SUPPORTING MATERIAL Tracing the origin of dioxins in Baltic air using an atmospheric modeling approach

Transcription

1 SUPPORTING MATERIAL Tracing the origin of dioxins in Baltic air using an atmospheric modeling approach Victor Shatalov 1, Jana H. Johansson 2, Karin Wiberg 3, Ian T. Cousins 2 1 Meteorological Synthesizing Centre East (MSC East), EMEP, Moscow, Russia 2 Department of Applied Environmental Science (ITM), Stockholm University, Svante Arrhenius väg 8, Stockholm, Sweden 3 Department of Aquatic Sciences and Assessment, Swedish University of Agricultural Sciences (SLU), 75 7 Uppsala, Sweden CONTENT The supporting material is 19 pages. It includes 3 additional tables and 18 additional figures. Additional material includes information on physical chemical property inputs, basis for adjustment of emission scenarios, further model comparisons with monitoring data and further contributions of various source areas to deposition fluxes in the Baltic for additional congeners and emission scenarios. Corresponding Author: Ian T. Cousins, e mail: ian.cousins@itm.su.se, Tel () , fax: + 46 () S1

2 Table S1. Physical chemical input Parameters 1,2,3,7,8,9 HxCDD 1,2,3,4,6,7,8,9 OCDD 2,3,4,7,8 PeCDF 1,2,3,4,5.6.7,8 OCDF Henry's law coefficient, value for 1C (Pa/m 3 mol) 6.97E E E E 2 Washout ratio for the gas phase calculated using the Henry coefficient 1.2E+4 7.2E+4 1.8E+4 1.2E+4 Subcooled liquid vapor pressure, value for 1C (Pa) 3.19E E E E 6 Aerodynamic diameter (µm) Degradation in the atmosphere, winter (1/s) 2.43E 8 4.5E 9 2.7E 8 2.7E 9 Degradation in the atmosphere, spring/fall (1/s) 2.16E 7 4.E 8 2.4E 7 2.4E 8 Degradation in the atmosphere, summer (1/s) 5.4E 7 1.E 7 6.E 7 6.E 8 Degradation in the ocean, gas (1/s) 1.3E E E 8 1.E 9 Degradation in the ocean, particles (1/s) 1.3E E E 9 1.E 1 Degradation rate in soil (1/s) 2.75E E 1 3.5E 1 7.7E 1 Molar volume (cm 3 /mol) Octanol/water partition coefficient 2.22E E+8 6.3E+6 1.E+8 Organic carbon distribution coefficient (m 3/ kg) 9.1E+3 6.5E E+3 4.1E+4 Octanol/air partition coefficient, value for 1C 7.48E E E E+12 Molecular diffusion coefficient in water (m 2 /s) 6.9E E E E 1 Molecular diffusion coefficient in air (m 2 /s) 5.24E E E 6 5.3E 6 (a) Deficiency, fg TEQ/m E EE E EE E EE Deficiency and Poland Deficiency NNE N N S S S S S S S S S S S E E E NE NE SS , fg TEQ/m 3 Deficiency, fg TEQ/m E EE E EE E EE Deficiency and Black Triangle Deficiency BT NNE N N S S S S S S S S S S S E E E NE NE SS BT, fg TEQ/m 3 Figure S1. Comparison between deficiency and the contributions of Poland (a) and the Black Triangle for 2,3,4,7,8 PeCDF. The calculation deficiency is a measure of the model error and are calculated by subtracting the modeled concentration from the measured concentration (fg I TEQ/m 3 ). In both figures the x axis displays the compass sector from which air masses originated on each sampling event. S2

3 Figure S2. Location of the field stations at Aspvreten (58 8 N, 17 4 E), and Pallas (68 N, E). Dashed lines indicate the compass sector division applied when grouping samples due to air mass origin (the labels of the sectors for Pallas given in brackets). The locations used for estimation of wind direction frequencies over the Baltic Sea are indicated with a star: (57 1 N, 19 E) for the southern and central parts, (64 8 N, 23 E) for the Bothnian Bay. Table S2. Correlation coefficients between the contributions of the considered source groups to the average air concentrations and calculation deficiency (K corr ) and contributions of these sources to the overall air concentration (Fract). Belarus (BY), Denmark (DK), Estonia (EE), Finland (FI), France (), Germany (), Latvia (LV), Lithuania (LT), Norway (NO), Poland (PO), Sweden (), the Black Triangle region (BT), the Russian Federation (split into two source groups the northwestern part and the remaining part RW and RU), the rest of the European countries altogether (), emissions from shipping within the Baltic Sea (SH). Pollutant Parameter FI DK NO LT LV EE RU RW SH BY BT 23478PeCDF K corr Fract (%) HxCDD K corr Fract (%) OCDD K corr Fract (%) OCDF K corr Fract (%) Table S3. Comparison of measured congener profiles of PCDD/F air concentrations with that used in the emission inventory for modelling. Congener Aspvreten Eagle Harbor Sleeping Bear Dunes Sturgeon Point Emission inventory 2,3,4,7,8 PeCDF 32% % 39.7% 1,2,3,7,8,9 HxCDD % % 1.6% OCDD % 3.8% 4.2%.23% OCDF.3%.2.26%.21%. S3

