S1 SUPPORTING MATERIAL Using PUF disk passive samplers to simultaneously measure air concentrations of persistent organic pollutants (POPs) across the Tuscany Region, Italy Victor H. Estellano1, Karla Pozo1*, Tom Harner2, Simonetta Corsolini1 and Silvano Focardi1 1 Department of Environmental Sciences, University of Siena, Via Mattioli 4, 53100, Siena, Italy Atmospheric Science & Technology Directorate, Environment Canada, 4905 Dufferin Street, Toronto, Ontario, Canada 2 CONTENT Text S1. Oven conditions Text S2. OCPs, PCBs, PBDEs and PAHs screened and the target/qualified ions Figure S1. Schematic representation of the PUF disk sampler and photo of PAS deployed in this study. Figure S2. Map showing location of urban, rural and agricultural air sampling sites in the Tuscany region of central Italy. Table S1. Sampling sites information, temperature (°C) and deployment time Table S2. Air concentrations (pg m‐3) of individual PAH isomers, MDL, IDL and sample air volumes. Table S3. Air concentrations (pg m‐3) of the OCPs, PCBs and PBDEs, MDL, IDL and sample air volumes *Corresponding author Tel.: +39 0577 232879, Fax: +39 0577 232806, e‐mail: gallardokarla@gmail.com S2 Text S1: For OCPs, PAH and PCBs GC separation as performed on a capillary column ZB‐5ms (30m ∙ 0,25 mm internal ∙ 0,25 μm) from the Phenomenex. The oven temperature program was as follows: start at 50 °C (hold 2 minute), 50‐120 °C at 30 °C min‐1, 120‐280 °C at 6 °C min‐1 (hold 15 minute) at 6 °C min‐1. GC separation for PBDEs used a capillary column DB‐5HT (15 m ∙ 0.247 mm internal ∙ 0.10 μm) Agilent Technology (J&W Scientific). The oven temperature programs was as follow: start ‐1 ‐1 ‐1 at 100 °C (hold 2 minute), 100‐250 °C at 10 °C min , 250‐265 °C at 0.8 °C min , 265‐325 °C at 12 °C min (hold 12 minute). A sample of 2 μL was injected on splitless mode at 250 ºC. S2: PUF disk samples were analyzed for a suite of target compounds that included 19 OCPs, 15 PAHs, 21 PCBs and 27 PBDEs. The OCPs screened and the target/qualified ions (in brackets) were: α‐, β‐, ‐, ‐HCHs (181/219), hexachlorobenzene (284/286), aldrin (263/293), heptachlor (272/237), cis‐ and trans‐heptachlor epoxide (353/355), cis‐chlordane (373/237), trans‐chlordane (373/237), trans‐nonachlor (407/409), endosulfan I (195/237), endosulfan II (195/241), endosulfan sulphate (272/274), o,p’‐DDE, p,p’‐DDE (246/248), o,p’‐DDD, p,p’‐DDD (235/237), o,p’‐DDT, p,p’‐DDT (235/237) (Ultra Scientific, North Kingstown, RI, USA). PAHs congeners and target/qualified ions were monitored as follow: acenaphthylene (152), acenaphthene (154), fluorene (166), phenanthrene (178), anthracene (178), fluoranthene (202), pyrene (202), benz(a)anthracene (228), chrysene (228), benzo(b)fluoranthene (252), benzo(k)fluoranthene (252), benzo(a)pyrene (252), indeno(1,2,3‐cd)pyrene (276), dibenzo(a,h)anthracene (278/276), benzo(g,h,i)perylene (276) (Supelco Analytica, USA). PCBs