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Application of sulfur microparticles for solid-phase extraction of polycyclic aromatic hydrocarbons from sea water and wastewater samples

Original Research Article Analytica Chimica Acta, Volume 714, 10 February 2012, Pages 89-97 Vahid Khalili-Fard, Kamal Ghanemi, Yadollah Nikpour, Mehdi Fallah-Mehrjardi Abstract The application of sulfur microparticles as efficient adsorbents for the solid-phase extraction (SPE) and determination of trace amounts of 10 polycyclic aromatic hydrocarbons (PAHs) was investigated in sea water and wastewater samples using high performance liquid chromatography coupled with an ultraviolet detector (HPLCUV). Parameters influencing the preconcentration of PAHs such as the amount of sulfur, solution flow rate and volume, elution solvent, type and concentration of organic modifier, and salt effect were examined. The results showed that at a flow rate of 10 mL min1 for the sample solutions (100 mL), the PAHs could be adsorbed on the sulfur microparticles and then eluted by 2.0 mL of acetonitrile. For HPLCUV analysis of extracted PAHs, the calibration curves were linear in the range of 0.0580.0 g L1; the coefficients of determinations (r2) were between 0.9934 and 0.9995. The relative standard deviations (RSDs) for eight replicates at two concentration levels (0.5 and 4.0 g L1) of PAHs were lower than 7.3%, under optimized conditions. The limits of detection (LODs, <!-- no-mfc -->S/N<!-- /no-mfc --> = 3) of the proposed method for the studied PAHs were 0.0070.048 g L1. The recoveries of spiked PAHs (0.5 and 4 g L1) in the wastewater and sea water samples ranged from 78% to 108%. The simplicity of experimental procedure, high extraction efficiency, short sample analysis, and using of low cost sorbent demonstrate the potential

of this approach for routine trace PAH analysis in water and wastewater samples. 2. Triacontyl modified silica gel as a sorbent for the preconcentration of polycyclic aromatic hydrocarbons in aqueous samples prior to gas chromatographic-mass spectrometry determination Chinese Chemical Letters, Volume 21, Issue 6, June 2010, Pages 730-733 Yan Liu, Hai Fang Li, Jing Hua Zhang, Tsuneaki Maeda, Jin Ming Lin Abstract Triacontyl modified silica gel as a sorbent coupled with gas chromatographymass spectrometry (GCMS) was developed to determine EPA prior 16 polycyclic aromatic hydrocarbons (PAHs) in water samples. Various parameters of solid-phase extraction such as organic modifier solvent, eluent, sample flow rate and volume were optimized. The developed method was found to yield a linear calibration curve in the concentration range of 0.05 8 g/L with respect to naphthalene, acenaphthylene, acenaphthene and 0.018 g/L for dibenz[a,h]anthracene and 0.0514 g/L for fluorene, phenanthrene, anthracene and 0.01 14 g/L for the rest of analytes. Furthermore, the good accuracy and repeatability of the method made sure the requirements for achieving reliable analysis of PAHs in the environmental water samples, and the recoveries of optimal method were in the range of 80120% except to higher volatility PAHs. C30-bonded silica was proved to be an efficient sorbent for extraction of high molecular weight PAHs. 3. Enrichment of polycyclic aromatic hydrocarbons in seawater with magnesium oxide microspheres as a solidphase extraction sorbent Abstract

The enrichment of polycyclic aromatic hydrocarbons (PAHs) in water samples with magnesium oxide (MgO) microspheres was evaluated, and four 35-ring PAHs were used as probes to validate the adsorption capacity of the material. Factors affecting the recovery of PAHs were investigated in detail, including the type and concentration of organic modifiers, elution solvents, particle size of the adsorbent, volume and flow rate of the samples, and the lifetime of MgO cartridges. The recoveries of four PAHs extracted from 20 mL of seawater spiked with standard PAHs ranged from 85.8% to 102.0% under the optimised conditions. The limits of detection varied from 1.83 ng L1 to 16.03 ng L1, indicating that the analytical method was highly sensitive. Additionally, the proposed method was successfully used to enrich PAHs in seawater. Compared to conventional methods, the proposed method consumed less organic modifier (5% acetone), and cheaper sorbents with comparable extraction efficiency were employed. Article Outline 4. Multiwalled carbon nanotubes/cryogel composite, a new sorbent for determination of trace polycyclic aromatic hydrocarbons Original Research Article Microchemical Journal, Volume 96, Issue 2, November 2010, Pages 317-323 Pamornrat Kueseng, Chongdee Thammakhet, Panote Thavarungkul, Proespichaya Kanatharana Abstract A new cost-effective sorbent, multiwalled carbon nanotubes/poly (vinyl alcohol) cryogel composite (MWCNTs/PVA), was prepared under frozen conditions for the extraction and preconcentration of trace polycyclic aromatic hydrocarbons (PAHs) in water samples. This was followed by high performance liquid chromatography (HPLC) with fluorescence detection. The proposed method provided a high enrichment factor with an extremely high extraction efficiency (8998%) of three spiked levels of three

