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Supplement of Emission of Volatile Halogenated Organic Compounds Over Various Dead Sea Landscapes

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Supplement of Emission of Volatile Halogenated Organic Compounds Over Various Dead Sea Landscapes Supplement of Atmos. Chem. Phys., 19, 7667–7690, 2019 https://doi.org/10.5194/acp-19-7667-2019-supplement © Author(s) 2019. This work is distributed under the Creative Commons Attribution 4.0 License. Supplement of Emission of volatile halogenated organic compounds over various Dead Sea landscapes Moshe Shechner et al. Correspondence to: Eran Tas ([email protected]) The copyright of individual parts of the supplement might differ from the CC BY 4.0 License. 33 S1. Lifetime and main sink pathways for the investigated VHOCs 34 Table S1. Average lifetimes and primary removal pathways for the VHOCsa. 35 Species Average lifetime Primary removal pathway c CHBr3 15 days J >OH 36 CH2Br2 94 days OH 37 CHBr2Cl 32 days OH>J 38 CHBrCl 41 days OH>J 2 39 C2HCl3 5 days OH 40 CHCl3 112 days OH 41 CH3I 4 days J>OH 42 b CH3Br 1.8 years OH>loss in soil>loss in ocean b 43 CH3Cl 1.57 years OH>loss in ocean>loss in soil 44 45 46 a See more details in (Carpenter et al., 2014). 47 b Partial lifetime against reaction with OH. 48 c J, photolysis first-order rate coefficient. S2 49 S2. Specification of the mass spectrometry instrumentation and techniques 50 51 Table S2. Specification of instrumentation and techniques used to analyze the sampled gas and corresponding 52 precision. 53 54 Species Systema Precision (%)55 CHBr3 D, MSD 1.6 56 57 CH2Br2 D 1.6 58 59 CHBr2Cl D 9.3 60 61 CHBrCl2 D 2.0 62 CH2Cl2 C, MSD 4.5 63 64 C2HCl3 MSD 5.0 65 66 C, D , MSD 1.1 CHCl3 67 68 CH3I C,D 1.1 69 CH3Br MSD 1.7 70 71 CH3Cl B, MSD 1.5 72 73 74 a Indicates the applied column and detector for quantifying species concentration: B, DB-1 column + flame 75 ionization detector (FID); C, DB-5 column + electron-capture detector (ECD); D, RESTEK1701 column + ECD; 76 MSD , DB-5 MS column + mass spectrometer. S3 77 S3. Measured VHOC mixing ratios 78 Table S3 compares the measured mixing ratios at the different measurement sites and reported 79 values for the global marine boundary layer (MBL). 80 81 Table S3. Comparison of VHOC mixing ratios (in pptv) measured at the Dead Sea to their corresponding values 82 at the marine boundary layer (MBL). Unless otherwise specified, the table presents median, minimum and 83 maximum VHOC mixing ratios measured at different sites at the Dead Sea (see Table 1 in the main text for site 84 abbreviations) and in the MBL as reported by Carpenter et al. (2014). Species Median/ BARE− BARE− COAST− COAST− TMRX− WM− SEA− All sites MBL range MSMR MSD EGD TKM ET KLY KDM Median 11.3 11.0 8.0 2.6 4.7 3.1 11.0 6.2 1.2 CHBr 3 Range 5.6−16.3 6.0−22.6 4.4−16.8 3.6−1.9 2.9−7.1 2.3−3. 5 5.4−16.5 1.9−22.6 0.4-4.0 Median 0.9 2.7 1.8 0.8 1.3 1.1 1.4 1.1 0.9 CH Br 2 2 Range 0.9−1.0 0.7−18.6 0.9−5.1 0.9−0.8 0.9−1.6 1.0−1.2 1.1−1.7 0.7−18.6 0.6-1.7 Median 4.8 4.1 2.2 1.2 2.2 0.9 1.3 2.4 0.3 CHBr Cl 2 Range 3.2 −5.4 2.2−11.0 0.4−6.5 7.5−0.5 0.6−3.6 0.5−1.0 0.5−2.2 0.4−11.0 0.1-0.8 Median 2.6 2.5 1.6 1.0 2.4 0.9 2.0 1.4 0.3 CHBrCl 2 Range 2.6−3.7 0.9−9.6 1.0−3.0 0.5−1.4 0.7−3.9 0.6−1.1 1.3−2.7 0.5−9.6 0.1-0.9 Median 1.15 1.7 1.3 1.6 1.1 2.7 1.2 1.5 0.5 C HCl 2 3 Range 0.84-1.22 1.0−2.7 0.3−10.5 0.4−2.9 0.4−1.5 1.0−4.1 0.8−1.6 0.4−10.5 0.05-2 Median 16.9 19.8 18.2 18.7 19.0 19.8 17.3 18.63 7.5 CHCl 3 Range 15.9−20. 5 18.8−25.3 14.5−27.9 15.4−20.1 18.4−57.2 18.8−5.3 16.5−18.2 14.5−57.2 7.3-7.8 Median 0.8 1.3 1.2 1.5 1.3 1.1 1.4 1.2 0.8 CH I 3 Range 0.8−0.8 1.0−1.5 0.4−2.1 1.5−1.2 0.8−2.8 0.7−1.6 1.2−1.6 0.4−2.8 0.3-2.1 Mean 8.6 10.6 9.29 9.12 10.2 8.45 9.65 9.1 7.01a CH Br 3 Range 8.1−9.4 7.8−13.8 7.5−13.3 8.5−7.5 8.3−13.8 7.8−9.2 9.1−10.2 7.5−13.8 6.95-7.07a Mean 601 592 617 614 744 633 596 601 540a CH Cl 3 Range 583−608 549−672 531−732 583−545 581−685* 591−668 583−608 531−732* 537-542a 85 86 aMean and range for 2012 based on flask measurements by the US National Oceanic and Atmospheric 87 Administration (NOAA) (http://www.esrl.noaa.gov/gmd/dv/site/) and in situ measurements by the Advanced 88 Global Atmospheric Gases Experiment (AGAGE) (http://agage.eas.gatech.edu/). Measurements are taken from 89 ground stations, which do not represent the MBL in all cases. See Table 1 in the main text for site abbreviations. 