The direct effect of the harbour. micropollutant concentration. Workshop Characterization of atmospheric pollution in harbour areas 26 June 2013

Transcription

1 pollution in harbour areas 26 June 2013 The direct effect of the harbour of Brindisi on organic micropollutant concentration Elena Gregoris, Andrea Gambaro Institute for the dynamics of the environmental processes National Research Council (IDPA CNR), Venice Department of Environmental Science Informatics and Statistics, University Ca Foscari of Venice

2 Introduction Overview INTRODUCTION Polyciclic aromatic hydrocarbons (PAHs) METHOD Sampling design, pre analytical procedure and analysis Interpretation of results BRINDISI HARBOUR PAHsconcentration Effect of harbour on PAHs concentration Sources estimation Health effect 2/21

3 Introduction Polyciclic aromatic hydrocarbons (PAHs) Anthracene PAHs is mostly produced by incomplete combustion and pyrolysis of fossil fuel, wood or waste and release of petroleum products. Why are we interested in? Several PAHs are probable or possible cancirogenic for humans They can persist in the environment for a long time, bioaccumulate and they are affected by long range transport Italian limit value (D. M. 25/11/1994) Benzo[a]pyrene []py < 1 ng/m 3 3/21

4 Method Sampling High volume sampler GAS PHASE PUF polyurethane foam PARTICULATE PHASE AirFlowPUF Analitica Strumenti QFF Quartz Fiber Filter porosity 1 μm 4/21

5 Method Sampling design We used two high volume samplers: 1) One sampler collects air from all directions 2) One sampler is programmed to activate when the wind blows from a selected sector. Sampler a 360 Sampler wind select HARBOUR AREA 5/21

6 Method Pre analytical procedure EXTRACTION using a mixture n hexane /dichloromethane 1:1 v/v. Experimental conditions: 100 C / 1000 psi 7 minutes / x 3 cycles. Internal Standard method: 13 C acenaphtylene; 13 C phenanthrene; PURIFICATION by adding the extract to a neutral silica column (30 ml n hexane / 30 ml n hexane/dichloromethane 1:1 v/v) 13 C benzo[a]pyrene Recovery standard: 13 C chrysene PowerPrep Purification System FLS PLE Pressurized liquid extractor FLS Piazza et al. Anal Bioanal Chem 405 (2013) /21

7 Method Analysis and quantification Gas chromatograph mass spectrometer HRGC LRMS Quadrupole Agilent 5975C 7890A Operative conditions: EI 70 ev; 60 m fused silica capillary column (0.25 mm I. D.; 0.25 μm). GC Programme: 70 C (1.5 min); 10 C/min to 150 C (10 min); 3 C/min to 280 C (28 min); 20 C/min to 300 C (0 min); 305 for 30 min (post run). SIM mode acquisition. Masses: 152.1, 154.1, 158.1, 166.1, 178.1, 184.1, 202.1, 228.1, 234.1, 252.1, 256.3, 276.1, QUANTIFICATION 1. Evaluation of the instrumental response factor (F) 2. Comparison of the native compound peak area with that of the internal standard, by correcting for F. 7/21

8 Method Interpretation of results ΣPAHs from 360 sampling (Q 360 ) ΣPAHs from harbour sampling (Q P ) P Evaluation of the direct effect of the harbour area on micropollutant concentration Q P Q GENERAL EFFECT OF HARBOUR Considering also the variability of wind direction and intensity Wind dependent! % PAHs? Harbour (%) Q P,h Q P,h Q A,h 100 Q h P P Q P h Q h P Q h P P 100 Sampling site 8/21

9 BRINDISI HARBOUR

10 Brindisi Harbour Sampling site Airport Harbour Harbour Industrial area Urban area Industrial area A: The roof of the building of the Consortium for Industrial Development Area (ASI) of Brindisi 10/21

