Analysis of Nitroaromatics: A Comparison Between Gas Chromatography, Liquid Chromatography and their Hyphenation with Solid Phase Micro-Extraction

Author(s): Puthiyaveettilparambu Y. Ajmal, Rahul C. Bhangare, Mahesh Tiwari, Sanjay K. Sahu*.

Journal Name: Current Chromatography

Volume 6 , Issue 1 , 2019

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Abstract:

Background: A major class of nitro-explosives being used in military and commercial purposes belongs to organic compounds containing nitro (NO2) groups like nitrobenzene, nitrotoluenes, and nitramines. Apart from being energetic materials, these substances are inherently toxic to human beings. These substances may find their way into different environmental matrices from the site of their military or commercial applications. They are present in nature at ultra-trace levels.

Methods: Chromatographic techniques have been widely used for the detection and quantification of nitro-explosives from various environmental matrices. The current study involves a comparison of the performance of liquid and gas chromatography with and without pre-concentration techniques like Solid Phase Micro-extraction (SPME) to detect ultra-trace levels nitrobenzene and nitrotoluenes in water.

Results: The addition of SPME to chromatographic techniques significantly improves the quality of the analysis in terms of ease and sensitivity. Both SPME-HPLC and SPME-GC are equally competent techniques for the analysis of nitroaromatic explosives from water. Detection limits were improved by upto 5 orders of magnitude by these methods.

Conclusion: The methodology for determining nitroaromatic explosives in water samples has been optimized and validated after trying four different methods and comparing their performance. GC and HPLC techniques used alone cannot be sensitive enough to detect these compounds at ultra-trace levels. Both SPME-HPLC-UV and SPME-GC-FID are equally competent techniques. SPME method has been proved to be an excellent tool with no requirement of any tedious sample preparation and chemical processing of the samples.

Keywords: Nitroaromatic explosives, SPME, HPLC-UV, GC-FID, TNT, RDX.

