP Model Description. EMEP Status Report 2003. Det
Meteorologisk Institutt, Oslo.
Simpson, D., Fagerli, H., Jonson, J.E., Tsyro, S., Wind, P., Tuovinen, J.-P., 2006.
Transboundary Acidification, Eutrophication and Ground Level Ozone in
Europe, Part I, Unified EMEP Model Description. Norwegian Meteorological
Office, Blindern. 1, 1–104. 1-8-2003.
Simpson, D., Ashmore, M., Emberson, L., Tuovinen, J.-P., 2007. A comparison of two
different approaches for mapping potential ozone damage to vegetation. A
model study. Environmental Pollution 146, 715–725.
Simpson, I.J., Meinardi, S., Blake, D.R., Blake, N.J., Rowland, F.S., Atlas, E., Flocke, F.,
2002. A biomass burning source of C-1-C-4 alkyl nitrates. Geophysical Research
Letters 29, 2168.
Singh, H.B., Tabazadeh, A., Evans, M.J., Field, B.D., Jacob, D.J., Sachse, G., Crawford, J.H.,
Shetter, R., Brune, W.H., 2003. Oxygenated volatile organic chemicals in the oceans:
inferences and implications based on atmospheric observations and air–sea
exchange models. Geophysical Research Letters 30 (16), 1862. doi:10.1029/
2003GL017933.
Sinha, V., Williams, J., Meyerhofer, M., Riebesell, U., Paulino, A.I., Larsen, A., 2007.
Air–sea fluxes of methanol, acetone, acetaldehyde, isoprene and DMS from
a Norwegian fjord following a phytoplankton bloom in a mesocosm experi-
ment. Atmospheric Chemistry and Physics 7, 739–755.
Sitch, S., Cox, P.M., Collins, W.J., Huntingford, C., 2007. Indirect radiative forcing of climate
change through ozone effects on the land-carbon sink. Nature 488, 791–794.
Skiba, U., Fowler, D., Smith, K.A., 1997. Nitric oxide emissions from agricultural soils
in temperate and tropical climates: sources, controls and mitigation options.
Nutrient Cycling in Agroecosystems 48, 139–153.
Skiba, U., 1998. Soil nitrous oxide and nitric oxide emissions as indicators of
elevated atmospheric N deposition rates in seminatural ecosystems. Environ-
mental Pollution 102, 457–461.
Skiba, U., Di Marco, C., Hargreaves, K., Sneath, R., McCartney, L., 2006. Nitrous oxide
emissions from a dung heap measured by chambers and plume methods.
Agricultural Ecosystem & Environment 112, 135–139.
Slemr, F., Seiler, W., 1984. Field measurements of NO AND NO2 emissions from
fertilized and unfertilized soil. Journal of Atmospheric Chemistry 2, 1–24.
Slinn, W.G.N., 1982. Predictions for particle deposition to vegetative canopies.
Atmospheric Environment 16, 1785–1794.
Smart, D.R., Bloom, A.J., 2001. Wheat leaves emit nitrous oxide during nitrate
assimilation. Proceedings of the National Academy of Sciences of the United
States of America 98, 7875–7878.
Smith, R.I., Fowler, D., Sutton, M.A., Flechard, C., Coyle, M., 2000. Regional estima-
tion of pollutant gas deposition in the UK: model description, sensitivity
analyses and outputs. Atmospheric Environment 34, 3757–3777.
Soerensen, L.L., Pryor, S.C., De Leeuw, G., Schulz, M., 2005. Flux divergence of nitric
acid in the marine atmospheric surface layer. Journal of Geophysical Research –
Atmospheres 110. doi:10.1029/2004JD005403.
Solberg, S., Hov, Ø., Søvde, A., Isaksen, I.S.A., Coddeville, P., De Backer, H., Forster, C.,
Orsolini, Y., Uhse, K., 2008. European surface ozone in the extreme summer 2003.
Journal of Geophysical Research 113, D07307. doi:10.1029/2007/JD009098.
Sorimachi, A., Sakamoto, K., Ishihara, H., Fukuyama, T., Utiyama, M., Liu, H.,
Wang, W., Tang, D., Dong, X., Quan, H., 2003. Measurements of sulfur dioxide
and ozone dry deposition over short vegetation in northern China – a prelimi-
nary study. Atmospheric Environment 37, 3157–3166.
Sorimachi, A., Sakamoto, K., Sakai, M., Ishihara, H., Fukuyama, T., Utiyama, M.,
Liu, H., Wang, W., Tang, D., Dong, X., Quan, H., 2004. Laboratory and field
measurements of dry deposition of sulfur dioxide onto Chinese loess surfaces.
Environmental Science & Technology 38, 3396–3404.