standard PAHs with relative standard deviations of less than 8%. The low detection limits of the method were 5, 8 and 5 ng L 1 for benzo(a)anthracene, benzo(b)fluoranthene and benzo(a)pyrene, respectively. This method was successfully applied for the determination of the three PAHs in real water samples where they were found in the range of 7 to 22 ng L 1. The major advantages of MWCNTs/PVA over the commercial C18 is that it can be operated at a higher loading flow rate without sorbent clogging and requires a shorter time for completion without any loss of extraction efficiency. 5,. Use of cotton as a sorbent for on-line precolumn enrichment of polycyclic aromatic hydrocarbons in waters prior to liquid chromatography determination Original Research Article Microchemical Journal, Volume 77, Issue 1, May 2004, Pages 1922 Jing-fu Liu, Yu-guang Chi, Gui-bin Jiang, Chao Tai, Jing-tian Hu Abstract Using cotton as a solid-phase extraction sorbent of the precolumn, an on-line coupled precolumn preconcentration-liquid chromatography system with fluorescence detection was developed for the determination of PAHs in aqueous samples. Four PAHs including fluorene, phenanthrene, fluoranthene and benzo[k]fluoranthene were preconcentrated by a precolumn packed with 30 mg of absorbent cotton and then separated by C18 analytical column. When 100 ml of sample was enriched, the proposed procedure provided detection limits in the range of 0.5 57 ng l1. Several water samples spiked with PAHs were analyzed with recoveries in the range of 92119% at spiking level of 100 ng l1 for fluorene, phenanthrene and fluoranthene, and 10 ng l1 for benzo[k]fluoranthene, respectively. 6. Evaluation of single-walled carbon nanohorns as sorbent in dispersive micro solid-phase extractionOriginal

Research Article Analytica Chimica Acta, Volume 714, 10 February 2012, Pages 76-81 Juan Manuel Jimnez-Soto, Soledad Crdenas, Miguel Valcrcel Abstract A new dispersive micro solid-phase extraction method which uses single-walled carbon nanohorns (SWNHs) as sorbent is proposed. The procedure combines the excellent sorbent properties of the nanoparticles with the efficiency of the dispersion of the material in the sample matrix. Under these conditions, the interaction with the analytes is maximized. The determination of polycyclic aromatic hydrocarbons was selected as model analytical problem. Two dispersion strategies were evaluated, being the functionalization via microwave irradiation better than the use of a surfactant. The extraction was accomplished by adding 1 mL of oxidized SWHNs (o-SWNHs) dispersion to 10 mL of water sample. After extraction, the mixture was passed through a disposable Nylon filter were the nanoparticles enriched with the PAHs were retained. The elution was carried out with 100 L of hexane. The limits of detection achieved were between 30 and 60 ng L1 with a precision (as repeatability) better than 12.5%. The recoveries obtained for the analytes in three different water samples were acceptable in all instances. The performance of oSWNHs was favourably compared with that provided by carboxylated single-walled carbon nanotubes and thermally treated carbon nanocones. 7. Determination of 16 polycyclic aromatic hydrocarbons in environmental water samples by solid-phase extraction using multi-walled carbon nanotubes as adsorbent coupled with gas chromatographymass spectrometry Original Research Article Journal of Chromatography A, Volume 1217, Issue 34, 20 August 2010, Pages 5462-5469 Jiping Ma, Ronghui Xiao, Jinhua Li, Junbao Yu, Yanqing Zhang, Lingxin Chen