11 Brindisi Harbour PAHs concentration Conc (ng/m 3 ) 360 SAMPLING HARBOUR SECTOR SAMPLING Average (Range) Average (Range) Acenaphtylene (n. d ) (n. d ) Acenaphtene (n. d ) (n. d ) Fluorene ( ) ( ) Phenanthrene ( ) 2.05 ( ) Anthracene ( ) (n. d ) Fluoranthene ( ) Pyrene ( ) 1.32 ( ) Benzo[a]Anthracene ( ) ( ) Chrysene ( ) ( ) Benzo[b]Fluoranthene ( ) ( ) Benzo[k]Fluoranthene ( ) ( ) Benzo[a]Pyrene ( ) 094) ( ) Benzo[ghi]Perylene ( ) ( ) Indeno[1,2,3 c,d]pyrene ( ) (n. d ) Dibenzo[a,h]Anthracene (n. d ) (n. d ) Σ 15 PAH 4.28 ( ) 5.73 ( ) Benzo[a]pyrene < 1 ng/m 3 D. M. 25/11/ /21

12 Brindisi Harbour PAHs concentration gas particle distribution 360 SAMPLING HARBOUR SECTOR SAMPLING Conc (ng/m 3 ) Gas phase Particulate phase Gas phase Particulate phase Average (Range) Average (Range) Average (Range) Average (Range) Acenaphtylene (n. d ) 007) (n. d ) 013) (n. d ) 097) (n. d ) 041) Acenaphtene (n. d ) (n. d ) (n. d ) (n. d ) Fluorene ( ) (n. d ) ( ) (n. d ) Phenanthrene ( ) (n. d ) 1.54 ( ) (n. d ) Anthracene ( ) (n. d ) (n. d ) (n. d ) Fluoranthene ( ) ( ) 095) ( ) (n. d ) Pyrene ( ) ( ) ( ) (n. d ) Benzo[a]Anthracene ( ) ( ) (n. d ) ( ) Chrysene ( ) ( ) ( ) ( ) Benzo[b]Fluoranthene ( ) ( ) (n. d ) ( ) Benzo[k]Fluoranthene ( ) ( ) (n. d ) ( ) Benzo[a]Pyrene ( ) ( ) (n. d ) ( ) Benzo[ghi]Perylene (n. d ) ( ) (n. d ) (n. d ) Indeno[1,2,3 c,d]pyrene (n. d ) ( ) (n. d ) (n. d ) Dibenzo[a,h]Anthracene (n. d ) 0004) (n. d ) 050) (n. d. 0002) 0.002) (n. d ) 036) Σ 15 PAH 3.49 ( ) ( ) 4.27 ( ) 1.74 ( ) 18% 82% GAS PARTICULATE 30% 70% GAS PARTICULATE 12/21

13 Brindisi Harbour PAHs concentration congener distribution 360 sampling Harbour sector sampling BbF 4% CHR 9% PYR 23% PHE 19% FLA 30% ACY ACE FL PHE ANT FLA BaA 4% PYR BaA CHR BbF BkF BaP BhiP BghiP CHR 3% PYR 23% FLA 16% FL 9% PHE 36% ACY ACE FL PHE ANT FLA PYR BaA CHR BbF BkF BaP BhiP BghiP IcdP Gas % ACY Particulate ACE FL PHE ANT FLA PYR BaA CHR BbF BkF BaP Bg hip Ic cdp Da aha % Gas Particulate AC CY AC CE FL PH HE AN NT FL LA PY YR Ba aa CH HR Bb bf B kf Ba ap Bgh hip Icd dp Dah ha 13/21

14 Brindisi Harbour Effect of harbour on PAHs concentration ε: 27 % (12 48 %) χ : 55 % (29 87 %) INTERPRETATION One person, staying in the sampling site, during the sampling has 27% of PAHs intake coming from the harbour χ (%) INTERPRETATION The general contribute of harbour to PAHs concentration in Brindisi is 55%. χ (%) tonnage nage x10 6 Ton 14/21

