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Quantitative Analysis of PAHs and Metals

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PAH standards, including 1-methylnaphthalene, 2-methylnaphthalene, anthracene, fluorene, phenanthrene, fluoranthene, benz(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, benzo(g,h,i)perylene, dibenz(a,h)anthracene and indeo(1,2,3-cd)pyrene, were purchased from AccuStandard Inc. (USA). phenanthrene-d10 (1000 mg/L in dichloromethane) was purchased from ANPEL Laboratory Technologies Inc. (Shanghai) as internal standard for PAHs’ determination. Internal standard was added for quantification before instrumental analysis. Standard solutions of 14 PAHs with different concentrations (10, 25, 50, 100, 200, 500 and 1000 ng/mL) were prepared with dichloromethane to construct calibration curves. Stock standard solutions of Al, Fe, Cu, Zn, Ni at concentrations of 1000 mg/L were purchased from Guobiao (Beijing) Testing & Certification Co., Ltd. Standard solutions of five metallic elements with different concentrations (0.1, 0.5, 1, 2, 5 and 10 mg/L) were prepared with 2% nitric acid to construct calibration curves.
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Polycyclic Aromatic Hydrocarbon Analysis

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Reagents mainly included anhydrous sodium sulfate (purchased from Chengdu Kelong Chemical Reagent Factory, Chengdu, China) and dichloromethane at chromatographic-grade purity (provided by Waters Company, Milford, MA, USA). The 16PAHs in a standard (made by AccuStandard Inc., New Haven, CT, USA) were Naphthalene (NAP), Acenaphthylene (ACY), Acenaphthene (ACE), Fluorene (FLU), Phenanthrene (PHE), Anthracene (ANT), Fluoranthene (FLA), Pyrene (PYR), Benzo(a)Anthracene (BaA), Chrysene (CHR), Benzo(b)Fluoranthene (BbF), Benzo(k)Fluoranthene (BkF), Benzo(a)Pyrene (BaP), Indeno(1,2,3-c,d)Pyrene (InP), Dibenzo(a, h)Anthracene (DBA), and Benzo(g,h,i)perylene (BgP). Extraction kits for QuEChERS were procured from Agilent Technologies Inc. (Santa Clara, CA, USA) and had the following composition: 150 mg C18, 50 mg PSA, and 900 mg Na2SO4.
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3

PAHs Quantification Using HPLC

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A standard mixture containing 16 PAHs: naphthalene (NAP), acenaphthylene (ACY), acenaphthene (ACE), fluorene (FLU), phenanthrene (PHE), anthracene (ANT), fluoranthene (FLA), pyrene (PYR), benz(а)anthracene (BаA), chrysene (CHR), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(а)pyrsne (BаP), indeno(1,2,3-c,d)pyrene (InP), dibenz(а, h)anthracene (DBA), benzo(g,h,i)perylene (BgP), was purchased from AccuStandard Inc. (New Haven, CT, USA). High Performance Liquid Chromatography (HPLC) grade dichloromethane was purchased from Waters Company (Milford, MA, USA). The other reagents were all analytical grade. QuEChERS extraction kits containing 50 mg C18, 150 mg PSA and 900 mg Na2SO4 were provided by Agilent Technologies Inc. (Santa Clara, CA, USA). Milli-Q water was used to perform the analytical procedures.
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4

Certified PAHs Standard Solution Protocol

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A certified solution of 16 USEPA priority PAHs with a concentration of 0.2 mg/ml for each, containing naphthalene (Nap), acenaphthylene (Acy), acenaphthene (Ace), fluorene (Fle), phenanthrene (Phe), anthracene (Ant), fluoranthene (Flu), pyrene (Pyr), benz(a)anthracene (BaA), chrysene (Chr), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), dibenz(a,h)anthracene (DahA), indeno(1,2,3‐cd)pyrene (IcdP), and benzo(g,h,i)perylene (BghiP), was obtained from AccuStandard (New Haven, USA). In the present study, all solvents and reagents were of HPLC grade and analytical grade, respectively. Acetonitrile, methanol, acetone, n‐hexane, and dichloromethane were all obtained from Merck (Darmstadt, Germany). Ultrapure water was produced by a Milli‐Q purification water system (Millipore Co., USA).
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