Sorimachi, A., Sakamoto, K., 2007. Laboratory measurement of the dry deposition of
sulfur dioxide onto northern Chinese soil samples. Atmospheric Environment
41, 2862–2869.
Sorjamaa, R., Svenningsson, B., Raatikainen, T., Henning, S., Bilde, M., Laaksonen, A.,
2004. The role of surfactants in Köhler theory reconsidered. Atmospheric
Chemistry and Physics 4 (8), 2107–2117.
Sparks, J.P., Roberts, J.M., Monson, R.K., 2003. The uptake of gaseous organic
nitrogen by leaves: a significant global nitrogen transfer process. Geophysical
Research Letters 30, 2189. doi: 2110.1029/2003GL018578.
Spindler, G., Teichmann, U., Sutton, M.A., 2001. Ammonia dry deposition over
grassland: micrometeorological flux gradient measurements and bi-directional
flux calculations using an inferential model. Quarterly Journal of the Royal
Meteorological Society 127, 795–814.
Spirig, C., Guenther, A., Greenberg, J.P., Calanca, P., Tarvainen, V., 2004. Tethered
balloon measurements of biogenic volatile organic compounds at a Boreal
forest site. Atmospheric Chemistry and Physics 4, 215–229.
Spirig, C., Neftel, A., Ammann, C., Dommen, J., Grabmer, W., Thielmann, A.,
Schaub, A., Beauchamp, J., Wisthaler, A., Hansel, A., 2005. Eddy covariance flux
measurements of biogenic VOCs during ECHO 2003 using proton transfer
reaction mass spectrometry. Atmospheric Chemistry and Physics 5, 465–481.
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Spracklen, D.V., Arnold, S.R., Carslaw, K.S., Sciare, J., Pio, C., 2008. Globally significant
oceanic source of organic carbon aerosol. Geophysical Research Letters 35,
L12811. doi:10.1029/2008GL033359.
Stark, J.D., Smart, D.R., Hart, S.C., Haubensak, K.A., 2002. Regulation of nitric oxide
emissions from forest and rangeland soils of western North America. Ecology
83, 2278–2292.
Staudt, M., Bertin, N., Frenzel, B., Seufert, G., 2000. Seasonal variation in amount
and composition of monoterpenes emitted by young Pinus pinea trees –
implications for emission modeling. Journal of Atmospheric Chemistry 35,
77–99.
Staudt, M., Mir, C., Joffre, R., Rambal, S., Bonin, A., Landais, D., Lumaret, R.,
2004. Isoprenoid emissions of Quercus spp. (Q. suber and Q. ilex) in mixed
stands contrasting in interspecific genetic introgression. New Phytologist
163, 573–584.
Stehfest, E., Bouwman, L., 2006. N2O and NO emission from agricultural fields and
soils under natural vegetation: summarizing available measurement data and
modeling of global annual emissions. Nutrient Cycling in Agroecosystems 74,
207–228.
Steinbrecher, R., Klauer, M., Hauff, K., Stockwell, W.R., Jaeschke, W., Dietrich, T.,
Herbert, F., 2000. Biogenic and anthropogenic fluxes of non-methane hydro-
carbons over an urban-impacted forest, Frankfurter Stadtwald, Germany.
Atmospheric Environment 34, 3779–3788.
Stemmler, K., Ammann, M., Donders, C., Kleffmann, J., George, C., 2006. Photo-
sensitized reduction of nitrogen dioxide on humic acid as a source of nitrous
acid. Nature 440, 195–198.
Stevenson, D.S., Dentener, F.J., Schulz, M.G., Ellingsen, K., van Noije, T.P.C., Wild, O.,
Zeng, G., Amann, M., Atherton, C.S., Bell, N., Bergmann, D.J., Bey, I., Butler, T.,
Cofala, J., Collins, W.J., Derwent, R.G., Doherty, R.M., Drevet, J., Eskes, H.J.,
Fiore, A.M., Gauss, M., Hauglustaine, D.A., Horowicz, L.W., Isaksen, I.S.A.,
Krol, M.C., Lamarque, J.-F., Lawrence, M.G., Montanaro, V., Müller, J.-F., Pitari, G.,
Prather, M.J., Pyle, J.A., Rast, S., Rodriguez, J.M., Sanderson, M.G., Savage, N.H.,
Shindell, D.T., Strahan, S.E., Sudo, K., Szopa, S., 2006. Multimodel ensemble
simulations of present-day and near-future tropospheric ozone. Journal of
Geophysical Research 111, D08301. doi:10.1029/2005JD006338.
Sun, J., Ariya, P.A., 2006. Atmospheric organic and bio-aerosols as cloud conden-
sation nuclei (CCN): a review. Atmospheric Environment 40, 795–820.
