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Atmospheric deposition of nitrogen and sulfur over Southern Europe with focus on the Mediterranean and the Black Sea: WRF/CMAQ modeling. U. Im 1,2 , S. Christodoulaki 1,3 , K. Violaki 1 , P. Zarmpas 1 , M. Kocak 4 , N. Daskalakis 1,2 , N. Mihalopoulos 1 , M. Kanakidou 1
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Atmospheric deposition of nitrogen and sulfur over Southern Europe with focus on the Mediterranean and the Black Sea: WRF/CMAQ modeling U. Im1,2, S. Christodoulaki1,3, K. Violaki1, P. Zarmpas1, M. Kocak4, N. Daskalakis1,2, N. Mihalopoulos1, M. Kanakidou1 [1] Environmental Chemical Processes Laboratory, Department of Chemistry, University of Crete, Voutes Campus, P.O.Box 2208, 71003, Heraklion, Greece [2] Institute of Chemical Engineering Sciences, Foundation for Research and Technology Hellas (FORTH), Patras, Greece [3] Institute of Oceanography, Hellenic Center for Marine Research, P.O. Box 2214, 71003, Heraklion, Crete, Greece [4] Institute of Marine Sciences, Middle East Technical University, Erdemli, Mersin, Turkey Paper , under review Atmos Environ, 2013
INTRODUCTION BACKGROUND • Nitrogen (N) and Sulfur (S) impact on: • Atmospheric chemistry (O3 chemistry, SIA HNO3, H2SO4) • Ecosystem (deposition: fertilization, acidification and accumulation) • N and S have both anthropogenic and natural sources • Emissions and deposition of N/S species will further increase/decrease in the future. Duce et al., Science, 2008 ACCENT 2013, September 2013, Urbino, Italy
Chl “a” distribution along Mediterranean MOTIVATION N/P ratio in seawater from 22-28 >> than the normal (18) Europe’s Environment, 1998.
HNO3 NO3- NO3- NH3 NH4+ NH4+ NOx NOy Dry Deposition Wet Deposition Total Deposition Bacteries Cilies Phytoplanton Mesozooplancton Particulate Nitrogen 500 m Sediment traps 1500 m MOTIVATION NO3- NH4+
MOTIVATION Kouvarakis et al., GBC, 2001
FOCUS ON MEDITERRANEAN & BLACK SEA • The results obtained during this study showed that airborne DIN alone is more than sufficient to explain new production in the East Mediterranean Sea. Dry deposition alone accounts for about a factor of two of the collected PON and both dry and wet deposition account for about 370% of the PON. • Observations have limited geographical coverage. • CTMs provide integrated view (temporal and spatial variations) (local to global). • Few modeling studies dedicated to the atmospheric deposition of N and S to the Mediterranean and the Black Seas.
METHODS – MODEL CONFIGURATION WRF METEOROLOGICAL MODEL • WRF/CMAQ • 171×123×23 grid cells • 30 km horizontal resolution • Vertical extent ~16 km • CB-V chemical mechanism (Yardwood et al., 2005) • AERO5 aerosol mechanism (Foley et al., GeosciModDev, 2010) • NCEP meteorology for 2008 • Monthly mean chemical boundary conditions (global model TM4-ECPL: Myriokefalitakis et al., ACP, 2011) • Model setup: Im and Kanakidou, ACP, 2012 & Im et al STOTENV, under review, 2013 • Natural Emissions and Biomass burning Emissions are calculated on line. MOSSES ANTHROPOGENIC EMISSIONS MODEL NCAR FINN BIOMASS BURNING EMISSIONS MODEL INITIAL/BOUNDARY CONDITIONS (TM4-ECPL) NATURAL EMISSIONS (MEGAN BIOGENIC+GOCART DUST) CHEMISTRY AND TRANSPORT MODEL (CMAQ) ACCENT 2013, September 2013, Urbino, Italy
