Development of a Needle Trap Device Packed with HKUST-1 Sorbent for Sampling and Analysis of BTEX in Air

: pp. 314 – 327
Center of Excellence for Occupational Health, Occupational Health and Safety Research Center, School of Public Health, Hamadan University of Medical Sciences
Center of Excellence for Occupational Health, Occupational Health and Safety Research Center, School of Public Health, Hamadan University of Medical Sciences
Faculty of Chemistry, Bu-Ali-Sina University
Center of Excellence for Occupational Health, Occupational Health and Safety Research Center, School of Public Health, Hamadan University of Medical Sciences
Faculty of Chemistry, Bu-Ali-Sina University

In this study, we developed a needle trap device packed with HKUST-1 (Cu-based metal-organic framework) for the sampling and analysis of benzene, toluene, ethylbenzene, and xylene (BTEX) in ambient air for the first time. The HKUST-1 was synthesized via the electrochemical process. Afterwards, the adsorbent was packed into 22 gauge needles. To provide the different concentrations of BTEX, the syringe pump was connected to the glass chamber to inject a specific rate of the BTEX compounds. Design-expert software (version 7) was used to optimize the analytical parameters including breakthrough volume, desorption conditions and sampling conditions. The best desorption conditions were achieved at 548 K for 6 min, and the best sampling conditions were determined at 309 K of sampling temperature and 20 % of relative humidity. According to the results, the limit of quantification (LOQ) and limit of detection (LOD) of the developed needle trap device (NTD) were in the range of 0.52–1.41 and 0.16–0.5 mg/m3, respectively. In addition, the repeatability and reproducibility of the method were calculated to be in the range of 5.5–13.2 and 5.3–12.3 %, respectively. The analysis of needles stored in the refrigerator (>277 K) and room temperature (298 K) showed that the NTD can store the BTEX analytes for at least 10 and 6 days, respectively. Our findings indicated that the NTD packed with HKUST-1 sorbent can be used as a trustworthy and useful technique for the determination of BTEX in air. 

[1] Durmusoglu, E.; Taspinar, F.; Karademir, A. Health Risk Assessment of BTEX Emissions in the Landfill Environment. J. Hazard. Mater. 2010, 176, 870-877.
[2] IARC Monographs on the Evaluation of Carcinogenic Risks to Humans, v. 100F; International Agency for Research on Cancer: Lyon, 2012.
[3] Riboni, N.; Trzcinski, J.W.; Bianchi, F.; Massera, C.; Pinalli, R.; Sidisky, L.; Dalcanale, E.; Careri, M. Conformationally Blocked Quinoxaline Cavitand as Solid-Phase Microextraction Coating for the Selective Detection of BTEX in Air. Anal. Chim. Acta 2016, 905, 79-84.
[4] Ma J-Q., Liu L., Wang X.; Chen, L.-Z.; Lin, J.-M.; Zhao, R.-S. Development of Dispersive Solid-Phase Extraction with Polyphenylene Conjugated Microporous Polymers for Sensitive Determination of Phenoxycarboxylic Acids in Environmental Water Samples. J. Hazard. Mater. 2019, 371, 433-439.
[5] Wang, R.; Ma, X.; Zhang, X.; Li, X.; Li, D.; Dang, Y. C8-Modified Magnetic Graphene Oxide Based Solid-Phase Extraction Coupled with Dispersive Liquid-Liquid Microextraction for Detection of Trace Phthalate Acid Esters in Water Samples. Ecotox. Environ. Safe. 2019, 170, 789-795.
[6] Lendor, S.; Hassani, S.-A.; Boyaci, E.; Singh, V.; Womelsdorf, T.; Pawliszyn, J. Solid Phase Microextraction-Based Miniaturized Probe and Protocol for Extraction of Neurotransmitters from Brains in Vivo. Anal. Chem. 2019, 91, 4896-4905.