Sutka, R.L., Ostrom, N.E., Ostrom, P.H., Gandhi, H., Breznak, J.A., 2003. Nitrogen
isotopomer site preference of N2O produced by Nitrosomonas europaea and
Methylococcus capsulatus Bath. Rapid Communications in Mass Spectrometry
17, 738–745.
Sutton, M.A., Fowler, D., Moncrieff, J.B., 1993a. The exchange of atmospheric
ammonia with vegetated surfaces. I: unfertilized vegetation. Quarterly Journal
of the Royal Meteorological Society 119, 1023–1045.
Sutton, M.A., Pitcairn, C.E.R., Fowler, D., 1993b. The exchange of ammonia between the
atmosphere and plant communities. Advanced Ecology Research 24, 301–393.
Sutton, M.A., Fowler, D., 1993. A model for inferring bi-directional fluxes of
ammonia over plant canopies. In: Proceedings of the WMO Conference on the
Measurement and Modelling of Atmospheric Composition Changes Including
Pollutant Transport. World Meteorological Organization, Geneva, pp. 179–182.
Sutton, M.A., Asman, W.A.H., Schjørring, J.K., 1994. Dry deposition of reduced
nitrogen. Tellus 46B, 255–273.
Sutton, M.A., Schjørring, J.K., Wyers, G.P., 1995. Plant atmosphere exchange of ammonia.
Philosophical Transactions of the Royal Society, London A351 (1656), 261–276.
Sutton, M.A., Perthue, E., Fowler, D., Storeton-West, R.L., Cape, J.N., Arends, B.G.,
Möls, J.J., 1997. Vertical distribution and fluxes of ammonia at Great Dun Fell. In:
Fuzzi, S. (Ed.), Special Issue on the Great Dun Fell Cloud Experiment 1993.
Atmospheric Environment, vol. 31, pp. 2615–2625.
Sutton, M.A., Burkhardt, J.K., Guerin, D., Nemitz, E., Fowler, D., 1998. Development of
resistance models to describe measurement of bi-directional ammonia surface–
atmosphere exchange. Atmospheric Environment 32, 473–480.
Sutton, M.A., Nemitz, E., Fowler, D., Wyers, G.P., Otjes, R.P., Schjoerring, J.K.,
Husted, S., Nielsen, K., San José, R., Moreno, J., Gallagher, M.W., Gut, A., 2000a.
Fluxes of ammonia over oilseed rape: overview of the EXAMINE experiment.
Agricultural and Forest Meteorology (Ammonia Special Issue) 105 (4),
327–349.
Sutton, M.A., Nemitz, E., Milford, C., Fowler, D., Moreno, J., San Jose, R., Wyers, G.P.,
Otjes, R., Harrison, R., Husted, S., Schjoerring, J.K., 2000b. Micrometeorological
measurements of net ammonia fluxes over oilseed rape during two vegetation
periods. Agricultural and Forest Meteorology (Ammonia Exchange Special
Issue) 105 (4), 351–369.
Sutton, M.A., Milford, C., Nemitz, E., Theobald, M.R., Hill, P.W., Fowler, D.,
Schjoerring, J.K., Mattsson, M.E., Nielsen, K.H., Husted, S., Erisman, J.W., Otjes, R.,
Hensen, A., Mosquera, J., Cellier, P., Loubet, B., David, M., Genermont, S., Neftel, A.,
Blatter, A., Herrmann, B., Jones, S.K., Horvath, L., Führer, E., Mantzanas, K.,
Koukoura, Z., Gallagher, M., Williams, P., Flynn, M., Riedo, M., 2001. Biosphere–
atmosphere interactions of ammonia with grasslands: experimental strategy and
results from a new European initiative. Plant and Soil 228, 131–145.
Sutton, M.A., Milford, C., Nemitz, E., Theobald, M.R., Riedo, M., Hargreaves, K.J., Hill, P.W.,
Dragosits, U., Fowler, D., Schjoerring, J.K., Mattsson, M.E., Husted, S., Erisman, J.W.,
Hensen, A., Mosquera, J., Otjes, R., Cellier, P., Loubet, B., David, M., Neftel, A.,
Hermann, B., Jones, S.K., Blatter, A., Horvath, L., Weidinger, T., Meszaros, R., Raso, J.,
Mantzanas, K., Koukoura, Z., Gallagher, M., Dorsey, J., Flynn, M., Lehman, B.,
Burkhardt, J., Daemmgen, U., 2002. Ammonia exchange with vegetation: measure-
ment, modelling & application. In: Midgley, P.M., Reuther, M. (Eds.), Transport and
Chemical Transformation in the Troposphere. Margraf Verlag, pp. 49–60.
