Concentration and Influence Factors of Organochlorine Pesticides In

Supporting Information

Concentration and influence factors of organochlorine pesticides in atmospheric particles in a coastal island in Fujian, southeast China Liping Jiao1,2**+, Qibin Lao2,3,4+, Liqi Chen2*, Fajin Chen4, Xia Sun2, Meixun Zhao1

1 Key Laboratory of Marine Chemistry Theory and Technology (Ocean University of China), Ministry of Education; Laboratory for Marine Ecology and Environmental Science, Qingdao National Laboratory for Marine Science and Technology, Qingdao 266071, China 2 Key Laboratory of Global Change and Marine-Atmospheric Chemistry of State Oceanic Administration (SOA), Third Institute of Oceanography, SOA, Xiamen 361005, China 3 Marine Environmental Monitoring Center of Beihai, SOA, Beihai 536000, China 4 Guangdong Ocean University, Guangdong Province Key Laboratory for Coastal Ocean Variation and Disaster Prediction, Zhanjiang 524088, China

Index

Information regarding sampling and analysis

Text S1 Details on the sample pretreatment and analysis

3 Figure Figure S1: Frequency of wind direction at Pingtan Island from January 2006 to November 2007 Figure S2: Temporal variations of wind speed and ambient air temperature at Pingtan Island during the sampling periods Figure S3. Backward air mass trajectories during sampling periods.

5 Tables Table S1 Method detection limits (MDLs，pg m-3) and recoveries (R，%) of OCP Table S2 Introduction of each parameter for the estimation of incremental lifetime cancer risk Table S3. Correlation matrix between atmospheric OCPs and meteorological parameters Table S4. Spearman’s coefficients (Rs) between the residual levels of OCPs and TOC in APM of Pingtan Island Table S5 Cancer risk due to human exposure to OCPs via atmospheric particulates

Text S1 Details of the sample pretreatment and analysis A mixed-OCP standard containing 20 compounds (including α-HCH; β-HCH; γ-HCH; δ- HCH; Aldrin; Dieldrin; Endrin; Heptachlor; Heptachlor exoxide; α-chlordane; γ-chlordane; endosulfan I; endosulfan II; P, P’-DDT, P, P’-DDD, P, P’-DDE, Endrin aldehyde, Endosulfan sulfate, Endrin ketone, Methoxychlor) and the surrogate and internal standards (PCB30 and

PCB209) were purchased from Accustandard, US. Unless otherwise stated, all organic reagents were HPLC grade. Briefly, the samples were taken from the freezer to the desiccator to warm at room temperature for 24~48 h. Then, a quarter of each filter sample was cut and spiked with 60 μL surrogate standard; the filter samples were extracted using an accelerated solvent extraction instrument (ASE 200, Dionex, US), using 1:1 dichloromethane / hexane as the extracting solvent at 100°C and 1000-1500 psi (6.9~10.3×106 Pa) with a 3-min temperature ramp time, followed by a 5- min static extraction; the procedure was repeated twice with fresh solvent. The extract was concentrated and transferred into hexane using a rotary evaporation and then concentrated again to 1 mL under a gentle stream of nitrogen. Finally, the concentrated extract was further cleaned with a chromatography column. Then eluted with 100 mL of hexane / dichloromethane (v/v 1:1). The eluate was concentrated to 0.1 mL under a gentle stream of nitrogen and transferred into hexane for analysis. The determination of the OCPs was performed on a gas chromatography/electron capture detector (GC/ECD) (Agilent 7890A with Ni63 ECD) equipped with a DB-5 MS column (60 m×0.25 mm×0.25μm film thickness). The temperature of the detector and injector was 300°C and 270°C, respectively. The oven temperature started at 80°C, increased to 210°C at 10 °C /min, then increased to 250°C at a rate of 0.8 °C /min, and at last increased to 290°C at 10 °C /min before being held for 12 min. 1 μL of each sample was injected in splitless mode. Nitrogen was used as the carrier gas with a flow rate of 30 mL min-1. To determine the TOC and δ13C, part of the sample filter was analyzed by element analysis isotope mass spectrometry (Flash EA 1112 HT- Delta V Advantages, Thermo). The carrier gas flow rate is 90 mL/min, the temperature of the combustion tube and chromatographic column was 960°C 13 and 45°C, respectively. The value of δ CTOC was based on the PDB international standard, and calculated by the formula: R13 C/ 12 C   δ13C(per mil)  sample  1  1000 (1)  13 12   RC/ C VPDB 

N 60

20 >= 10 10 8 - 10 6 - 8 0 W E 4 - 6 10 2 - 4 0 - 2 20 Frequency (%) Frequency 30

40 50 60 S

Figure S1. Frequency of wind direction at Pingtan Island from January 2006 to November 2007

12 35 Pingtan (Jan. 2006 - Nov. 2007) Wind speed 10 30 Temperature

8 25

6 20 Temperature

Wind speed (m/s) Wind speed 4 15

2 10

0 5 2006 2007 Time

Figure S2. Temporal variations of wind speed and ambient air temperature at Pingtan Island during the sampling periods

Figure S3. Cont.