[7] Ghavidel, F.; Shahtaheri, S.J.; Jazani, R.K.; Torabbeigi, M.; Froushani, A.R.; Khadem, M. Optimization of Solid Phase Microextraction Procedure Followed by Gas Chromatography with Electron Capture Detector for Pesticides Butachlor and Chlorpyrifos. Am. J. Anal. Chem. 2014, 5, 535-546.
[8] Koziel, J.A.; Odziemkowski, M.; Pawliszyn, J. Sampling and Analysis of Airborne Particulate Matter and Aerosols Using In-Needle Trap and SPME Fiber Devices. Anal. Chem. 2001, 73, 47-54.
[9] Chen, J.; Zhang, B.; Zheng, D.; Dang, X.; Ai, Y.; Chen, H. A Novel Needle Trap Device Coupled with Gas Chromatography for Determination of Five Fatty Alcohols in Tea Samples. Anal. Methods 2018, 10, 5783-5789.
[10] Kleeblatt, J.; Schubert, J.K.; Zimmermann, R. Detection of Gaseous Compounds by Needle Trap Sampling and Direct Thermal-Desorption Photoionization Mass Spectrometry: Concept and Demonstrative Application to Breath Gas Analysis. Anal. Chem. 2015, 87, 1773-1781.
[11] Mesarchaki, E.; Yassaa, N.; Hein, D.; Lutterbeck, H.E.; Zindler, C.; Williams, J. A Novel Method for the Measurement of VOCs in Seawater Using Needle Trap Devices and GC–MS. Marine Chem. 2014, 159, 1-8.
[12] Reyes-Garcés, N.; Gómez-Ríos, G.A.; Souza Silva, É.A.; Pawliszyn, J. Coupling Needle Trap Devices with Gas Chromatography–Ion Mobility Spectrometry Detection as a Simple Approach for On-Site Quantitative Analysis. J. Chromatogr. A 2013, 1300, 193-198.
[13] Warren, J.M.; Parkinson, D.-R.; Pawliszyn, J. Assessment of Thiol Compounds from Garlic by Automated Headspace Derivatized In-Needle-NTD-GC-MS and Derivatized In-Fiber-SPME-GC-MS. J. Agricult. Food Chem. 2013, 61, 492-500.
[14] Eom, I.-Y.; Risticevic, S.; Pawliszyn, J. Simultaneous Sampling and Analysis of Indoor Air Infested with Cimex Lectularius L. (Hemiptera: Cimicidae) by Solid Phase Microextraction, Thin Film Microextraction and Needle Trap Device. Anal. Chim. Acta 2012, 716, 2-10.
[15] Vallecillos, L.; Borrull, F.; Sanchez, J.M.; Pocurull, E. Sorbent-Packed Needle Microextraction Trap for Synthetic Musks Determination in Wastewater Samples. Talanta 2015, 132, 548-556.
[16] Eom, I.-Y.; Jung, M.-J. Identification of Coffee Fragrances Using Needle Trap Device-Gas Chromatograph/Mass Spectrometry (NTD-GC/MS). Bull. Korean Chem. Soc. 2013, 34, 1703-1707.
[17] Trefz, P.; Kischkel, S.; Hein, D.; James, E.S.; Schubert, J.K.; Miekisch, W. Needle Trap Micro-Extraction for VOC Analysis: Effects of Packing Materials and Desorption Parameters. J. Chromatogr. A 2012, 1219, 29-38.
[18] Alizadeh, S.; Nematollahi, D. Electrochemically Assisted Self-Assembly Technique for the Fabrication of Mesoporous Metal–Organic Framework Thin Films: Composition of 3D Hexagonally Packed Crystals with 2D Honeycomb-like Mesopores. J. Am. Chem. Soc. 2017, 139, 4753-4761.
[19] Alizadeh, S.; Nematollahi, D. Convergent and Divergent Paired Electrodeposition of Metal-Organic Framework Thin Films. Sci. Rep. 2019, 9, 14325.
[20] Liu, C.; Yu, L-Q.; Zhao, Y-T.; Lv, Y-K. Recent Advances in Metal-Organic Frameworks for Adsorption of Common Aromatic Pollutants. Microchim. Acta 2018, 185, 342.