5265
Sutton, M.A., Nemitz, E., Erisman, J.W., Beier, C., Butterbach Bahl, K., Cellier, C., de
Vries, W., Cotrufo, F., Skiba, U., Di Marco, C., Jones, S., Laville, P., Soussana, J.F.,
Loubet, B., Twigg, M., Famulari, D., Whitehead, J., Gallagher, M.W., Neftel, A.,
Flechard, C., Herrmann, B., Calanca, P.L., Schjoerring, J.K., Daemmgen, U., Horvath, L.,
Tang, Y.S., Emmett, B.A., Tietema, A., Peñuelas, J., Kesik, M., Brueggemann, N.,
Pilegaard, K., Vesala, T., Campbell, C.L., Olesen, J.E., Dragosits, U., Theobald, M.R.,
Levy, P., Mobbs, D.C., Milne, R., Viovy, N., Vuichard, N., Smith, J.U., Smith, P.E.,
Bergamaschi, P., Fowler, D., Reis, S., 2007. Challenges in quantifying biosphere–
atmosphere exchange of nitrogen species. Environment Pollution 150, 125–139.
Sutton, M.A., Nemitz, E., Theobald, M.R., Milford, C., Dorsey, J.R., Gallagher, M.W.,
Hensen, A., Jongejan, P.A.C., Erisman, J.W., Mattsson, M.E., Schjoerring, J.K.,
Cellier, P., Loubet, B., Roche, R., Neftel, A., Herrmann, B., Jones, S.K., Lehman, B.E.,
Horvath, L., Weidinger, T., Rajkai, K., Burkhardt, J., Löpmeier, F.J., Dämmgen, U.,
2008a. Dynamics of ammonia exchange with cut grassland: strategy and
implementation of the GRAMINAE integrated experiment. Biogeosciences
Discussions 5, 3347–3407.
Sutton, M.A., Erisman, J.W., Dentener, F., Moeller, D., 2008b. Ammonia in the
environment: from ancient times to the present. Environmental Pollution 156
(3), 583–604.
Sutton, M.A., Reis, S., Baker, S.M.H. (Eds.), 2008c. Atmospheric Ammonia: Detecting
Emission Changes and Environmental Impacts. Springer.
Sutton, M.A., Reis, S., Baker, S.M.H. (Eds.), 2009a. Atmospheric Ammonia: Detecting
Emission Changes and Environmental Impacts. Springer, 464 pp.
Sutton, M.A., Nemitz, E., Milford, C., Campbell, C., Erisman, J.W., Hensen, A.,
Cellier, P., David, M., Loubet, B., Personne, E., Schjoerring, J.K., Mattsson, M.E.,
Dorsey, J.R., Gallagher, M.W., Horvath, L., Weidinger, T., Meszaros, R.,
Dämmgen, U., Neftel, A., Herrmann, B., Lehman, B., Flechard, C., Burkhardt, J.,
2009b. Dynamics of ammonia exchange with cut grassland: synthesis of results
and conclusions of the GRAMINAE integrated experiment. Biogeoscience
Discussions 6, 1121–1184.
Ta, W., Wei, C., Chen, F., 2005. Long-term measurements of SO2 dry deposition over
Gansu Province, China. Atmospheric Environment 39, 7095–7105.
Takahashi, A., Sato, K., Wakamatsu, T., Fujita, S., 2001. Atmospheric deposition of
acidifying components to a Japanese cedar forest. Water, Air and Soil Pollution
130, 559–564.
Takahashi, A., Sato, K., Wakamatsu, T., Fujita, S., Yoshikawa, K., 2002. Estimation of
dry deposition of sulfur to a forest using an inferential method. Influence of
canopy wetness on SO2 dry deposition. Journal of Japan Society for Atmospheric
Environment 37 (3), 192–205.
Tang, Y.S., Simmons, I., van Dijk, N., Di Marco, C., Nemitz, E., Dämmgen, U., Gilke, K.,
Djuricic, V., Vidic, S., Gliha, Z., Borovecki, D., Mitosinkova, M., Hanssen, J.E.,
Uggerud, T.H., Sanz, M.J., Sanz, P., Chorda, J.V., Flechard, C.R., Fauvel, Y., Ferm, M.,
Perrino, C., Sutton, M.A., 2009. European scale application of atmospheric
reactive nitrogen measurements in a low-cost approach to infer dry deposition
fluxes. Agriculture. Ecosystems & Environment 133, 183–195.
Tarrason, L., Nyiri, A., 2008. Transboundary Acidification, Eutrophication and Ground
Level Ozone in Europe in 2006. Norwegian Meterological Institute. 2008.
Theobald, M.R., Dragosits, U., Place, C.J., Smith, J.U., Sozanska, M., Brown, L.,
Scholefield, D., Del Prado, A., Webb, J., Whitehead, P.G., Angus, A., Hodge, I.D.,
Fowler, D., Sutton, M.A., 2004. Modelling nitrogen fluxes at the landscape scale.
