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Trace metals in PM: Spain

xavier.querol@idaea.csic.es. Trace metals in PM: Spain. Alastuey A., Querol X., Viana M.M., Pey J., Pérez N., Moreno T., Amato F., Pandolfi M., Cusack M., Ripoll A., and Reche C. Institute of Environmental Assessment and Water Research, CSIC, Barcelona, SPAIN

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Trace metals in PM: Spain

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  1. xavier.querol@idaea.csic.es Trace metals in PM: Spain Alastuey A., QuerolX., Viana M.M., Pey J., Pérez N., Moreno T., Amato F., Pandolfi M., Cusack M., Ripoll A., and Reche C. Institute of Environmental Assessment and Water Research, CSIC, Barcelona, SPAIN de la Rosa J., Gonzalez Castanedo Y., Sánchez de la Campa A. Huelva University - Unidad Asociada CSIC 12th TFMM Zurich 2011

  2. HM data in Spain Ministry of Environment and Marine and Rural Affairs • EMEP SITES • Heavy metals – Pb, Cd, Zn, Ni, As, Cu, Cr- in PM10 • HM – Pb, Cd, Zn, Ni, As, Cu, Cr- in precipitation and bulk deposition • Hg in PM and precipitation • HM in soils (Navarra) AQ networks • Heavy metals – Pb, Cd, Ni, As- in PM10 IDAEA-CSIC • Heavy metals in PM Contract S-G D Air Quality and Industrial Environment EVALUATION OF PM POLLUTION IN SPAIN

  3. Torrelavega Santander Ponferrada Madrid 2007 Melilla Monitoring sites N=38 Bemantes LLodio Alsasua L’Hospitalet Pamplona Burgos Montsec Montseny Sagrera El Perdón BCN-CSIC 1999-2000 Tarragona Monagrega Alcobendas 2001 Morella Madrid 2002-2003 Vila-real Onda L’Alcora 2002-2004 Palma Borriana 2004 El Saler Badajoz Puertollano Alacant 2003-2005 Bailén 2002-2010 Cartagena Huelva Algeciras Los Barrios La línea Santa Cruz Izaña Las Palmas PM Speciation

  4. ACTRIS SITES TFMM Zurich 2011

  5. Montseny Rural background site (750 masl)EUSAAR 2002 • High vol. Samplers PM10/2.5 • GRIMM Laser Spectrometer 1107 PM10/2.5/1 2007 • High vol. Samplers PM1 • Low vol samplers PM10/2.5 • CPC • MAAP: multi angle absorption photometer • Gaseous pollutants monitors 2010 • SMPS EUSAAR • AURORA 3000 Nephelometer

  6. Barcelona IDÆA CSICUrbanbackgroundsite Since 2002 • High vo. samplers PM10/2.5/1 • GRIMM Laser Spectrometer PM10/2.5/1 • CPC –(DMA) 2007 • MAAP: multi angle absorption photometer • Gaseous pollutants monitors 2010-2011 • SMPS • Surface area NSAM • ACSM

  7. Pyrenees: MontsecRemote background (1700 masl) Since 2005 • High vo. samplers PM10/ • GRIMM Laser Spectrometer PM10/2.5/1 2010 • High vo. samplers PM1 • MAAP: multi angle absorption photometer • Gaseous pollutants monitors • CPC –(DMA) • CIMEL Montsec, Ager 1700 masl Measurements: PM1/PM2.5/PM10 O3 Meteo Sampling PM10 October 2005

  8. Canaries: IzañaRemote background (2367 masl) Since 2002 • High vo. samplers TSP/PM2.5 • Online measurements PM10/2.5/1 2007 • High vo. samplers PM10/2.5/1 • MAAP: multi angle absorption photometer • Gaseous pollutants monitors • CPC –DMA • APS

  9. Bulk acidic digestion: HF:NNO3-:HClO4 OC, EC Ion Chromat.: NO3-, Cl-, SO4= ColorimetryFIA and ICP-AES: NH4+, K+, Ca2+, Mg2+,… ICP-AES: Al, Ca, K, Na, Mg, Fe, Ti, P ICP-MS: Li Be P Sc Ti V Cr Mn Co Ni Cu Zn Ga Ge As Se Rb Sr Y Zr Nb Mo Cd Sn Sb Cs Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho Tm Yb Lu Hf Ta W Tl Pb Bi Th U Leaching SAMPLE TREATMENT and ANALYSIS Components determined: 75-85% PM TFMM Zurich 2011