Figure S3. Backward air mass trajectories during sampling periods. 5

Table S1 Method detection limits (MDLs，pg m-3) and recoveries (R，%) of OCP Compounds MDL R Compounds MDL R α-HCH 0.093 91.3 Heptachlor exoxide0.080 80.5 β-HCH 0.105 95.6 EndosulfanⅠ 0.130 86.3 γ-HCH 0.112 97.8 EndosulfanⅡ 0.125 89.5 δ-HCH 0.090 96.9 Endosulfan sulfate0.110 94.1 P,P’-DDT 0.050 110.3 Aldrin 0.108 87.9 P,P’-DDD 0.085 104.8 Dieldrin 0.111 84.1 P,P’-DDE 0.115 103.6 Endrin 0.075 80.7 α-chlordane 0.074 84.2 Endrin aldehyde 0.094 97.4 γ-chlordane 0.092 88.9 Endrin ketone 0.065 89.4 Heptachlor 0.055 81.4 Methoxychlor 0.128 86.4

Table S2 Introduction of each parameter for the estimation of incremental lifetime cancer risk Logogram Parameters Moderate dose ADD Average daily dose IR Ingestion rate of particles (mg day-1) 0.56 mg day-1 (U.S. EPA) EF The exposure frequency 365 days year-1 ED Exposure duration 70 years AT Average time (days) 70 × 365 = 25550 days 3 -1 IRinhalation Inhalation rate 20 m day (SFT) SA Contact surface area of skin 3300 cm-1 (U.S. EPA) AF Dermal adherence factor 0.2 mg cm-1 (U.S. EPA) ABS Dermal adsorption fraction 0.1 (U.S. EPA) PEF Particle emission factor 1.36×109 m3 kg-1(U.S. EPA) BW Standard body weights 61.5 kg CF Conversion factor 1 × 10-6 kg mg-1

Table S3. Correlation matrix between atmospheric OCPs and meteorological parameters ∑HCHs ∑DDTs ∑Chl ∑Endo aldrin Dieldrin ∑Endrin Metho ∑OCPs TSP WS AP T WVP RH b ∑HCHs - 0.348b 0.519b - 0.391b 0.143a 0.363b - 0.630b 0.252 - 0.219b -0.166a -0.180b - b ∑DDTs 0.348b - 0.379b - 0.271b - - 0.368b 0.804b 0.379 - 0.207b -0.281b -0.286 - ∑Chl 0.519b 0.379b - 0.233b 0.505b - 0.225b 0.211b 0.633b 0.192b 0.476b -0.375b -0.383b -0.234b ∑Endo - - 0.233b - 0.196b - 0.167a - 0.170a - - - - 0.216b b aldrin 0.391b 0.271b 0.505b 0.196b - - 0.348b 0.523b 0.611b 0.300 - 0.182b -0.201b -0.182b - Dieldrin 0.143a - - - - - 0.372b - 0.167a - - - - - ∑Endrin 0.363b - 0.225b 0.167a 0.348b 0.372b - - 0.429b - - - - - b Metho - 0.368b 0.211b - 0.523b - - - 0.641b 0.382 - - -0.139a - - b ∑OCPs 0.630b 0.804b 0.633b 0.170a 0.611b 0.167a 0.429b 0.641b - 0.395 - 0.259b -0.296b -0.297b - TSP 0.252b 0.379b 0.300b 0.382b 0.395b WS - - 0.192b ------0.217b -0.178 -0.149a -0.165a AP 0.219b 0.207b 0.476b - 0.182b - - - 0.259b 0.217b - -0.840b -0.881b -0.355b T -0.166a -0.281b 0.375b - -0.201b - - 0.139a -0.296b 0.178b 0.840b - 0.967b - WVP -0.180b -0.286b 0.383b - 0.182b - - - -0.297b 0.149a 0.881b 0.967b - 0.249b RH - - 0.234b 0.216b - - - - - 0.165a 0.355b - 0.249b - a Correlation is significant at the 0.05level b Correlation is significant at the 0.01level

Table S4. Spearman’s coefficients (Rs) between the residual levels of OCPs and TOC in APM of Pingtan Island OCPs Rs P-value α-HCH 0.311a 0.016 β-HCH -0.076 0.563 γ-HCH 0.131 0.32 δHCH 0.067 0.609 ∑HCHs 0.088 0.502 p,p'-DDE 0.238 0.067 p,p'-DDD 0.313a 0.015 p,p'-DDT 0.16 0.221 ∑DDTs 0.222 0.089 TC -0.008 0.952 CC -0.024 0.853 HEPX 0.179 0.17 HEPT -0.027 0.838 ∑Chlordane 0.161 0.219 Endosulfan I -0.032 0.809 Endosulfan II 0.094 0.475 endosulfan sulfate 0.195 0.135 ∑Endosulfan 0.039 0.766 aldrin 0.04 0.764 Dieldrin -0.039 0.767 Endrin -0.018 0.889 endrin aldehyde 0.079 0.548 endrin ketone 0.014 0.913 Methoxychlor 0.247 0.057 ∑OCPs 0.277a 0.032 a Correlation is significant at the 0.05level

Table S5 Cancer risk due to human exposure to OCPs via atmospheric particulates

Ingestion Dermal contact Inhalaton Cancer risk HCHs 9.38411E-09 1.10598E-06 1.51555E-08 1.13052E-06 DDTs 9.15072E-09 1.07848E-06 1.47786E-08 1.10241E-06 Chlordanes 3.26467E-09 3.84765E-07 5.27252E-09 3.93302E-07 Endosulfan 9.16757E-10 1.08046E-07 1.48058E-09 1.10444E-07 aldrin 8.07264E-10 9.51418E-08 1.30375E-09 9.72528E-08 Dieldrin 5.82826E-10 6.86902E-08 9.41276E-10 7.02143E-08 Endrins 4.8536E-09 5.72032E-07 7.83867E-09 5.84724E-07 Methoxychlor 4.88807E-09 5.76094E-07 7.89433E-09 5.88876E-07 ∑OCPs 3.3848E-08 3.98923E-06 5.46653E-08 4.07775E-06