WASP Focus 4 (6), 135–142.
Thomas, R., 2007. Measurement of speciated aerosol fluxes. PhD thesis. In Physics
Department, University of Manchester, Manchester, 298 pp.
Thomas, R., Trebs, I., Otjes, R., Jongejan, P.A.C., ten Brink, H., Phillips, G., Korner, M.,
Meixner, F.X., Nemitz, E., 2009. An automated analyser to measure surface–
atmosphere exchange fluxes of water soluble inorganic aerosol compounds and
reactive trace gases. Environmental Science & Technology. doi:10.1021/
es8019403.
Tingey, D.T., Turner, D.P., Weber, J.A., 1991. Factors controlling the emissions of
monoterpenes and other volatile organic compounds. In: Sharkey, T.D.,
Holland, E.A., Mooney, H.A. (Eds.), Trace Gas Emissions by Plants.
Academic Press, Inc., San Diego/New York/Boston/London/Sydney/Tokyo/
Toronto, pp. 93–119.
Topping, D.O., McFiggans, G.B., Kiss, G., Varga, Z., Facchini, M.C., Decesari, S.,
Mircea, M., 2007. Surface tensions of multi-component mixed inorganic/organic
aqueous systems of atmospheric significance: measurements, model predic-
tions and importance for cloud activation predictions. Atmospheric Chemistry
and Physics 7 (9), 2371–2398.
Tost, H., Jöckel, P., Kerkweg, A., Pozzer, A., Sander, R., Lelieveld, J., 2007. Global cloud
and precipitation chemistry and wet deposition: tropospheric model simula-
tions with ECHAM5/MESSy1. Atmospheric Chemistry and Physics 7, 2733–2757.
http://www.atmos-chem-phys.net/7/2733/2007/.
Trebs, I., Lara, L.L., Zeri, L.M.M., Gatti, L.V., Artaxo, P., Dlugi, R., Slanina, J.,
Andreae, M.O., Meixner, F.X., 2006. Dry and wet deposition of inorganic
nitrogen compounds to a tropical pasture site (Rondonia, Brazil). Atmospheric
Chemistry and Physics 6, 447–469.
Tuovinen, J.P., Aurela, M., Laurila, T., 1998. Resistance to ozone deposition to a flark
fen in the northern aapa mire zone. Journal of Geophysical Research-
Atmospheres 203, 16953–16966.
Tuovinen, J.-P., 2000. Assessing vegetation exposure to ozone: properties of the
AOT40 index and modifications by deposition modelling. Environmental
Pollution 109, 361–372.
Tuovinen, J.-P., Simpson, D., Mikkelsen, T.N., Emberson, L.D., Ashmore, M.R.,
Aurela, M., Cambridge, H.M., Hovmand, M.F., Jensen, N.O., Laurila, T.,
Pilegaard, K., Ro-Poulsen, H., 2001. Comparisons of measured and modelled
5266 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
ozone deposition to forests in Northern Europe. Water, Air and Soil Pollution:
Focus 1, 263–274.
Tuovinen, J.-P., Ashmore, M., Emberson, L., Simpson, D., 2004. Testing and
improving the EMEP ozone deposition module. Atmospheric Environment 38,
2373–2385.
Tuovinen, J.-P., Simpson, D., Altimir, N., 2008. Modelling the Stomatal and Non-
stomatal Ozone Fluxes to Coniferous Forests in Northern Europe. EGU General
Assembly, 14–18 April 2008, Vienna, Austria, Geophysical Research Abstracts,
vol. 10. EGU2008-A-08272.
Tuovinen, J.-P., Simpson, D., 2008b. An aerodynamic correction for the European
ozone risk assessment methodology. Atmospheric Environment 42, 8371–8381.
Turner, N.C., Waggoner, P.E., Rich, S., 1974. Removal of ozone from the atmosphere
by soil and vegetation. Nature 250, 486–489.
Turnipseed, A.A., Huey, L.G., Nemitz, E., Stickel, R., Higgs, J., Tanner, D.J., Slusher, D.L.,
Sparks, J.P., Flocke, F., Guenther, A., 2006. Eddy covariance fluxes of peroxyacetyl
nitrates (PANs) and NOy to a coniferous forest. Journal of Geophysical Research
– Atmospheres 111, D09304. doi: 09310.01029/02005JD006631.
Twigg, M., Famulari, D., Fowler, D., Gallagher, M., Nemitz, E., Sutton, M.A.,
Whitehead, J., Rippey, B., 2005. Principles and development of tunable laser
diode absorption spectroscopy for measuring fluxes of ammonia and nitric acid.