15 Brindisi Harbour Sources estimation PHE, FLA e PYR 1. PAH MARKERS: Lighter PAHs FL, FLA, PYR Motor vehicles Incineration Diesel vehicles Oil combustion 2. DIAGNOSTIC FACTORS (DR): ANT ANT PHE <0.1 >0.1 petroleum combustion FLA FLA PYR <0.5 >0.5 gasoline diesel COMB TOT BaA BaA CHR 1 combustion <0.2 petroleum mix sources > 0.35 combustion BbF BkF IcdP IcdP BghiP >0.5 diesel diesel 15/21

16 Brindisi Harbour Sources estimation DR ANT/(ANT+PH HE) COMB/TOT Harbour Combustion gasoline diesel Petroleum FLA/(FLA+PYR) ine gasoli diese el 360 Harbour combustion sources BbF/BkF petrogenic sources A/(BaA+CHR) Ba Harbour Combustion Petrogenic+ combustion Petrogenic diesel IcdP/(IcdP+BghiP) Principal source: fuels Both diesel and gasoline 16/21

17 Brindisi Harbour Health effect TEQ 360 sampling Harbour sector sampling TEF Conc BaP conc Contribute Conc BaP conc Contribute ng/m 3 pg/m 3 TEF to TCA ng/m 3 pg/m 3 to TCA ACY ACY ACE ACE FL FL PHE PHE ANT ANT FLA FLA PYR PYR BaA BaA CHR CHR BbF BbF BkF BkF BaP BaP BghiP BghiP IcdP IcdP DahA DahA TCA: 128 pg/m 3 TCA: 130 pg/m 3 < 1 ng/m 3 17/21

18 Brindisi Harbour Health effect TEQ gas particle distribution 360 sampling Harbour sector sampling GAS PARTICULATE GAS PARTICULATE TEF Conc BaP conc % to Conc BaP conc % to Conc BaP conc % to Conc BaP conc % to TEF ng/m 3 pg/m 3 TCA ng/m 3 pg/m 3 TCA ng/m 3 pg/m 3 TCA ng/m 3 pg/m 3 TCA ACY ACY ACE ACE FL FL PHE PHE ANT ANT FLA FLA PYR PYR BaA BaA CHR CHR BbF BbF BkF BkF BaP BaP BghiP BghiP IcdP IcdP DahA DahA TCA: 31 pg/m 3 TCA: 96 pg/m 3 TCA: 25 pg/m 3 TCA: 105 pg/m 3 18/21

19 Conclusions Method: Using 2 high volume samplers; one of them programmed to turn on when the wind blows from the harbour sector Effect of harbour: abou Global contribute: 55 ± 19% Hypotethycal intake in the sampling site: 27 ± 10% Source analysis: Petroleum products as principal PAH concentration: sources 360 sampling: 4.2 ±3.5 ng/m 3 Both diesel and gasoline motors Harbour sector: 5.7 ± 2.7 ng/m 3 PAHs abundants in gas phase Health effect: High molecular PAHs mostly in B[a]P contribute for 39 58% to TCA particulate phase Benzo[a]pyrene and TCA < 1 ng/m 3 Particulate is more dangerous than gas 19/21

20 Aknowledgements ISAC CNR CNR Lecce: Daniele Contini Antonio Donateo Daniela Cesari Fabio Grasso University Ca Foscari of Venice Elena Argiriadis Elena Barbaro Gjulten Ndi Nedzip IDPA CNR Venice Elisa Morabito AND THANK YOU FOR YOUR ATTENTION 20/21

21 Comparison with Venice Harbour ΣPAHs BRINDISI from 360 sampling 4.2 ng/m 3 ( ng/m 3 ) from harbour direction sampling 5.7 ng/m 3 ( ng/m 3 ) Sampling site ΣPAHs VENICE from 360 sampling 24ng/m (1.5 52ng/m ) from harbour direction sampling 6.6 ng/m 3 ( ng/m 3 ) BRINDISI ε: 27% (12 48%) χ : 55% (29 87%) VENICE ε: 78% (43 100%) χ : 84% (50 100%) 21/21