دومین مهایش ملی ایمنی کار، سالمت و حمیط زیست a newly synthesized nanoporous silica as a novel stationary phase for Extraction and Separation of PAHs pollutants from environmental samples using Needle-trap SPME followed by GC/MS determination 1 Shahriar Shadabi,2Ali Reza Ghiasvand 1 student of phD and labor inspector, Department of Chemistry, Lorestan University, Khorramabad firstname.lastname@example.org 2 Professor of analytical chemistry, Department of Chemistry, Lorestan University, Khorramabad email@example.com Abstract Polycyclic aromatic hydrocarbons (PAHs) in environmental samples have carcinogenic and mutagenic properties of these compounds. Needle trap devices (NTDs), like solid-phase microextraction (SPME) fibers,represent a new approach to one-step solvent-free sample preparation and injection. The prepared Nanoporous silica material was immobilized inside of a needle (a length of 1 cm from the tip of needle) using epoxy glue, resulting in the development of a needle NT-SPME device. After completeness of the extraction, the proposed needle was directly injected into injection port of a GC/MS system for desorption and following determination of the PAHs. The obtained R2, RSDs and LODs were over the ranges of 0.993-0.998, 5.9-10.2% and 0.04–40.00 ng mL−1, respectively. The proposed NT-SPME method was successfully applied to the extraction and determination of PAHs in different water samples. Keywords: PAHs; Needle trap device; Nanoporous silica 1. Introduction Polycyclic aromatic hydrocarbons (PAHs) are a large group of organic compounds with two or more fused aromatic rings. They are formed during the incomplete burning of coal, oil and gas, garbage, or other organic substances like tobacco or charbroiled meat. Because of their high partition coefficients and low water solubilities, PAHs can be easily adsorbed onto the organic phase of solid particles. Solid-phase microextraction (SPME) is a new and growing sample preparation technique and an attractive alternative to classical extraction methods. In response to demand for more robust solid-phase microextraction (SPME) systems, a needle trap device (NTD) technique has recently been introduced [1-3]. The capacity of the needle trap device can be increased by using small size particles of sorbent for packing. Ordered nanoporous silica such as MCM-41, LUS-1 and SBA-15 with very high surface area, uniform open form structure and extremely narrow pore size distribution has great potential for application in many fields such as catalysts, preconcentration of metals, drug delivery and modified carbon paste electrodes [4,5]. In this paper, amino ethyl-functionalized SBA-15 is synthesized and used, for the first time, as coating of needle trap device and in combination with GC-MS . 2. Experimental 2.1. GC-MS analysis GC-MS analysis was conducted with a Shimadzu (Japan) model GC-17A gas chromatograph coupled to a Shimadzu model GCMS-QP5050 mass spectrometer. Compounds were separated on a 30 m × 0.22 mm i.d. fused-silica capillary column coated with 0.25 µm film of BP-5 (Shimadzu). 2.2. Preparing needle trap devices The schematic diagram of a needle trap device is shown in Fig. 1. To immobilize the sorbent, the mixture of the 5-min epoxy glue and the sorbent was packed into the needle. Before the glue cured, a syringe was connected to the needle trap, and the syringe was pushed and pulled to prevent the sorbent from blocking the needle trap. After the glue completely cured, the needle trap was conditioned in a GC injector at 300 ◦C for 5 h to remove impurities, and the NTD device was ready for use. During sampling, the needle was exposed to the sample, and the side hole was sealed with a septum. Active sampling required that the needle be connected with a pump or syringe . Fig. 1. Schematic of a needle trap device 2.3. Field samples Three different natural water samples were collected for the study. The Khoramrood (Khoramabad, Iran) river water sample was collected from a polluted part of the river in the city center, in March 2009. The petrochemistry of arak waste water sample (arak, Iran) was collected in a part polluted from some industries, in February 2009. The well water samples were collected from Dareh-garm of Khoramabad, Iran, in March 2009. The samples were stored at 4 °C before the analysis. 2.4. Optimization parameters To evaluate the ability of NTD for extracting aromatic compounds from water samples, a mixture of eight PAHs including naphthalene, acenaphthylene, acenaphthene, fluorene, anthracene, Phenanthrene, fluoranthene and pyrene was used. Effects of sonication time, Sampling volume, temperature, Desorption time and salt concentration on the extraction of the PAHs compounds by the proposed method were optimized using a one-at-a-time process. 2.5. Quantitative analysis Calibration curves were drawn using 10 spiking levels of PAHs in the concentration range of 0.1–1000 ng ml−1. For each level, three replicate extractions and determination were performed at optimal conditions. The values of correlation coefficient obtained, were between 0.993 and 0.998, showing an acceptable linearity in the dynamic ranges. The repeatability of the extraction by the proposed NTD was examined by seven replicated analysis of the PAHs compounds at 1 µg mL-1. The relative standard deviations (R.S.Ds.) were between 2.6 and 7.6% for the analytes. Limits of detection (LODs) calculated as three times the baseline noise under MS-SIM conditions, were in the range of 0.04–40.00 ng ml−1 3. Conclusions Needle trap devices are inexpensive, robust, and reusable, and are suitable for sampling and analyzing volatile organic compounds from many different environmental sample matrices due to their easy and convenient operation and handling, as well as their high concentration efficiency. In this paper, needle trap devices were prepared, evaluated, and applied for sampling PAHs pollutants from environmental matrices. It can be concluded that the new HPTES-SBA-15 NTD is a promising alternative to the commercial SPME fibers as it is robust, selective, highly porous and easily and inexpensively prepared. 4. References  A. R. Ghiasvand, S. Hosseinzadeh, J. Pawliszyn, J. Chromatogr. A 1124 (2006) 35–42.  Eom, A. Tugulea, J. Pawliszyn, J. Chromatogr. A, 1196 (2008) 3.  Wang, F. Fang, J. Pawliszyn, J. Chromatogr. A, 1072 (2005) 127.  L. Bonneviot, M. Morin, A. Badiei, Patent WO 01/55031 A1, 2001.  D. Zhao, Q. Huo, J. Feng, B.F. Chmelka, G.D. Stucky, J. Am. Chem. Soc. 120 (1998) 6024.  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