[1]
Yinon, J.; Zitrin, S. Toxicity and metabolism of Explosives; CRC press: Boca Raton, 1990.
[2]
Yinon, J.; Zitrin, S. Modern methods and applications in analysis of Explosives; Wiley & Sons: Chichester, 1993.
[3]
Turesky, R.J.; Le Marchand, L. Metabolism and biomarkers of heterocyclic aromatic amines in molecular epidemiology studies: lessons learned from aromatic amines. Chem. Res. Toxicol., 2011, 24, 1169-1214.
[4]
Kovacica, P.; Somanathana, R. Nitroaromatic compounds: environmental toxicity, carcinogenicity, mutagenicity, therapy and mechanism. J. Appl. Toxicol., 2014, 34, 810-824.
[5]
Shen, H.; Gao, J.; Wang, J. Assessment of toxicity of two nitroaromatic compounds in the freshwater fish Cyprinus carpio. Front. Environ. Sci. Eng., 2012, 6(4), 518-523.
[6]
Kirui, W.K.; Wu, S.; Kizito, S.; Carvalho, P.N.; Dong, R. Pathways of nitrobenzene degradation in horizontal subsurface flow constructed wetlands: effect of intermittent aeration and glucose addition. J. Environ. Manage., 2015, 166, 38-44.
[7]
Zhao, L.; Lu, Z.; Tan, S.; Ciren, J.; Tan, C. Effects of glucose and starch on the toxicity of nitrobenzene to plants and microbes in constructed wetlands. Sci. Total Environ., 2019, 658, 809-817.
[8]
Lin, Y.; Yin, J.; Wang, J.; Tian, W. Performance and microbial community in hybrid anaerobic baffled reactor-constructed wetland for nitrobenzene wastewater. Bioresour. Technol., 2012, 118, 128-135.
[9]
Lu, L.; Liu, W.; Wanga, J.; Zhong, H.; Liu, J.; Singh, A.K.; Kumar, A. Four new luminescent-organic frameworks exhibiting highly sensing of nitroaromatics: An experimental and computational insight. Inorg. Chim. Acta, 2019, 487, 257-263.
[10]
Sriyab, S.; Jorn-Iat, K.; Prompinit, P.; Wolschann, P.; Hannongbua, S.; Suramitr, S. Photophysical properties of 1-pyrene-based derivatives for nitroaromaticexplosives detection: Experimental and theoretical studies. J. Lumin., 2018, 203, 492-499.
[11]
Krishnan, S.; Suneesh, C.V. Fluorene-Triazine conjugated porous organic polymer framework for superamplified sensing of nitroaromatic explosives. J. Photochem. Photobiol., 2019, 371, 414-422.
[12]
Pawliszyn, J. SPME: Theory and practice ; (1997). Wiley; USA, 1997.
[13]
Wercinski, S.A.S. Solid Phase Micro-Extraction: A practical Guide; Marcel Dekker Inc.; New York 1999.
[14]
Aulakh, J.S.; Malik, A.K.; Kaur, V.; Schmitt-Kopplin, P. A review on Solid Phase Micro Extraction-High Performance Liquid Chromatography (SPME-HPLC) analysis of pesticides. Crit. Rev. in Anal. Chem., 2005, 35(1), 71-85.
[15]
Pawliszyn, J. Applications of Solid Phase Micro-extraction; The Royal Society of Chemistry: Cornwall, UK, 1999.
[16]
Muller, D.; Levy, A.; Shelef, R.; Abramovich-Bar, S.; Sonenfeld, D.; Tamiri, T. Improved method for the detection of TATP after explosion. J. Forensic Sci., 2004, 49, 935-938.
[17]
Furton, K.G.; Wu, L.M.; Almirall, J.R. Optimization of solid phase microextraction (SPME) for the recovery of explosives from aqueous and post explosion debris followed by gas and liquid chromatographic analysis. J. Forensic Sci., 2000, 45, 845-852.
[18]
Martin, D.; Ruiz, J. Analysis of polycyclic aromatic hydrocarbons in solid matrixes by solid-phase microextraction coupled to a direct extraction device. Talanta, 2007, 71, 751-757.
[19]
Vaz, J.M. Screening direct analysis of PAHS in atmospheric particulate matter with SPME. Talanta, 2003, 60, 687-693.
[20]
Malik, A.K.; Kaur, V.; Verma, N. A review on solid phase microextraction-High performance liquid chromatography as a novel tool for the analysis of toxic metal ions. Talanta, 2006, 68, 842-849.
[21]
Halasz, A.; Groom, C.; Zhou, E.; Paquet, L.; Beulieu, C.; Deschamps, S.; Corriveau, A.; Thiboutot, S.; Ampleman, G.; Dubois, C.; Hawari, J. Detection of explosives and their degradation products in the soil environments. J. Chromatogr. A, 2002, 963, 411-418.
[22]
Díez, S.; Bayona, J.M. Determination of Hg and organo-mercury species following SPME: a review. Talanta, 2008, 77, 21-27.
[23]
Monteil-Rivera, F.; Beaulieu, C.; Deschamps, S.; Paquet, L.; Hawari, J. Determination of explosives in environmental water samples by solid-phase microextraction-liquid chromatography. J. Chromatogr. A, 2004, 1048, 213-221.
[24]
Wu, L.; Almirall, J.R.; Furton, K.G. An improved interface for coupling Solid-Phase Microextraction (SPME) to High Performance Liquid Chromatography (HPLC) applied to the analysis of explosives. J. High Resolut. Chromatogr., 1999, 22(5), 279-282.
[25]
Miriany, A.M.; Fernandez, M.D.R.; da Silva, G.; Alexandra, R.; Leiliane, C.A.; Zenilda, L.C. Analysis of alkylphenols and phthalates in vegetables using SPME and comprehensive two-dimensional gas chromatography. Curr. Chromatogr., 2018, 5(1), 65-71.
[26]
Bhangare, R.C.; Ajmal, P.Y.; Tiwari, M.; Sahu, S.K.; Pandit, G.G. Rapid and solventless analysis of polychlorinated biphenyls in packaged milk using gas chromatography. Curr. Chromatogr., 3(1) 2016 64-72
[27]
Darrach, M.R.; Ghutijian, A.; Plett, G.A. Trace explosives signatures from World War II unexploded undersea ordance. Environ. Sci. Technol., 1998, 32(9), 1354-1358.


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Article Details

VOLUME: 6
ISSUE: 1
Year: 2019
Page: [42 - 51]
Pages: 10
DOI: 10.2174/2213240606666190423122358

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