Abstract

Here, we present a surface-enhanced Raman spectroscopy (SERS) nanosensor for environmental pollutants detection. This study was conducted on three polycyclic aromatic hydrocarbons (PAHs): benzo[a]pyrene (BaP), fluoranthene (FL), and naphthalene (NAP). SERS substrates were chemically functionalized using 4-dodecyl benzenediazonium-tetrafluoroborate and SERS analyses were conducted to detect the pollutants alone and in mixtures. Compounds were first measured in water-methanol (9:1 volume ratio) samples. Investigation on solutions containing concentrations ranging from 10−6 g L−1 to 10−3 g L−1 provided data to plot calibration curves and to determine the performance of the sensor. The calculated limit of detection (LOD) was 0.026 mg L−1 (10−7 mol L−1) for BaP, 0.064 mg L−1 (3.2 × 10−7 mol L−1) for FL, and 3.94 mg L−1 (3.1 × 10−5 mol L−1) for NAP, respectively. The correlation between the calculated LOD values and the octanol-water partition coefficient (Kow) of the investigated PAHs suggests that the developed nanosensor is particularly suitable for detecting highly non-polar PAH compounds. Measurements conducted on a mixture of the three analytes (i) demonstrated the ability of the developed technology to detect and identify the three analytes in the mixture; (ii) provided the exact quantitation of pollutants in a mixture. Moreover, we optimized the surface regeneration step for the nanosensor.

Highlights

  • As part of the latest European Water Framework Directives (Directives 2000/60/EC, 2006/118/EC, and 2006/11/EC), the development of analytical tools allowing on-site, accurate, and sensitive detection of pollutants in environmental waters is of primary importance

  • The substrates were immersed in a diazonium salt (DS-C10 H21 ) solution and incubated at +4 ◦ C for 12 h

  • We demonstrated a novel approach for the decoration of a SERS nanosensor for the

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Summary

Introduction

As part of the latest European Water Framework Directives (Directives 2000/60/EC, 2006/118/EC, and 2006/11/EC), the development of analytical tools allowing on-site, accurate, and sensitive detection of pollutants in environmental waters is of primary importance. Stir-bar sorptive extraction (SBSE) [12] combined with gas chromatography (GC) [13,14,15], high performance liquid chromatography (HPLC) [15,16], mass spectrometry (MS) [17], Raman spectroscopy [10], or capillary electrophoresis (CE) have led to accurate results down to pg L−1 concentrations for chlorinated solvents [16], benzene, toluene, ethylbenzene, and xylenes (BTEXs) [10], and polycyclic aromatic hydrocarbons (PAHs) [9,15] Despite their high sensitivity, procedures using these passive sensors are ill-suited for on-site monitoring due to their limitations regarding the co-injection of solvents [18,19] and the desorption procedure under high temperature and/or pressure [20]. QCM is suitable for investigating the preconcentration of organic contaminants using coated polymers or calixarenes [22,23,24,25,26,27,28,29,31,32], the use of QCM-based sensors for the detection of various organic compounds in natural samples has not been reported as far as we know, probably because they cannot identify individual compounds

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