congeners were: PCBs 3Cl:‐ 17, 18, 28/31, 33 (256/2589), PCBs‐4Cl: 52, 44, 56/60 (290/292), PCBs‐5Cl: 95,101,99, 118, 105 (326/328), PCBs‐6Cl: 149, 153, 138 (360/362), PCBs‐7Cl: 170,180 (394/396), PCB‐8Cl: 194 (428/430), PCB‐10CL: 209 (496/498). For PBDEs the congeners were: 3, 7, 15, 17, 47, 49, 66, 71, 77, 85, 99, 100, 119, 126, 138, 153, 154, 156, 183, 184, 191, 196, 197, 206, 207 and 209 (79/81) (Supelco Analytica, USA). Figure S1. Schematic representation of the PUF disk sampler and photo of PAS deployed. S3 Figure S2. Map showing location of urban, rural and agricultural air sampling sites in the Tuscany region of central Italy. Table S1. Sampling sites information, temperature (°C) and deployment time Sampling sites Categories Latitude N Longitude E T (°C) days Started Final Fogliano Grosso Galuzzo Scarlino Sam Gimignano ColleVE Abbadia S.S Arcidoso Poggibonsi Follonica costa Piombino Arezzo Follonica centro Siena centro Follonica nord Prato (Galciana) Grosseto center Siena nord Montalcino Val d'orcia Ru Ru Ru Ru Ru Ru Ag Ur Ur Ur Ur Ur Ur Ur Ur Ur Ag Ag Ag 43°15'45.18'' 43°44'11.58'' 42°54'13.39'' 43°27'03.10'' 43°25'07.81'' 42°52'17.72" 42°51'45.12" 43°26'27.54'' 42°55'11.68'' 42°56'16.73'' 43°28'16.36'' 42°55'46.99'' 43°19'56.86'' 42°55'47.28'' 43°53'07.73'' 42°45'47.66'' 43°21'37.80'' 43° 2'51.84" 42°56'36.57" 11°18'45.22'' 11°13'28.74'' 10°52'28.99'' 11°03'46.01'' 11° 07'49.34'' 11°40'18.45" 11°32'43.08" 11° 09'41.33'' 10°45'38.63'' 10°30'37.87'' 11°51'20.09'' 10°44'23.46'' 11°18'49.18'' 10°45'23.58'' 11°03'27.14'' 11°07'11.39'' 11°18'47.88'' 11°29'25.14" 11°38'22.03" 16 18 16 16 17 15 16 17 18 18 18 18 16 18 18 18 16 16 16 90 69 162 86 82 60 60 82 112 103 127 93 138 93 112 102 91 60 60 10/05/08 23/04/08 07/04/08 01/04/08 06/04/08 09/07/08 09/07/08 05/04/08 02/04/08 12/04/08 05/04/08 05/04/08 05/04/08 05/04/08 06/04/08 07/04/08 01/04/08 09/07/08 08/08/08 01/07/08 16/09/08 26/06/08 26/06/08 09/09/08 09/09/08 26/06/08 23/07/08 24/07/08 10/08/08 07/07/08 21/08/08 07/07/08 27/07/08 26/07/08 01/07/08 09/01/08 09/07/08 09/91/08 Abbreviations: T(°C) average Temperature; (days) sampling days. Ru = Rural, UR = Urban and Ag = Agricultural. S4 Table S2. Air concentrations (pg m‐3) of PAHs at each sampling site, MDL, IDL and sampled air volumes (VAIR) Acepht AceP Fl Phe An Flu Py BaA Chry BbF Total ∑PAHs <1 <1 370 860 <1 80 50 <1 <1 870 <1 100 <1 <1 1 300 320 1 800 <1 60 <1 <1 <1 <1 40 70 50 30 110 200 170 90 340 230 <1 120 210 180 50 40 260 80 150 90 280 210 70 180 220 280 120 370 420 150 290 650 240 190 170 1 000 190 770 200 770 560 280 790 1 200 1 200 440 1 600 1 360 1 300 1 350 1 400 1 400 860 <1 <1 <1 <1 <1 70 60 <1 <1 <1 <1 <1 <1 <1 <1 <1 <1 <1 60 50 190 60 260 50 300 170 110 220 360 330 80 430 420 450 470 300 470 610 30 120 40 200 50 170 140 70 200 220 280 60 340 240 350 440 290 370 210 < 0.2 < 0.2 < 0.2 < 0.2 < 0.2 11 14 < 0.2 8 15 8 < 0.2 13 10 < 0.2 < 0.2 < 