4 Figure S3. (a) Comparison of values of toxicity of 1,2,3,7,8,9 HxCDD calculated using the first scenario with air concentrations observed at Aspvreten and Pallas for 26 and 27 in fg I TEQ/m 3 and unitless measured to modeled concentration ratios. In both figures the x axis displays the compass sector from which air masses originated on each sampling event. The compass sectors are defined according to Sellström et al., (29); see Figure S2 in the Supplementary data. The vertical line in the figures marks the division of values based on measurements conducted in Aspvreten and in Pallas. The bold horizontal line in intersecting the x axis at 1. indicates perfect agreement between measured and modeled air concentrations. S4

5 Figure S4. (a) Comparison of values of toxicity of OCDD calculated using the first scenario with air concentrations observed at Aspvreten and Pallas for 26 and 27 in fg I TEQ/m 3 and unitless measured to modeled concentration ratios. In both figures the x axis displays the compass sector from which air masses originated on each sampling event. The compass sectors are defined according to Sellström et al., (29); see Figure S2 in the Supplementary data. The vertical line in the figures marks the division of values based on measurements conducted in Aspvreten and in Pallas. The bold horizontal line in intersecting the x axis at 1. indicates perfect agreement between measured and modeled air concentrations. S5

6 Figure S5. (a) Comparison of values of toxicity of OCDF calculated using the first scenario with air concentrations observed at Aspvreten and Pallas for 26 and 27 in fg I TEQ/m 3 and unitless measured to modeled concentration ratios. In both figures the x axis displays the compass sector from which air masses originated on each sampling event. The compass sectors are defined according to Sellström et al., (29); see Figure S2 in the Supplementary data. The vertical line in the figures marks the division of values based on measurements conducted in Aspvreten and in Pallas. The bold horizontal line in intersecting the x axis at 1. indicates perfect agreement between measured and modeled air concentrations. S6

7 Figure S6. (a) Comparison of values of toxicity of 2,3,4,7,8 PeCDF calculated using the second scenario with air concentrations observed at Aspvreten and Pallas for 26 and 27 in fg I TEQ/m 3 and unitless measured to modeled concentration ratios. In both figures the x axis displays the compass sector from which air masses originated on each sampling event. The compass sectors are defined according to Sellström et al., (29); see Figure S2 in the Supplementary data. The vertical line in the figures marks the division of values based on measurements conducted in Aspvreten and in Pallas. The bold horizontal line in intersecting the x axis at 1. indicates perfect agreement between measured and modeled air concentrations. S7

8 Figure S7. (a) Comparison of values of toxicity of 1,2,3,7,8,9 HxCDD calculated using the second scenario with air concentrations observed at Aspvreten and Pallas for 26 and 27 in fg I TEQ/m 3 and unitless measured to modeled concentration ratios. In both figures the x axis displays the compass sector from which air masses originated on each sampling event. The compass sectors are defined according to Sellström et al., (29); see Figure S2 in the Supplementary data. The vertical line in the figures marks the division of values based on measurements conducted in Aspvreten and in Pallas. The bold horizontal line in intersecting the x axis at 1. indicates perfect agreement between measured and modeled air concentrations. S8

9 Figure S8. (a) Comparison of values of toxicity of OCDF calculated using the second scenario with air concentrations observed at Aspvreten and Pallas for 26 and 27 in fg I TEQ/m 3 and unitless measured to modeled concentration ratios. In both figures the x axis displays the compass sector from which air masses originated on each sampling event. The compass sectors are defined according to Sellström et al., (29); see Figure S2 in the Supplementary data. The vertical line in the figures marks the division of values based on measurements conducted in Aspvreten and in Pallas. The bold horizontal line in intersecting the x axis at 1. indicates perfect agreement between measured and modeled air concentrations. S9

10 Figure S9. (a) Comparison of values of toxicity of OCDD calculated using the second scenario with air concentrations observed at Aspvreten and Pallas for 26 and 27 in fg I TEQ/m 3 and unitless measured to modeled concentration ratios. In both figures the x axis displays the compass sector from which air masses originated on each sampling event. The compass sectors are defined according to Sellström et al., (29); see Figure S2 in the Supplementary data. The vertical line in the figures marks the division of values based on measurements conducted in Aspvreten and in Pallas. The bold horizontal line in intersecting the x axis at 1. indicates perfect agreement between measured and modeled air concentrations. S1

11 Figure S1. (a) Comparison of values of toxicity of 2,3,4,7,8 PeCDF calculated using the third scenario with air concentrations observed at Aspvreten and Pallas for 26 and 27 in fg I TEQ/m 3 and unitless measured to modeled concentration ratios. In both figures the x axis displays the compass sector from which air masses originated on each sampling event. The compass sectors are defined according to Sellström et al., (29); see Figure S2 in the Supplementary data. The vertical line in the figures marks the division of values based on measurements conducted in Aspvreten and in Pallas. The bold horizontal line in intersecting the x axis at 1. indicates perfect agreement between measured and modeled air concentrations. S11