  10. TFMM Zurich 2011

  11. Concentration range of metals in urban areas 1000 Conc. Range in Urban areas of Spain* 100 * Querol et al. (2007) 10 1 0.1 0.01 TFMM Zurich 2011

  12. Mean annual levels Trace elements PM10 37 sites Spain 1999-2009 (ng/m3) TFMM Zurich 2011

  13. Crustal related elements Li, Ti, Ga, Rb, La, Ce, Nd TFMM Zurich 2011

  14. Crustal related elements TFMM Zurich 2011

  15. Crustal related elements TFMM Zurich 2011

  16. Crustal related elements • Li, Ti, Ga, Rb, La, Ce, Nd TFMM Zurich 2011

  17. Crustal related elements • K: mineral; biomass combustion TFMM Zurich 2011

  18. Traffic related elements TFMM Zurich 2011

  19. Traffic related elements • Traffic: brake wear • Industrial activities TFMM Zurich 2011

  20. PhD of F. Amato, CSIC TFMM Zurich 2011

  21. Meridiana Ronda de Dalt Obres Av. Diagonal Ronda Litoral Plaça Cerdà Sortida Port TFMM Zurich 2011 Sb ( µg/g PM10)

  22. Traffic related elements • Decrease of industrial emissions TFMM Zurich 2011

  23. Traffic related elements • Brake wear • Pyrite smelter TFMM Zurich 2011

  24. Traffic related elements • Lead gasoline • Ceramic industry TFMM Zurich 2011

  25. Traffic related elements • Decrease of industrial emissions • Unleadgasoline TFMM Zurich 2011

  26. Combustion and industrial related elements • Oil combustion 12th TFMM Zurich 2011

  27. Combustion and industrial related elements • Metallurgy • Oil combustion TFMM Zurich 2011

  28. Combustion and industrial related elements TFMM Zurich 2011

  29. Combustion and industrial related elements Moreno T. et. al. (2008) Environmental Science and Technology TFMM Zurich 2011

  30. Combustion and industrial related elements 12th TFMM Zurich 2011

  31. Combustion and industrial related elements TFMM Zurich 2011

  32. Combustion and industrial related elements • Ceramic: enamel • Cu-Sulphuric • Coal combustion TFMM Zurich 2011

  33. Combustion and industrial related elements • Metallurgy • Ceramic TFMM Zurich 2011

  34. Combustion and industrial related elements TFMM Zurich 2011

  35. Combustion and industrial related elements • Metallurgy TFMM Zurich 2011

  36. Combustion and industrial related elements • Wind turbine • Refinery TFMM Zurich 2011

  37. Combustion and industrial related elements • Metallurgy • Industry SiMn TFMM Zurich 2011

  38. Conclusions • PM is a complex and sometimes reactive mixture of components and in many cases scientific tools are need to identify main sources of pollution • The speciation studies may allow a complete and detailed quantification of source apportionment • PM speciation at more than 35 sites in Spain for > 1year period: rural and urban background, urban-industrial and traffic sites • Spatial variability of major and trace metals: indicate major sources and anomalies • V and Ni (SO42-, NH4+, V, Ni) is the tracing group from oil combustion • V/Ni ratio could be a good tracer for shipping emissions • La/Ce ratio is a tracer for refinery equipped with zeolitic FCC • Coal combustion (As) traceable only in specific areas • Tire and brake wear emissions coupled with high traffic volumes bring relatively high Fe, Mn, Cu, Sb, Ba and Zn levels to urban agglomerations, in the past restricted to specific hotspots with low population (smelting, steel,….) • Clear decrease of concentrations of industrial related elements TFMM Zurich 2011

  39. Acknowledgements: Ministry of the Environment of Spain, Ministry of Sciences and Innovation of Spain Regional AQ monitoring networks: Generalitat Valenciana, Generalitat de Catalunya Andalucía, Baleares, Canarias, Castilla-León, Castilla la Mancha, Euskadi, Extremadura, Galicia, Madrid, Murcia. • Thank you for your attention ! • andres.alastuey@idaea.csic.es • xavier.querol@idaea.csic.es

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