Journal of Chromatography A, 1345 (2014) 1–8 Contents lists available at ScienceDirect Journal of Chromatography A j o ur na l ho me page: www.elsevier.com/locate/chroma Water analysis of the sixteen environmental protection agency—polycyclic aromatic hydrocarbons via solid-phase nanoextraction-gas chromatography/mass spectrometry Walter B. Wilson, Udienza Hewitt, Mattheu Miller, Andres D. Campiglia ∗ Department of Chemistry, 4000 Central Florida Blvd, Physical Sciences Room 255, University of Central Florida, Orlando, FL 32816-2366, USA a r t i c l e i n f o Article history: Received 20 December 2013 Received in revised form 19 March 2014 Accepted 30 March 2014 Available online 4 April 2014 Keywords: Polycyclic aromatic hydrocarbons Solid-phase nanoextraction Gas chromatography-mass spectrometry Gold nanoparticles Water analysis a b s t r a c t The growing concern with a sustainable environment poses a new challenge to analytical chemists facing the routine monitoring of polycyclic aromatic hydrocarbons (PAHs) in water samples. The new method presented here meets several features of green analytical chemistry. PAHs are extracted from 500 L of water sample with 1 mL of a gold nanoparticles aqueous solution and released with 100 L of organic solvents for subsequent analysis via gas chromatography/mass spectrometry. The relative standard devi- ations of the overall procedure ranged from 2.4 (acenaphthene) to 7.8% (dibenz[a,h]anthracene). The limits of detection were excellent as well and varied from 4.94 (fluoranthene) to 65.5 ng L -1 (fluorene). The excellent analytical figures of merit, the simplicity of the experimental procedure, the short analysis time and the reduced solvent consumption demonstrate the potential of this approach for the routine monitoring of the sixteen priority pollutants via and environmentally friendly methodology. © 2014 Elsevier B.V. All rights reserved. 1. Introduction The fact that polycyclic aromatic hydrocarbons (PAHs), which originate from many natural and anthropogenic sources, can induce cancer has been documented in numerous epi- demiological studies [1–6]. The US Environmental Protection Agency (EPA) includes sixteen PAHs in its priority pollutants list, namely benz[a]anthracene (B[a]A), benzo[b]fluoranthene (B[b]F), benzo[k]fluoranthene (B[k]F), benzo[a]pyrene (B[a]P), dibenz[a,h]anthracene (DB[a,h]A), indeno[1,2,3-cd]pyrene (I[1,2,3- cd]P), naphthalene (Nap), acenaphthylene (Aceny), acenaph- thene (Acen), fluorene (Flu), phenanthrene (Phen), anthracene (Ant), fluoranthene (Fluo), pyrene (Pyr), chrysene (Chr), and benzo[ghi]perylene (B[ghi]P) [7]. Since a primary route of human exposure to PAHs is contaminated water, the routine monitoring of the sixteen EPA-PAHs is recommended in water samples taken from municipal wells and agricultural irrigation sources such as ponds, lakes and rivers [8–21]. Maximum contaminant levels (MCL) of regulated PAHs range from 10 to 200 ng L -1 [7,22]. The EPA recommends MCL not to exceed 200 ng L -1 . The European Union and the World Health Orga- nization (WHO) have set a 10 ng L -1 MCL value for the highly ∗ Corresponding author. Tel.: +1 4078234162. E-mail address: andres.campiglia@ucf.edu (A.D. Campiglia). toxic B[a]P and 200 ng L -1 MCL values for Fluo, B[b]F, B[k]F, B[ghi]P, and I[1,2,3-cd]P. These rather low concentration levels make water analysis a particularly challenging task. The clas- sic approach follows the sequence of sample preparation and chromatographic analysis. By removing PAHs from the water sample into an organic solvent suitable for chromatographic anal- ysis, sample preparation pre-concentrates PAHs, simplifies matrix composition and facilitates analytical resolution in the chromato- graphic column. Solid-phase extraction (SPE) is nowadays the recommended method for water samples [23]. When compared to liquid–liquid extraction, SPE reduces solvent consumption, pre- vents emulsions and provides better extraction efficiency. The main disadvantage of SPE is its long processing time. The extrac- tion of 1 L of water – which is the recommended volume to reach detectable PAHs concentrations by classic chromatographic approaches [23] – adds approximately 1 h to the total analysis time. High-performance liquid chromatography (HPLC) and gas chro- matography/mass spectrometry (GC/MS) are the basis of EPA methodology. Ultraviolet absorption (254 nm) and room temper- ature fluorescence detection are widely used in HPLC, but the selectivity of these detectors is modest. Since PAHs identification is solely based on retention times, unambiguous PAH identification requires complete chromatographic resolution in the separation column. When HPLC is applied to “unfamiliar” samples, a suppor- ting analytical technique such as GC/MS is recommended to verify http://dx.doi.org/10.1016/j.chroma.2014.03.082 0021-9673/© 2014 Elsevier B.V. All rights reserved.