EMISSIONS ANNUAL TOTAL N & S EMISSIONS ANNUAL SECTORAL N EMISSIONS Im et al. (2013) AtmEnv. Under Review ACCENT 2013, September 2013, Urbino, Italy • Anthropogenic Emissions • INERIS 10 km inventory for Europe • CIRCE global emissions for remaining • parts around the Mediterranean and • Asia (Pozzer et al., ACP, 2012) • 2 km emissions for Istanbul (Markakis • et al., APR 2012) and Athens (Markakis et al., WASP & APR, 2010)
OBSERVATIONS EMEP wet deposition: 45 stations, 2008 http://www.emep.int/ Mihalopoulos unpublished data: 2008. Finokalia station, Greece, dry deposition http://finokalia.chemistry.uoc.gr Medinets and Medinets, TurJFishAqua, 2012: Zmiinyi station, Black Sea, 2008 Markaki et al., MarChem, 2010:5 stations 2001-2003 Kocak et al., BioGeoSci, 2010: Erdemli, Turkey station, 2006-2007 Im et al. (2013) AtmEnv. Under Review ACCENT 2013, September 2013, Urbino, Italy
MODEL VALIDATION ANNUAL DEPOSITION FLUXES SO4= PRECIPITATION COMPARISON* WITH EMEP WET DEPOSITION, 2008 Normalized mean error between modeled &observed N deposition fluxes (N*: Total N as in the observations) NO3- NH4+ *Statistics are based on daily mean data ACCENT 2013, September 2013, Urbino, Italy 10
N DEPOSITION OVER EUROPE, THE MEDITERRANEAN & THE BLACK SEA ACCENT 2013, September 2013, Urbino, Italy
S DEPOSITION OVER EUROPE, THE MEDITERRANEAN & THE BLACK SEA ACCENT 2013, September 2013, Urbino, Italy
IMPORTANCE & IMPACTS OF N DEPOSITION LAND • 19% of total N (0.93 Tg-N yr-1) is deposited over forests. • 84% of the forested regions receive fluxes larger than the critical nitrogen load of 1 g-N m-2yr-1. OCEAN Annual N deposition over forests Atm=2.02 TgN yr-1 River=1.08 TgN yr-1 ASW=1.4 TgN yr-1 N (g-N m-2 yr-1) GW=0.3 TgN yr-1 ACCENT 2013, September 2013, Urbino, Italy
IMPACTS OF N DEPOSITION OVER MARINE ECOSYSTEMS This work This work Atm. N Dep. 0.36 TgN yr-1 Atm. N Dep. 0.8 g N m-2 yr-1 N C production 2.4 TgC yr-1 N C Sedimentation 1.6 TgC yr-1 Theodosi et al., BioGeoSciDisc, 2013 Sedimentation 0.16 gN m-2 yr-1 Kouvarakis et al., GBC, 2001 BLACK SEA EAST MED. SEA • The excess of N accumulates then in the water column and could explain the anomalous N/P ratio observed in the Eastern Mediterranean (Christodoulaki et al., JMarineSys, 2013). ACCENT 2013, September 2013, Urbino, Italy
CONCLUSIONS • The Mediterranean Sea receives 2.02 Tg-N yr-1and 1.36 Tg-S yr-1 while the Black Sea receives 0.36 Tg-N yr-1 and0.17 Tg-S yr-1. • Results compare reasonably with observations and previous model studies over Europe although some underestimation is seen depending on species and season. • A significant amount of the deposited N and S is transported to the Mediterranean basin. • The critical nitrogen load (1 g-N m-2yr-1)is exceeded in 84% of the European forested areas. • Atmospheric deposition plays a predominant role on the open Mediterranean and Black Seas ecosystems functioning. • Excess N accumulates in the East Med Sea due to atmospheric N and is leading to high N/P ratios. ACCENT 2013, September 2013, Urbino, Italy
THANK YOU ACKNOWLEDGEMENTS U. Im N. Daskalakis M. Kanakidou PEGASOS S. Christodoulaki N. Mihalopoulos K. Violaki ACCENT 2013, September 2013, Urbino, Italy
FOCUS ON MEDITERRANEAN & BLACK SEA MOTIVATION • Pollution receptor regions, seasonality. • Semi-closed ecosystem • East Mediterranean Sea is oligotrophic • Observations have limited geographical coverage. • CTMs provide integrated view (temporal and spatial variations) (local to global). • Few modeling studies dedicated to the atmospheric deposition of N and S to the Mediterranean and the Black Seas. Lelieveld et al., Science, 2002 ACCENT 2013, September 2013, Urbino, Italy