Dipartimento di Chimica Università di Firenze, Sesto Fiorentino, Florence,
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1 Approccio integrato per l identificazione di aerosol derivante da emissioni navali nel Mediterraneo centrale da misure di PM 10 a Lampedusa (35.5 N, 12.6 E) e Capo Granitola (36.6 N, 12.6 E) S. Becagli 1,*, F. Anello 2, C. Bommarito 2, F. Cassola 3,4, M. Chiari 5, G. Calzolai 5, A. di Sarra 6, M. Giannoni 1,5, J.- L. Gómez-Amo 6,7, F. Lucarelli 5, M. Marconi 1, D. Meloni 6, F. Monteleone 2, S. Nava 5, G. Pace 6, M. Severi 1, D. M. Sferlazzo 8, R. Traversi 1, and R. Udisti 1 1 Dipartimento di Chimica Università di Firenze, Sesto Fiorentino, Florence, ENEA, Laboratorio per le Osservazioni e Analisi della Terra, Palermo, Dipartimento di Fisica & INFN, Università di Genova, Genova, I ARPAL-Unità Operativa CFMI-PC, Genova, Dipartimento di Fisica e Astronomia & INFN-Firenze, Sesto Fiorentino, Florence, ENEA Laboratorio per le Osservazioni e Analisi della Terra, Roma, Dep. de Física de la Tierra y Termodinámica, Universitat de València, València, ENEA, Laboratorio per le Osservazioni e Analisi della Terra, Lampedusa, 92010
2 The project proposes a multi-scale modelobservation integrated strategy with satellite and field observations in the Mediterranean basin based on 3 different approaches: long, enhanced and short observation periods. ChArMEx (The Chemistry-Aerosol Mediterranean Experiment) Assessment of the present and future state of the atmospheric environment and of its impacts in the Mediterranean basin. Objectives of the project are to set up a coordinated experimental and modeling international effort based on updated tools for an estimation of regional budgets of tropospheric trace species, of their trends, and of their impacts on air quality, marine biogeochemistry, and regional climate
3 June-July 2013 Capo Granitola 36.6 N, 12.6 E Lampedusa 35.5 N, 12.6 E
4
5 Lampedusa
6 Capo Granitola Istituto per l'ambiente Marino Costiero del CNR
7 Lampedusa Teflon filter ICP AES s.b.hno 3 H 2 O 2 Metals, La, Ce PIXE: elements total content Ions Chromatography Na +, NH 4+, K +, Mg 2+, Ca 2+, Cl -, NO 3-, SO 4 2-, MSA, Ac, For, Gly, Ox ICP AES Soluble fraction HNO 3 ph1.5 Metals
8 Lampedusa quartz filter Thermo-Optical Analyser: EC/OC
9 Capo Granitola quartz filter Thermo-Optical Analyser: EC/OC ICP AES s.b.hno 3 H 2 O 2 Metals, La, Ce Ions Chromatography Na +, NH 4+, K +, Mg 2+, Ca 2+, Cl -, NO 3-, SO 4 2-, MSA, Ac, For, Gly, Ox ICP AES Soluble fraction HNO 3 ph1.5 Metals
10 LMP - OA =OC*2.1 CGR - OA =OC*1.8 SSA =1.46 *ssna +Cl Dust = Al/0.08
11 Mistral event
12
13 Sea -breeze regime
14 Identification of ship source chemical tracers, other than V and Ni, the rare earth elements (La, Ce) high resolution back-trajectories, based on data from a high resolution regional model; information on the vertical mixing in the atmospheric boundary layer; coincidences between the high resolution backtrajectories and the position of different types of ships in the Sicily channel.
15 Ship event: V sol > 6 ng m -3 Pure Sharan dust events : Si tot > 800 ng m -3 and V < 6ng m -3 Slope (±error) R 2 n. V sol / V tot ship events 0.80 (±0.02) V sol / V tot pure Saharan dust events 0.40 (±0.02) Ni sol / Ni tot ship events 0.77 (±0.02) Ni sol / Ni tot events pure Saharan dust 0.45 (±0.02) Soluble compounds such as sodium vanadates and nickel idroxides are formed during heavy fuel oil combustion.
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19 10 June 31 July June 30 June 2013
20 Correlation between V concentration and number of ships It was assumed that the ship plume influenced the sampled air mass if: the trajectory passed at less than 15 km from the position of the ship the altitude of the air mass was lower than 500 m all trajectory-ship coincidences occurring within the last 36 hours before sampling were considered
21 Evaluation of the stability of boundary layer The TI index was calculated as the difference between the temperature at the altitude of the maximum and the temperature at the surface. A positive TI indicates an inversion, and the TI value provides an indication of the intensity of the inversion.
22 n. ships total n. merchant sh. n. fishing ship TI
23 Quantification of ship aerosol: minimum value approach
24 nssso 4 2- NO 3 - OC PM10 (nssso 2-4 /V) ship =200 (NO 3- /V) ship =10 (OC/V) ship =40 LPD OM=2.1*OC CGR OM=1.8*OC LMP CGR LMP CGR LMP CGR LMP CGR Mean ship contr. mg/m 3 (%) 1.3 (33%) 2.0 (30%) (4.5%) 0.10 (7.2%) 0.26 (14%) 0.40 (8.1%) 1.9 (11%) 3.0 (8.5%) Max ship contr. mg/m 3 (%) 7.2 (66%) 8.6 (75%) 0.36 (50%) 0.43 (80%) 1.4 (92%) 1.7 (21%) 10.6 (48%) 12.6 (42%)
25 Conclusioni V and Ni in the aerosol were unambiguously associated with the ship source; this attribution was based on the V to Ni ratio and La/Ce ratio coincidences between airmass trajectories and travelling ships. planetary boundary layer vertical structure Merchant ships (cargo and tankers) appeared to produce a larger impact on the measured aerosol than fishing vessels Ship emissions contributed by at least 30% to the total amount of sulphate, by at least 4-7% to the total amount of nitrate, and by at least 8-14% to the total amount of organic aerosol. All these contributions covered at least 11% of PM 10 at LMP (1.9 mg/m 3 ), and about 8% of PM 10 at CGR (2.8 mg/m 3 ).
26 Grazie per l attenzione!
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