[21] Li, J-R.; Sculley, J.; Zhou, H-C. Metal–Organic Frameworks for Separations. Chem. Rev. 2012, 112, 869-932.
[22] Lin, K-S.; Adhikari, A.K.; Ku, C-N.; Chiang, C.-L.; Kuo, H. Synthesis and Characterization of Porous HKUST-1 Metal Organic Frameworks for Hydrogen Storage. Int. J. Hydrogen Energ. 2012, 37, 13865-13871.
[23] Chui, S.S.-Y.; Lo, S.M.-F.; Charmant, J.P.H.; Orpen, A.G.; Williams, I.D. A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n. Science 1999, 283, 1148-1150.
[24] Bentley, J.; Foo, G.S.; Rungta, M.; Sangar, N.; Sievers, C.; Sholl, D.S.; Nair, S. Effects of Open Metal Site Availability on Adsorption Capacity and Olefin/Paraffin Selectivity in the Metal–Organic Framework Cu3(BTC)2. Ind. Eng. Chem. Res. 2016, 55, 5043-5053.
[25] NIOSH Manual of Analytical Methods; Eller, P., Cassinelli, M., Eds.; Diane Publ., 1994.
[26] Poormohammadi, A.; Bahrami, A.; Farhadian, M.; Ghorbani-Shahna, F.; Ghiasvand, A. Development of Carbotrap B-Packed Needle Trap Device for Determination of Volatile Organic Compounds in Air. J. Chromatogr. A 2017, 1527, 33-42.
[27] Witek-Krowiak, A.; Chojnacka, K.; Podstawczyk, D.; Dawiec, A.; Pokomeda, K. Application of Response Surface Methodology and Artificial Neural Network Methods in Modelling and optimization of Biosorption Process. Biores. Technol. 2014, 160, 150-160.
[28] Soury, S.; Bahrami, A.; Alizadeh, S.; Ghorbani-Shahna, F.; Nematollahi, D. Development of a Needle Trap Device Packed with Zinc Based Metal-Organic Framework Sorbent for the Sampling and Analysis of Polycyclic Aromatic Hydrocarbons in the Air. Microchem. J. 2019, 148, 346-354.
[29] Thompson, M.; Ellison, S.L.R.; Wood, R. Harmonized Guidelines for Single-Laboratory Validation of Methods of Analysis (IUPAC Technical Report). Pure Appl. Chem. 2002, 74, 835-855.
[30] Zali, S.; Jalali, F.; Es-haghi, A.; Shamsipur, M. New Nanostructure of Polydimethylsiloxane Coating as a Solid-Phase Microextraction Fiber: Application to Analysis of BTEX in Aquatic Environmental Samples. J. Chromatogr. B 2016, 1033, 287-295.
[31] Orazbayeva, D.; Kenessov, B.; Koziel, J.A.; Nassyrova, D.; Lyabukhova, N.V. Quantification of BTEX in Soil by Headspace SPME–GC–MS Using Combined Standard Addition and Internal Standard Calibration. Chromatographia 2017, 80, 1249-1256.
[32] Zhao, Z.; Wang, S.; Yang, Y.; Li, X.; Li, J.; Li, Z. Competitive Adsorption and Selectivity of Benzene and Water Vapor on the Microporous Metal Organic Frameworks (HKUST-1). Chem. Eng. J. 2015, 259, 79-89.
[33] Wang, A.; Fang, F.; Pawliszyn, J. Sampling and Determination of Volatile Organic Compounds with Needle Trap Devices. J. Chromatogr. A 2005, 1072, 127-135.
[34] Zeverdegani, S.K.; Bahrami, A.; Rismanchian, M.; Shahna, F.G. Analysis of Xylene in Aqueous Media Using Needle-Trap Microextraction with a Carbon Nanotube Sorbent. J. Sep. Sci. 2014, 37, 1850-1855.
[35] Warren, J.M.; Pawliszyn, J. Development and Evaluation of Needle Trap Device Geometry and Packing Methods for Automated and Manual Analysis. J. Chromatogr. A 2011, 1218, 8982-8988.