First ACCENT Symposium Proceedings. Urbino, 12–16. September 2005.
Ulbrich, I.M., Canagaratna, M.R., Zhang, Q., Worsnop, D.R., Jimenez, J.L. 2009.
Interpretation of organic components from positive matrix Factorization of
aerosol mass spectrometric data. Atmospheric Chemistry and Physics Discus-
sions 9, 2891–2918.
UNECE, 2004. Mapping critical levels for vegetation. In: Manual on Methodologies
and Criteria for Modelling and Mapping Critical Loads & Levels and Air Pollution
Effects, Risks and Trends. UNECE Convention on Long-range Transboundary Air
Pollution, Geneva Available at: www.icpmapping.org (Chapter 3).
Utiyama, M., Fukuyama, T., Sakamoto, K., Ishihara, H., Sorimachi, A., Tanonaka, T.,
Dong, X., Quan, H., Wang, W., Tang, D., 2005. Sulfur dioxide dry deposition on
the loess surface–surface reaction concept for measuring dry deposition flux.
Atmospheric Environment 39, 329–335.
Vaattovaara, P., Huttunen, P.E., Yoon, Y.J., Joutsensaari, J., Lehtinen, K.E.J., O’Dowd, C.D.,
Laaksonen, A., 2006. The composition of nucleation and Aitken modes particles
during coastal nucleation events: evidence for marine secondary organic contri-
bution. Atmospheric Chemistry and Physics 6, 4601–4616.
Van Hove, L.W.A., Adema, E.H., Vredenberg, W.J., Pieters, G.A., 1989. A study of the
adsorption of NH3 and SO2 on leaf surfaces. Atmospheric Environment 23,
1479–1486.
Van Oijen, M., Rougier, J., Smith, R., 2005. Bayesian calibration of process-based
forest models: bridging the gap between models and data. Tree Physiology 25,
915–927.
Van Oss, R., Duyzer, J., Wyers, P., 1998. The influence of gas-to-particle conversion
on measurements of ammonia exchange over forest. Atmospheric Environment
32, 465–471.
Vautard, R., Honoré, C., Beekmann, M., Rouil, L., 2005. Simularion of ozone during
the August 2003 heat wave and emission control scenarios. Atmospheric
Environment 39, 2957–2967.
Velasco, E., Lamb, B., Pressley, S., Allwine, E., Westberg, H., Jobson, B.T.,
Alexander, M., Prazeller, P., Molina, L., Molina, M., 2005. Flux measurements of
volatile organic compounds from an urban landscape. Geophysical Research
Letters 32 (20).
Venterea, R.T., Rolston, D.E., 2000. Mechanisms and kinetics of nitric and nitrous
oxide production during nitrification in agricultural soil. Global Change Biology
6, 303–316.
Venterea, R.T., Rolston, D.E., Cardon, Z.G., 2005. Effects of soil moisture, physical,
and chemical characteristics on abiotic nitric oxide production. Nutrient Cycling
in Agroecosystems 72, 27–40.
Vesala, T., Jarvi, L., Launiainen, S., Sogachev, A., Rannik, Ü., Mammarella, I., Siivola, E.,
Keronen, P., Rinne, J., Riikonen, A., Nikinmaa, E., 2007. Surface–atmosphere
interactions over complex urban terrain in Helsinki, Finland. Tellus B 60,
188–199.
Vigano, I., van Weelden, H., Holzinger, R., Keppler, F., McLeod, A., Rockmann, T.,
2008. Effect of UV radiation and temperature on the emission of methane from
plant biomass and structural components. Biogeosciences 5, 937–947.
Vitel, H., Kromer, B., Moessner, M., Platt, U., 2002. New technique for measurements
of atmospheric vertical trace gas profiles using DOAS. Environmental Science
and Pollution 9, 17–26.
Voisin, D., Legrand, M., Chaumerliac, N., 2000. Scavenging of acidic gases (HCOOH,
CH3COOH, HNO3, HCl, and SO2) and ammonia in mixed liquid-solid water
clouds at the Puy de Dôme mountain (France). Journal of Geophysical Research
105 (D5), 6817–6836.
Vong, R.J., Vickers, D., Covert, D.S., 2004. Eddy correlation measurements of aerosol
deposition to grass. Tellus Series B – Chemical and Physical Meteorology 56B,
105–117.
Walker, J.T., Robarge, W.P., Wuc, Y., Meyers, T.P., 2006. Measurement of bi-direc-
tional ammonia fluxes over soybean using the modified Bowen-ratio technique.
Agricultural and Forest Meteorology 138, 54–68.
Wang, T.J., Zhang, Y., Zhang, M., Hu, Z.Y., Xu, C.K., Zhao, Y.W., 2003. Atmospheric
sulfur deposition and the sulfur nutrition of crops at an agricultural site in
Jiangxi province of China. Tellus 55B, 893–900.