A solid-phase extraction (SPE) using multi-walled carbon nanotubes (MWCNTs) as adsorbent coupled with gas chromatographymass spectrometry (GCMS) method was developed for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) in environmental water samples. Several condition parameters, such as extraction adsorbents, elution solvents and volumes, and sample loading flow rate and volume were optimized to obtain high SPE recoveries and extraction efficiency. 150 mg MWCNTs as sorbent presented high extraction efficiency of 16 PAHs due to the large specific surface area and high adsorption capacity of MWCNTs compared with the commercial C18 column (250 mg/2 mL). The calibration curves of 16 PAHs extracted were linear in the range of 205000 ng L1, with the correlation coefficients (r2) between 0.9848 and 0.9991. The method attained good precisions (relative standard deviation, RSD) from 1.2% to 12.1% for standard PAHs aqueous solutions; method recoveries ranged in 76.0125.5%, 74.5127.0%, and 70.0122.0% for real spiked samples from river water, tap water and seawater, respectively. Limits of detection (LODs, S/N = 3) of the method were determined from 2.0 to 8.5 ng L1. The optimized method was successfully applied to the determination of 16 PAHs in real environmental water samples. 9.Development of micro-solid phase extraction with titanate nanotube array modified by cetyltrimethylammonium bromide for sensitive determination of polycyclic aromatic hydrocarbons from environmental water samples Original Research Article Journal of Hazardous Materials, Volume 193, 15 October 2011, Pages 82-89 Yunrui Huang, Qingxiang Zhou, Guohong Xie This paper described a simple and novel analytical technique for the determination of polycyclic aromatic hydrocarbons (PAHs) in environmental water samples. A micro-solid phase extraction (SPE) was developed utilizing cetyltrimethylammonium bromide

modified ordered TiO2nanotube array. The experimental results indicated that modified TiO2 nanotube arrays demonstrated an excellent merit on the preconcentration of PAHs, and there were excellent linear relationships between peak area and the concentration of PAHs in the range of 0.2100 g L1and 1.0 100 g L1, respectively. The detection limits of proposed method for the targeted PAHs were in the range of 0.026 0.82 g L1 (S/N = 3). The real-world environmental water samples were used to validate the applicability of the proposed method and good spiked recoveries were in the range of 75.0 114%. All these results demonstrated that this new -SPE technique was a viable alternative to conventional enrichment techniques for the extraction and analysis of PAHs in complex samples.

11.Flow injection solid-phase extraction using multi-walled carbon nanotubes packed micro-column for the determination of polycyclic aromatic hydrocarbons in water by gas chromatographymass spectrometry Original Research Article Journal of Chromatography A, Volume 1217, Issue 17, 23 April 2010, Pages 2911-2917 Hong Wu, Xuecui Wang, Bing Liu, Jie Lu, Baixiang Du, Luxin Zhang, Jingjing Ji, Qiaoyu Yue, Baoping Han A flow injection solid-phase extraction preconcentration system using a multi-walled carbon nanotubes (MWCNTs) packed microcolumn was developed for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) in water by gas chromatography mass spectrometry (GCMS). The preconcentration of PAHs on the MWCNTs was carried out based on the adsorption retention of analytes by on-line introducing the sample into the microcolumn system. Methanol was introduced to elute the retained analytes for GCMS analysis using selected ion monitoring (SIM) mode. Important influence factors were studied in detail, such as

sample acidity, sample flow rate, eluent flow rate and volume, dimensions of MWCNTs and amounts of packing material. Limits of detection of 16 PAHs for an extraction of 50 mL water sample were in the range of 0.0010.15 g L1, and the precisions (RSD) were in the range of 414%. The optimized method was successfully applied to the determination of 16 PAHs in surface waters, with recoveries in the range of 7293% for real spiked sample. 12. Anilinesilica nanocomposite as a novel solid phase microextraction fiber coating Original Research Article Journal of Chromatography A, Volume 1238, 18 May 2012, Pages 22-29 Habib Bagheri, Ali Roostaie Abstract A new unbreakable solid phase microextraction (SPME) fiber coating based on anilinesilica nanocomposite was electrodeposited on a stainless steel wire. The electropolymerization process was carried out at a constant deposition potential, applied to the corresponding aqueous electrolyte containing aniline and silica nanoparticles. The scanning electron microscopy (SEM) images showed the nonsmooth and the porous surface structure of the prepared nanocomposite. The applicability of the new fiber coating was examined by headspace-solid phase microextraction (HS-SPME) of some environmentally important polycyclic aromatic hydrocarbons (PAHs), as model compounds, from aqueous samples. Subsequently, the extracted analytes were transferred into a gas chromatography (GC) by thermal desorption. Parameters affecting the synthesizing and extraction processes including the voltage of power supply, the weight ratio of components, the time of electrodeposition, extraction time and temperature, the ionic strength, and desorption temperature and time were optimized. Eventually, the developed method was validated by gas chromatographymass spectrometry (GCMS). At the optimum conditions, the relative standard deviation

