Source apportionment of particulate matter (PM10) collected within PMinter using the macro-tracer approach

Transcription

1 Source apportionment of particulate matter (PM1) collected within PMinter using the macro-tracer approach A. Kasper-Giebl 1, M. Kistler 1, E.C.Cetintas 1, E.Schreiner 1, C.Ramirez Santa-Cruz 1, S.Szidat 2, Y. Zhang 2, H.Bauer 1, 1 Institut of Chemical Technologies and Analytics, Vienna University of Technology 2 University Bern, Department of Chemistry and Biochemistry

2 PM1 sampling at PMinter sites Chemical analyses Sources of PM Macro-tracer approach Urban impact Comparison of Methods used for source apportionment Description of PM1 sources in the border region of Austria and Slovenia, in order to understand the origin of European PM1 short-time limit value (5 µg/m³) exceedances, commonly observed in this region during wintertime.

3 1 2 Sampling in Carinthia Klagenfurt Völkermarkterstraße (1), urban Klagenfurt-Ost, Limmersdorf (2), background Ebenthal Zell (3) 3 (Photos:

4 1 2 Sampling in Styria Leibnitz (1), urban Arnfels Remschnigg (2), background (Photos:

5 1 Maribor - Center Maribor - Vrbanski plato 2 Sampling in Slowenia Maribor Center (1), urban Vrabanski Plato (2), background

6 Styria (2) Carinthia (1) Google Maps Maribor (3)

7 PM1 (µg/m³) PM1 concentrations at PMinter sites January 29 th until Feb 28 th Leibnitz Maribor Center Klag.-Völkermarkterstr. Ebenthal-Zell Arnfels-Remschnigg Vrbanski Plato Klag.-Ost (Limmers) 24h EU-Limit

8 SO4 [ µg/m³] PM1 (µg/m³) Sulfate concentrations at PMinter sites January 29 th until Feb 28 th Leibnitz Leibnitz Maribor Maribor Center Klag. Klag.-Völkermarkterstr. Ebenthal Zell Ebenthal-Zell Arnfels Arnfels-Remschnigg Vrbanski Plato Klag. Klag.-Ost Limmersd. (Limmers) 24h EU-Limit

9 Analysis was performed at the Vienna University of Technology and at the University of Bern ( 14 C) selected metals (Ø47 mm) ae water (Ø5 mm) 14 C (Ø47 mm) EC/OC (2xØ1 mm) anions (5xØ1 mm) cations(5xø1 mm) sugars (5xØ1 mm) Backup material HULIS (1x Ø1 mm)

10 Anions and Cations: aqueous extracts (ultra-pure water or methane sulphonic acid), ion Chromatography, Organic Carbon, Elemental Carbon: thermal-optical determination with an OC- EC analyzer (Sunset Laboratory Inc.) Anhydrosaccarides: aqueous extracts, ion chromatography with pulsed amperometric detection Selected Metals: X-ray fluorescence Aerosol Water: thermo-gravimetry 14 C: combustion to obtain total carbon, 14 C measurement with accelerator mass spectrometry Humic like substances (HULIS): solid phase extraction of aqueous extracts followed by the determination of organic carbon by combusiton and NDIR detection

11 PM1 concentration (µg/m³) Klag.-Völkermarkterstr. Klag.-Ost (Limmers) Ebenthal-Zell PM1 concentration (µg/m³) Leibnitz Arnfels- Remschnigg Elemental carbon (µg/m³) Klag.-Völkermarkterstr. Klag.-Ost (Limmers) Ebenthal-Zell Elemental carbon (µg/m³) Leibnitz Arnfels- Remschnigg Sulphate (µg/m³) Leibnitz Arnfels- Remschnigg Sulphate (µg/m³) Klag.-Völkermarkterstr. Klag.-Ost (Limmers) Ebenthal-Zell Concentration trends for selected parameters

12 Lev (µg/m³) 3, Klag.-Völkermarkterstr. 2,5 2, 1,5 Klag.-Ost (Limmers) Ebenthal-Zell y =,26x +,26 R² =,83 y =,19x +,56 R² =,84 y =,13x +,13 R² =,74 1,,5,, 2, 4, 6, 8, 1, 12, EC (µg/m³)

13 Sources for Particulate Matter natural sources anthropogenic sources primary aerosols secondary aerosols define specific sources Traffic exhaust, tire abrasion, de-icing salts, construction activites, industry, agriculture, wood combustion, power generation, wind blown dust, sea spray, vulcanoes,. formation of ammonium nitrate and sulfate from gaseous precursors, formation of secondary organic aerosols

14 Sources for Particulate Matter Macro-tracer Approach based on the chemical tracers determined in PM the major sources of PM are identified and quantified analyse macro-tracers in ambient PM samples multiply macro-tracer concentrations with conversion factors Macro-tracers have to be identified and analysed conversion factors have to be determined obtain contribution of respective PM sources Sources: Traffic, Wood smoke, De-icing salts, Mineral Dust (Carbonates), Secondary Inorganics, Not-defined Organic Matter Mineral Dust (Silicates), HULIS SOA, Aerosol Humidity

15 Macro-tracer Conversion Factors Derived Source Levoglucosan, Mannosan M WS PMinter =Levo*16.8 Wood burning small-scale residential heating EC EC D =EC-EC WS D EX =EC D +(EC D *.33) EC WS =M WS *.1 Traffic (Exhaust + Abrasion) EC D = from diesel D EX =Diesel emissions (Road, off-road) EC WS = from wood smoke D AB =D EX *.3 NaCl > 1% of PM1 De-icing salt Ca, Al, Si Ca*2.5; Si*2.7 Carbonates, Silicates Mineral dust Ammonium, Sulfate, Nitrate OC (NH 4 +SO 4 +NO 3 )*1.1 (for 1% moisture) OC ND =OC - OC D -OC WS, OM ND= OC ND*1.5 part of soil re-suspension Inorganic secondary aerosols Not defined OM OC D =EC D *.33 OC WS =Levo *6.8, bio-aerosol, secondary organic aerosols HULIS 1 Hulis as secondary organic aerosols Not identified in this approach - industrial emissions, coal combustion/other combustion sources References given in Bauer et al. 26