Webb, E.K., Pearman, G.I., Leuning, R., 1980. Correction of flux measurements for
density effects due to heat and water vapour transfer. Quarterly Journal of the
Royal Meteorological Society 106, 85–100.
Werner, C., Butterbach-Bahl, K., Haas, E., Hickler, T., Kiese, R., 2007. A global inventory
of N2O emissions from tropical rainforest soils using a detailed biogeochemical
model. Global Biogeochemical Cycles 21, GB3010. doi:10.1029/2006GB002909.
Wesely, M.L., 1983. Turbulent transport of ozone to surfaces common in the eastern
half of the United States. Advances in Environmental Science and Technology
12, 345–370.
Wesely, M.L., Cook, D.R., Hart, R.L., Speer, R.E., 1985. Measurements and parame-
terization of particulate sulfur dry deposition over grass. Journal of Geophysical
Research – Atmospheres 90, 2131–2143.
Wesely, M.L., 1989. Parameterization of surface resistance to gaseous dry deposition
in regional scale, numerical models. Atmospheric Environment 23, 1293–1304.
Wesely, M.L., Hicks, B.B., 2000. A review of the current status of knowledge on dry
deposition. Atmospheric Environment 34, 2261–2282.
Whitehead, J.D., Twigg, M., Famulari, D., Nemitz, E., Sutton, M.A., Gallagher, M.W.,
Fowler, D., 2008. Evaluation of laser absorption spectroscopic techniques for
eddy covariance flux measurements of ammonia. Environmental Science &
Technology. doi:10.1021/es071596u.
Whitehead, J.D., McFiggans, G.B., Gallagher, M.W., Flynn, M.J., 2009. Direct linkage
between tidally driven coastal ozone deposition fluxes, particle emission fluxes
and subsequent CCN formation. Geophysical Research Letters 36, L04806.
Wichink Kruit, R.J., van Pul, W.A.J., Otjes, R.P., Hofschreuder, P., Jacobs, A.F.G.,
Holtslag, A.A.M., 2007. Ammonia fluxes and derived canopy compensation
points over non-fertilized agricultural grassland in The Netherlands using the
new gradient ammoniadhigh accuracydmonitor (GRAHAM). Atmospheric
Environment 41, 1271–1287.
Wiedinmyer, C., Greenberg, J., Guenther, A., Hopkins, B., Baker, K., Geron, C.,
Palmer, P.I., Long, B.P., Turner, J.R., Petron, G., Pierce, T.E., Lamb, B., Westberg, H.,
Baugh, W., Harley, P., Koerber, M., Jannsen, M., 2005. The Ozarks Isoprene
Experiment (OZIE): measurements and model interpretations of the ‘isoprene
volcano’. Journal of Geophysical Research. doi:10.1029/2005JD005800.
Williams, J., Pöschl, U., Crutzen, P.J., Hansel, A., Holzinger, R., Warneke, C.,
Lindinger, W., Lelieveld, J., 2001. An atmospheric chemistry interpretation of
mass Scans obtained from a proton transfer mass spectrometer flown over the
tropical rainforest of Surinam. Journal Atmospheric Chemistry 38, 133–166.
Williams, J., 2004. Organic trace gases: an overview. Environmental Chemistry 1,
125–136.
Williams, J., Holzinger, R., Gros, V., Xu, X., Atlas, E., Wallace, D.W.R., 2004.
Measurements of organic species in air and seawater from the tropical Atlantic.
Geophysical Research Letters 31 (23), L23S06.
Wolfe, G.M., Yatavelli, R.L.N., Thornton, J.A., McKay, M., Goldstein, A.H., LaFranchi, B.,
Min, K.-E., Cohen, R.C., 2008. Eddy covariance fluxes of acyl preoxy nitrates
(PAN, PPN, and MPAN) above a Ponderosa pine forest. Atmospheric Chemistry
and Physics Discussions 8, 17495–17548.
Wolke, R., Sehili, A.M., Simmel, M., Knoth, O., Tilgner, A., Herrmann, H., 2005.
SPACCIM: a parcel model with detailed microphysics and complex multiphase
chemistry. Atmospheric Environment 39, 4375–4388.
Wrage, N., van Groenigen, J.W., Oenema, O., Baggs, E.M., 2005. A novel dual-isotope
labelling method for distinguishing between soil sources of N2O. Rapid
Communications in Mass Spectrometry 19, 3298–3306.
Wuebbles, D.J., Hayhoe, K., 2002. Atmospheric methane and global change. Earth-
Science Reviews 57, 177–210.