90 *Calculation excludes one CH3Cl measurement at TMRX−ET-1 (see Sect. 2.1.2 in main text). S4 91 Figure S1 compares the mixing ratios of the measured VHOCs at different distances from the 92 seawater, and individually for winter and spring. No clear impact of season or distance from the 93 seawater on the mixing ratios can be discerned in this figure, or for the sample taken at 94 SEA−KDM, the latter directly representing air masses over the seawater (Sect. 2.1.1 in the main 95 text). Additional discussion of these results is included in Sect. 3.2.1 in the main text. 96 97 Figure S1. Seasonal and spatial influences on measured mixing ratios of VHOCs. Measured VHOC mixing 98 ratios are presented vs. vertical height above surface level, separately for winter (blue) and spring (orange). Black 99 filled circles and error bars represent average and standard error of the mean, respectively. Values above and to S5 100 the right of the figure indicate the percentage of time during which average mixing ratios were higher in the spring 101 (left box) or in the winter (right box), individually for COAST–TKM, COAST–EGD and SEA−KDM sites, and 102 for all of these sites together (All), for all sites and all species, respectively (see Table 1 in the main text for 103 measurement site abbreviations). 104 105 S4. Sampling footprints 106 107 Table S4. Calculated footprint following the methodology of Schuepp et al. (1990). The table shows the date, 108 time, site name (and abbreviation), sampling heights and 80% and 90% footprints for the lowest (low) and highest 109 (high) canister during each measurement. Date Time Site name / Sampling 80% 80% 90% 90% dd/m/yyyy (local) measurement height footprint footprint footprint footprint abbreviation a (m) low (m) high (m) low (m) high (m) 08:45− BARE−MSMR / 2.5, 4.5, 7.0 293.5 954.9 621.7 2022.3 20/4/2016 08:55 BARE−MSMR-1 08:45− WM−KLY / 1.0,2.0,4.0 105.7 502.6 223.9 1064.5 21/4/2016 08:55 WM−KLY-1 08:45− TMRX−ET / 4.5, 5.5, 7.5 135.6 444.2 287.2 940.8 02/5/2016 08:55 TMRX−ET-1 08:45− WM−KLY / 1.0, 2.0, 4.0 105.7 502.6 223.9 1064.5 03/5/2016 08:55 WM−KLY-2 08:30− BARE−MSD / 1.25, 2.5, 5 126.2 643.3 267.3 1362.4 25/5/2016 08:40 BARE−MSD-1 08:30− BARE−MSD / 1.25, 2.5, 5 126.2 643.3 267.3 1362.4 26/5/2016 08:40 BARE−MSD-2 12:00− TMRX−ET / 4.5, 5.5, 7.5 135.6 444.2 287.2 940.8 30/5/2016 12:10 TMRX−ET-2 12:00− BARE−MSMR / 2.5, 4.5, 7 293.5 954.9 621.7 2022.3 31/5/2016 12:10 BARE−MSMR-2 12:00− BARE−MSD / 1.25, 2.5, 5 126.2 643.3 267.3 1362.4 11/7/2016 12:20 BARE−MSD-3 18:00− BARE−MSD / 1.25, 2.5, 5 126.2 643.3 267.3 1362.4 11/7/2016 18:20 BARE−MSD-4 11:20− COAST−TKM-SD / 1, 2.5, 6.5 126.8 932.0 268.6 1973.9 21/2/2017 11:40 COAST−TKM-SD-w 11:00− COAST−TKM-LD / 1.5, 3, 7 94.1 717.5 199.3 1519.6 22/2/2017 11:20 COAST−TKM-LD-w 11:20− COAST−EGD-SD / 1, 2.5, 6.5 126.8 932.0 268.6 1973.9 28/2/2017 11:40 COAST−EGD-SD-w 11:07– COAST−EGD-MD / 1, 2.5, 6.5 126.8 932.0 268.6 1973.9 01/3/2017 11:27 COAST−EGD-MD-w 11:00– COAST−EGD-LD / 1, 2.5, 6.5 126.8 932.0 268.6 1973.9 02/3/2017 11:20 COAST−EGD-LD-w 11:30– COAS-EGD-SD / 1, 2.5, 6.5 126.8 932.0 268.6 1973.9 25/4/2017 11:50 COAST−EGD-SD-s 11:00– COAST−EGD-MD / 1, 2.5, 6.5 98.3 722.5 208.2 1530.2 26/4/2017 11:20 COAST− EGD-MD-s 11:00- COAST−EGD-LD / 1, 2.5, 6.5 126.8 932.0 268.6 1973.9 27/4/2017 11:20 COAST−EGD-LD-s 12:10– COAST−TKM-SD / 1, 2.5, 6.5 126.8 932.0 268.6 1973.9 03/5/2017 12:30 COAST−TKM-SD-s 10:30– COAST−TKM-LD / 1.5, 3, 7 94.1 717.5 199.3 1519.6 04/5/2017 10:50 COAST−TKM-LD-s S6 110 a Suffixes "s" and "w" refer to samples taken during the spring and winter, respectively.
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