16 1% 5% 7% 11% Klag. - Völkermarkterstr. Winter 211 (8 days) Traffic (Exhaust+Abrasion) Contribution of PM Sources 8 day average for Klagenfurt Völkermarkterstraße PM1: 72 µg/m³ 15% 22% Wood smoke Sec.Org (HULIS) Sec.Inorg 3% De-icing salt Mineral dust 33% 3% H2O Rest OM Not identified PM 22% 13% Klag. - Völkermakterstr. Winter 211 (31 days) Contribution of PM Sources 31 day average for Klagenfurt Völkermarkterstraße PM1: 61 µg/m³ 3% 4% 5% 28% 25% Traffic (Exhaust+Abrasion) Wood smoke Sec.Inorg De-icing salt Mineral dust (Carbonates) Rest OM Not identified PM

17 PM1 - different sources [µg/m³] 7 6 traffic exhaust traffic exhaust traffic abrasion traffic abrasion wood smoke wood smoke non defined non OMdefined sec. OMinorg. aerosol de-icing salt sec. inorg. carbonates aerosol de-icing salt silicates carbonatesnon defined non PM1 defined PM1 SIA: µg/m³ WB: 8 23 µg/m³ TRAFFIC Ex : <1 6 µg/m³ Klagenfurt Leibnitz Maribor Limmersdorf Arnfels Vrbanski Plato E. Zell

18 PM1 - relative contribution of sources [%] 1% traffic exhaust traffic abrasion wood smoke non defined OM sec. inorg. aerosol de-icing salt carbonates non defined PM1 9% 8% 7% 6% 5% 4% 3% 2% 1% % Klagenfurt Leibnitz Maribor Limmersdorf Arnfels Vrbanski Plato E. Zell urban locations highest contribution of traffic lowest PM1 concentrations highest contribution of secondary aerosol residential area - highest contribution of wood burning

19 [µg/m³] [µg/m³] [µg/m³] [µg/m³] Urban impact - defined as the difference between the urban and the background sites averages of entire sampling period i.e. mainly Feb traffic exhaust traffic abrasion 4 w ood smoke non defined organic matter secondary inorganic aerosol de-icing salt carbonates non defined PM Klagenfurt Limmersdorf UI Klagenfurt Klagenfurt Limmersdorf UI Carinthia Leibnitz Arnfels UI Leibnitz M aribor Vrbanski Plato UI M aribor

20 [µg/m³] [µg/m³] Urban Impact for days with PM1 concentrations above and below 5 µg/m³ at the urban sites Traffic (Exh.+Abras.) Wood smoke Sec.Inorg De-icing Mineral 8 dust (Carb.) Rest OM not ident.pm 7 6 PM1 > 5 µg/m³ PM1 < 5 µg/m³ PM1 > 5 µg/m³ PM1 < 5 µg/m³ UI/urban PM1 [%] UI/urban PM1 [%] Klagenfurt Leibnitz 56 5 Maribor Klagenfurt Limmersd. UI Klagenfurt Limmersd. UI 8 Traffic (Exh.+Abr.) Wood smoke Sec.Inorg De-icing Min. dust (Carb.) Rest OM not ident. PM 7 6 PM1 > 5 µg/m³ PM1 < 5 µg/m³ Traffic (Exh.+Abr.) Wood smoke Sec.Inorg De-icing Min. dust (Carb.) Rest OM not ident. PM PM1 > 5 µg/m³ PM1 < 5 µg/m³ Leibnitz Arnfels UI Leibnitz Arnfels UI Maribor Vrb. Plato UI Maribor Vrb. Plato UI

21 Elemental Carbon (EC) Organic Carbon (OC) Different sources of carbonaceous aerosols SOC SOC Modern 14 C level Fossil 14 C level

22 Sample preparation and 14 C measurement > Sample preparation Sealing of filter samples in glass ampoules filled with CuO Oxidation to CO 2 at 85 C > 14 C measurement with accelerator mass spectrometry Transfer of CO 2 to gas ion source Sample sizes: 3-5 µgc MICADAS (Mini Carbon Dating System)

23 [µg/m³] Comparison of Methods used for source apportionment Aeth BC from Woodburning Macro-tracer- EC from Woodburning Aeth Woodburning (BC+OC) Macro-tracer Woodburning (OC+EC) 14 C non fossil (EC+OC) Aethalometer data from Grisa Mocnik, Aerosol

24 PM1 - relative contribution of sources [%] Summary and Conclusions Most of PM mass at PMinter sites is formed by secondary inorganics which are produced from gaseous precursors (nitrogen dioxides, sulfur dioxide, ammonia) (28 54 %) Wood smoke (25 45 %) Traffic + traffic related emissions (3 13 %) Secondary organics Thus the reduction of elevated PM1 levels needs actions on both the local and the regional scale. 1% 9% 8% 7% 6% 5% 4% 3% 2% 1% % traffic exhaust traffic abrasion wood smoke non defined OM sec. inorg. aerosol de-icing salt carbonates non defined PM1 Klagenfurt Leibnitz Maribor Limmersdorf Arnfels Vrbanski Plato E. Zell