Wyers, G.P., Otjes, R.P., Slanina, J., 1993. A continuous-flow denuder for the
measurement of ambient concentrations and surface-exchange fluxes of
ammonia. Atmospheric Environment 27, 2085–2090.
Wyers, G.P., Duyzer, J.H., 1997. Micrometeorological measurement of the dry
deposition flux of sulphate and nitrate aerosols to coniferous forest. Atmo-
spheric Environment 31, 333–343.
Wyers, G.P., Erisman, J.W., 1998. Ammonia exchange over coniferous forest.
Atmospheric Environment 32 (3), 441–451.
Xu, Y., Carmichael, G.R., 1998. Modeling the dry deposition velocity of sulfur dioxide
and sulfate in Asia. Journal of Applied Meteorology 37, 1084–1099.
Xu, C.K., Hu, Z.Y., Cai, Z.C., Wang, T.J., He, Y.Q., Cao, Z.H., 2004. Atmospheric sulfur
deposition for a red soil broadleaf forest in southern China. Pedosphere 14 (3),
323–330.
Yan, X., Shi, S., Du, L., Xing, G., 2000. Pathways of N2O emission from rice paddy soil.
Soil Biology and Biochemistry 32, 437–440.
Yassaa, N., Peeken, I., Zöllner, E., Bluhm, K., Arnold, S., Spracklen, D., Wernli, H.,
Williams, J., 2008. Evidence for marineproduction of monoterpenes, Environ-
mental Chemistry 6, 391–401.
Yienger, J., Levy, H., 1995. Empirical model of global soil–biogenic NOx emissions.
Journal of Geophysical Research 100, 11447–11464.
Yin, Y., Carslaw, K.S., Feingold, G., 2005. Vertical transport of aerosols in a mixed-
phase convective cloud and the feedback on cloud development. Quarterly
Journal of the Royal Meteorological Society 131, 221–245.
Yoon, Y.J., Ceburnis, D., Cavalli, F., Jourdan, O., Putaud, J.P., Facchini, M.C., Decesari, S.,
Fuzzi, S., Jennings, S.G., O’Dowd, C.D., 2007. Seasonal characteristics of the
physico-chemical properties of North Atlantic marine atmospheric aerosols.
Journal of Geophysical Research 112, D04206. doi: 0.1029/2005JD007044.
Yun, H.J., Yi, S.M., Kim, Y.P., 2002. Dry deposition fluxes of ambient particulate heavy
metals in a small city, Korea. Atmospheric Environment 36, 5449–5458.
Zhang, L.F., Boeckx, P., Chen, G.X., Van Cleemput, O., 2000. Nitrous oxide emission
from herbicide-treated soybean. Biology and Fertility of Soils 32, 173–176.
Zhang, L., Gong, S., Padro, J., Barrie, L., 2001. A size-segregated particle dry depo-
sition scheme for an atmospheric aerosol module. Atmospheric Environment
35, 549–560.
 D. Fowler et al. / Atmospheric Environment 43 (2009) 5193–5267
Zhang, L., Brook, J.R., Vet, R., 2002. On ozone dry deposition – with emphasis on non-
stomatal uptake and wet canopies. Atmospheric Environment 36, 4787–4799.
Zhang, L., Brook, J.R., Vet, R., 2003a. Evaluation of a non-stomatal resistance param-
eterization for SO2 dry deposition. Atmospheric Environment 37, 2941–2947.
Zhang, L., Brook, J.R., Vet, R., 2003b. A revised parametrization for gaseous dry depo-
sition in air-quality models. Atmospheric Chemistry and Physics 3, 2067–2082.
Zhang, L., Vet, R., 2006. A review of current knowledge concerning size-dependent
aerosol removal. China Particuology 4 (6), 272–282.
Zimmerman, P.R., Greenberg, J.P., Westberg, C.A., 1988. Measurements of atmo-
spheric hydrocarbons and biogenic emission fluxes in the Amazon boundary
layer. Journal of Geophysical Research 93, 1407–1416.
5267
Zimmermann, F., Plessow, K., Queck, R., Bernhofer, C., Matschullat, J., 2006.
Atmospheric N- and S-fluxes to a spruce forestdcomparison of inferential
modelling and the throughfall method. Atmospheric Environment 40,
4782–4796.
Zorn, S.R., Drewnick, F., Schott, M., Hoffmann, T., Borrmann, S., 2008. Charac-
terization of the South Atlantic marine boundary layer aerosol using an
aerodyne aerosol mass spectrometer. Atmospheric Chemistry and Physics 8,
4711–4728.
Zou, J.W., Huang, Y., Sun, W.J., Zheng, X.H., Wang, Y.S., 2005. Contribution of plants
to N2O emissions in soil-winter wheat ecosystem: pot and field experiments.
Plant and Soil 269, 205–211.