(%RSD) values for a double distilled water spiked with the selected PAHs at 40 ng L1 were 613% (n = 3) while the limit of detection (LOD) results were between 1 and 3 ng L1. The calibration graphs were linear in the concentration range from 20 to 4000 ng L1 (R2 > 0.995). Finally the developed method was applied to the analysis of Kalan dam, rain and tap water samples and the relative recovery values were found to be in the range of 76109%, under optimized conditions. In addition, the synthesis of the nanocomposite coating was carried out conveniently while it is rather inexpensive, easy, simple, rapid and highly durable and can be used frequently. 14,. Talanta Available online 27 September 2012 In Press, Corrected Proof Note to users

Facile and tunable fabrication of Fe3O4/graphene oxide nanocomposites and their application in the magnetic solid-phase extraction of polycyclic aromatic hydrocarbons from environmental water samples

Qiang Hana, b, Zonghua Wangb, Jianfei Xiab, Sha Chena,

Xiaoqiong Zhanga, Mingyu Dinga,


a ,

Beijing Key Laboratory for Microanalytical Methods and

Instrumentation, Department of Chemistry, Tsinghua University, Beijing 100084, China

Laboratory of Fiber Materials and Modern Textile, the Growing

Base for State Key Laboratory, Qingdao University, Shandong 266071, China

http://dx.doi.org/10.1016/j.talanta.2012.09.046, How to Cite or Link Using DOI Permissions & Reprints Purchase $41.95

Abstract An electrostatic self-assembly approach was employed to prepare Fe3O4/graphene oxide nanocomposites, and their application in the magnetic solid-phase extraction of polycyclic aromatic hydrocarbons from environmental samples was investigated. With the highly hydrophilic graphene oxide sheets and positively charged surface of the Fe3O4 nanoparticles, the nanocomposites

were synthesized through electrostatic interaction in aqueous solution. Simultaneously, the different loading amounts of Fe3O4 onto the graphene oxide were easily controlled by changing the proportion of the initial precursors. The identity of the hybrid materials was confirmed using transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and a vibrating sample magnetometer. Five polycyclic aromatic hydrocarbons were selected as model analytes to validate the extraction performance of the Fe3O4/GO nanocomposite as a MSPE sorbent. The excellent adsorption property was attributed to the dominant roles of stacking interaction and hydrophobic interaction. After optimizing the conditions, the results indicated that the recoveries of these compounds were in the range of 76.8103.2%, with relative standard deviations ranging between 1.7% and 11.7%; the limits of detection were in the range of 0.09 0.19 ng mL1. 16. Journal of Environmental Sciences Volume 23, Issue 5, May 2011, Pages 860867

TiO2 nanotubes as solid-phase extraction adsorbent for the determination of polycyclic aromatic hydrocarbons in environmental water samples

Bochra Bejaoui Kefia, Latifa Latrous El Atracheb, Hafedh Kochkara, Abdelhamid Ghorbelc
a ,

Laboratoire des Matriaux Utiles, Institut National de Recherche

et d'Analyse Physico-chimique, ple technologique Sidi-Thabet 2020 Tunis, Tunisia

Laboratoire de Chimie Analytique et Electrochimie, Dpartement

de Chimie, Facult des Sciences de Tunis, Campus Universitaire, 2092 EL Manar Tunis, Tunisia

Laboratoire de Chimie des Matriaux et Catalyse, Facult des

Sciences de Tunis, Campus Universitaire, 2092 EL Manar Tunis, Tunisia

http://dx.doi.org/10.1016/S1001-0742(10)60481-0, How to Cite or Link Using DOI Permissions & Reprints Purchase $31.50

Abstract
An analytical method based on TiO2 nanotubes solid-phase extraction (SPE) combined with gas chromatography (GC) was established for the analysis of seven poly cyclic aromatic hydrocarbons (PAHs): acenaphtylene, acenaphthene, anthracene, fluorene, phenanthrene, fluoranthene and pyrene. Factors affecting the extraction efficiency including the eluent type and its volume, adsorbent amount, sample volume, sample pH and sample flow rate were optimized. The characteristic data of analytical performance were determined to investigate the sensitivity and precision of the method. Under the optimized extraction conditions, the method showed good linearity in the range of 0.01-0.8 g/mL, repeatability of the extraction (RSD were between 6.7% and 13.5%, n = 5) and satisfactory detection limits (0.017-0.059 ng/mL). The developed method was successfully applied to the analysis of surface water (tap, river and dam) samples. The recoveries of PAHs spiked in environmental water samples ranged from 90% to 100%. All the results indicated the potential application of titanate nanotubes as solid-phase extraction adsorbents to pre-treat water samples.