12 Figure S11. (a) Comparison of values of toxicity of 1,2,3,7,8,9 HxCDD calculated using the third scenario with air concentrations observed at Aspvreten and Pallas for 26 and 27 in fg I TEQ/m 3 and unitless measured to modeled concentration ratios. In both figures the x axis displays the compass sector from which air masses originated on each sampling event. The compass sectors are defined according to Sellström et al., (29); see Figure S2 in the Supplementary data. The vertical line in the figures marks the division of values based on measurements conducted in Aspvreten and in Pallas. The bold horizontal line in intersecting the x axis at 1. indicates perfect agreement between measured and modeled air concentrations. S12

13 Figure S12. (a) Comparison of values of toxicity of OCDF calculated using the third scenario with air concentrations observed at Aspvreten and Pallas for 26 and 27 in fg I TEQ/m 3 and unitless measured to modeled concentration ratios. In both figures the x axis displays the compass sector from which air masses originated on each sampling event. The compass sectors are defined according to Sellström et al., (29); see Figure S2 in the Supplementary data. The vertical line in the figures marks the division of values based on measurements conducted in Aspvreten and in Pallas. The bold horizontal line in intersecting the x axis at 1. indicates perfect agreement between measured and modeled air concentrations. S13

14 Figure S13. (a) Comparison of values of toxicity of OCDD calculated using the third scenario with air concentrations observed at Aspvreten and Pallas for 26 and 27 in fg I TEQ/m 3 and unitless measured to modeled concentration ratios. In both figures the x axis displays the compass sector from which air masses originated on each sampling event. The compass sectors are defined according to Sellström et al., (29); see Figure S2 in the Supplementary data. The vertical line in the figures marks the division of values based on measurements conducted in Aspvreten and in Pallas. The bold horizontal line in intersecting the x axis at 1. indicates perfect agreement between measured and modeled air concentrations. S14

15 Measurements, pg TEQ/m 2 /month Measurements Direct deposition Dec Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Calculations, pg TEQ/m 2 /month Figure S14. Comparison of values of direct deposition flux of 2,3,4,7,8 PeCDF calculated using the first scenario with measurements at Vindeln. The scales for calculations and measurements are different! S15

16 2,3,4,7,8 PeCDF pg TEQ/m 2 /month Measurements Direct deposition pg TEQ/m 2 /month Measurements Direct deposition pg TEQ/m 2 /month pg TEQ/m 2 /month Dec Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov 1,2,3,7,8,9 HxCDD a (a) 1 Measurements.9 Direct deposition Dec Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov OCDD (a).7 Measurements.6 Direct deposition pg TEQ/m 2 /month pg TEQ/m 2 /month 1.4 Measurements 1.2 Direct deposition Measurements.6 Direct deposition Dec Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov (a) OCDF pg TEQ/m 2 /month Measurements Direct deposition pg TEQ/m 2 /month Measurements Direct deposition.1.1 Dec Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Figure S15. Comparison of observed deposition flux of 2,3,4,7,8 PeCDF, 1,2,3,7,8,9 HxCDD, OCDD and OCDF with those calculated under second (a) and third scenarios, pg I TEQ/m 2 month. S16

17 Gulf of Bothnia Baltic Proper RW 1 33% 33% 8% 6% 11% 12% DK 12% 16% 3 Gulf of Finland Gulf of Riga 6% 6% 18% RW 27% 3 6% 8% 18% 9% LV 18% 36% 7% 3% 22% Belt Sea DK 5 1% 3% 26% Kattegat 7% DK 4 Figure S16. Contributions of various source groups to the deposition flux of 1,2,3,7,8,9 HxCDD to the sub basins of the Baltic Sea calculated using the first scenario. S17

18 Gulf of Bothnia Baltic Proper RU FI 3% 1% RW 11% 1 18% 39% RW DK 7% 7% 1 2% 42% Gulf of Finland Gulf of Riga LV EE RU 9% 1 RW 32% 33% 3% 16% RW 6% 1 LV 22% 3 8% 6% 3% Belt Sea 7% DK 38% 6% 8% Kattegat 9% 39% 3 DK 3% Figure S17. Contributions of various source groups to the deposition flux of OCDD to the sub basins of the Baltic Sea calculated using the first scenario. S18

19 Gulf of Bothnia Baltic Proper 1 4% 8% 6% 9% 41% 11% FI 27% DK 11% 1 Gulf of Finland Gulf of Riga FI 18% 43% 6% 17% 4 6% 7% RW 16% 8% 9% LV 1% 7% 3% Belt Sea 9% 3% Kattegat 7% DK 39% 29% DK 48% 33% Figure S18. Contributions of various source groups to the deposition flux of OCDF to the sub basins of the Baltic Sea calculated using the first scenario. S19