0.2 15 15 < 0.2 < 0.2 < 0.2 30 14 20 20 10 20 50 30 0 30 20 30 50 40 30 40 4 < 0.7 < 0.7 < 0.7 < 0.7 10 11 < 0.7 < 0.7 < 0.7 < 0.7 < 0.7 9 < 0.7 < 0.7 < 0.7 < 0.7 10 16 290 1 600 750 2 300 450 1 800 1 300 600 1 500 3 100 2 200 900 3 100 2 700 3 500 3 100 4 700 2 700 2 100 MDL 1 0.5 1 1 1 2 1 0.2 0.2 0.7 IDL 2 1 2 2 2 4 2 0.4 0.4 1.4 Fogliano Grosso Galuzzo Scarlino San Gimignano Colle_V_E Abbadia S.S. Arcidosso Poggibonsi Follonica costa Piombino Arezzo Follonica centro Siena centro Follonica nord Prato Grosseto Siena nord Montalcinio Val d'orcia 3 Vair, m (60 days) 50 50 110 170 170 230 230 240 240 240 Vair, m3 (160 days) 50 50 130 280 280 530 560 630 630 650 Abbreviations: BDL = below detection limit; Acepht (Acenaphtylene), AceP (Acenaphtene), Fl (Fluorene), Phe (Phenantrene), An (Antracene) Flu (Fluoranthrene), Py (Pyrene), BaA (Benzo(a)anthracene), Chry (Chrysene), BbF(Benzo(b)fluoranthene. S5 Table S3. Air concentrations (pg m‐3) of the OCPs, PCBs and PBDEs at each sampling site, MDL, IDL and sampled air volumes (VAIR) PBDEs Locations Fogliano Grosso Category Galuzzo Scarlino Sam Gimignano Rural ColleVE PCBs 47 99 3 < 0.3 OCPs 100 ∑PBDEs 28/31 52 2 5 <2 99 149 118 105 ∑PCBs α‐hch γ‐hch HCB Endo1 ppDDT <7 < 2 < 7.6 < 2 45 45 <5 <2 28 < 2 < 7.6 < 2 <2 28 <2 <7 < 2 < 7.6 < 2 <2 < 1.4 < 13 170 37 64 < 21 <5 340 23 < 13 170 <5 <8 21 < 13 < 21 < 0.3 < 0.3 < 0.5 <2 <7 < 2 < 7.6 < 2 <2 < 0.3 < 0.3 < 0.5 <2 <7 < 2 < 7.6 < 2 14 21 <2 <7 < 2 < 7.6 < 2 <2 <5 <8 150 < 13 < 21 30 <2 <7 < 2 < 7.6 < 2 <2 <5 <8 8 < 13 < 21 2 < 0.5 < 0.3 25 2 14 Poggibonsi < 0.3 < 0.3 < 0.5 <2 <7 < 2 < 7.6 < 2 16 Follonica costa < 0.3 < 0.3 < 0.5 <2 <7 < 2 < 7.6 < 2 <2 Piombino < 0.3 < 0.3 < 0.5 <2 <7 < 2 < 7.6 260 48 Arezzo Follonica centro < 0.3 < 0.3 < 0.5 <2 <7 < 2 < 7.6 < 2 <2 < 0.3 < 0.3 0.2 <2 <7 < 2 < 7.6 < 2 33 33 Siena centro < 0.3 < 0.3 < 0.5 <2 9 <2 <2 <2 14 Follonica nord < 0.3 < 0.3 < 0.5 11 15 < 2 < 7.6 < 2 33 59 Prato < 0.3 < 0.3 < 0.5 <2 <7 13 < 7.6 260 <2 270 Grosseto < 0.3 < 0.3 < 0.5 <2 <7 < 2 < 7.6 < 2 Val d'orcia <8 <5 < 0.3 < 0.5 5 Agricultural <5 < 0.3 < 0.5 19 Siena nord 270 2 Arcidoso Montalcino 170 1 990 < 0.3 Abbadia S.S. Urban 76 < 0.3 < 0.3 0.5 < 0.3 < 0.3 < 0.5 2 2 < 0.5 0.2 0.8 4 5 16 < 21 <5 <8 < 1.4 < 13 67 570 730 < 1.4 < 13 65 280 340 2 000 180 530 590 < 1.4 < 13 < 21 200 <8 < 1.4 1 400 < 21 <5 1 100 < 1.4 < 13 < 21 270 310 < 1.4 < 13 100 <5 <8 < 21 <2 480 760 310 31 < 1.4 1 100 22 < 13 < 21 <2 <7 < 2 < 7.6 < 2 <2 610 720 37 2 200 730 <2 <7 < 2 < 7.6 < 2 <2 <5 <8 12 < 13 < 21 <2 <7 < 2 < 7.6 < 2 <2 <5 <8 6 < 13 < 21 Media 9 50 150 270 30 340 80 SD 8 100 230 340 50 700 180 MDL 0.3 0.3 0.5 2 7 2 8 2 2 5 8 1.4 13 21 IDL 3 Vair, m (60 days) 3 Vair, m (160 days) 0.5 0.6 1 3 14 3 15 4 3 10 15 3 26 41 240 240 240 200 210 230 240 240 240 170 190 140 220 240 630 640 640 390 470 580 610 620 630 270 340 200 530 620 Abbreviations: Ru = Rural, UR = Urban and Ag = Agricultural.