Novel microextraction techniques for aqueous environmental analysis

NOVEL MICROEXTRACTION TECHNIQUES FOR AQUEOUS ENVIRONMENTAL ANALYSIS HII TOH MING (M.Sc., University of Technology Malaysia) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY DEPARTMENT OF CHEMISTRY NATIONAL UNIVERSITY OF SINGAPORE 2012 i Thesis Declaration The work in this thesis is the original work of HII TOH MING, performed independently under the supervision of PROF. LEE HIAN KEE, in Microextraction, Separation Science and Enviroanalytics Laboratory (S5-02-01), Chemistry Department, National University of Singapore, between Jan 2005 and Oct 2009. The content of the thesis has been partly published in: (1) T.M. Hii, C. Basheer, H.K. Lee, Commercial polymeric fiber as sorbent for solid-phase microextraction combined with high-performance liquid chromatography for the determination of polycyclic aromatic hydrocarbons in water, J. Chromatogr. A, 1216 (2009) 7520. 12 Oct 2013 HII TOH MING Name Signature Date ii Acknowledgements Many wonderful individuals have encouraged and inspired this work. I thank them all, with all my heart, and in particular I wish to thank: Prof Lee Hian Kee, project supervisor, for his guidance, encouragement, support and patience throughout my entire Ph.D. study. His passion and commitment for research truly motivated and inspired me to pursue what I believe in. Dr Chanbasha Basheer, Mdm Frances Lim, Dr Guo Liang, Dr Zhang Jie, Dr Wu Jingming, Dr Xu Li, Dr Lee Jingyi, mentors, colleagues and friends, who all contributed in many ways. National University of Singapore, which generously provided financial support, for my research scholarship, conference allowance and project funding. Dr Wang Sang, Dr Wang Chunlei, Dr Liu Mingtao, and church brothers and sisters in Silicon Valley, California, for their help, encouragement and prayers during the time I was writing the thesis. My family members, for their endless understanding and loving support. My baby Asher, my greatest inspiration in the present and my greatest hope for the future. Last, but certainly not least, my beloved wife, Cathy, for her life, joy and love. Soli Deo Gloria! iii Table of Contents Thesis Declaration i Acknowledgements ii Table of Contents iii Summary vii List of Tables ix List of Figures x Acronyms and Abbreviations xiii Chapter Introduction 1.1 The Blue Planet 1.2 Environment Analysis and Sample Preparation 1.3 Conventional Extraction Techniques 1.3.1 Liquid-Liquid Extraction 1.3.2 Soxhlet Extraction 1.3.3 Ultrasound-Assisted Extraction 10 1.3.4 Supercritical Fluid Extraction 12 1.3.5 Pressurized Liquid Extraction 13 1.3.6 Microwave-Assisted Extraction 15 1.3.7 Solid-Phase Extraction 17 1.3.8 Static Headspace 21 1.3.9 Purge and Trap 22 1.3.10 Comparison of Conventional Extraction Techniques 23 1.4 Solventless Microextraction Techniques 23 iv 1.4.1 Solid-Phase Microextraction 28 1.4.2 Stir Bar Sorptive Extraction 34 1.4.3 Single-Drop Microextraction 35 1.4.4 Hollow Fiber Liquid-Phase Microextraction 41 1.4.5 Dispersive Liquid-Liquid Microextraction 52 1.4.6 Comparison of Solventless Microextraction Techniques 58 1.5 Derivatization in Microextraction 58 1.6 Objective of This Work 64 Chapter Commercial Polymeric Fiber as Sorbent for Solid-Phase 66 Microextraction Combined with High-Performance Liquid Chromatography for the Determination of Polycyclic Aromatic Hydrocarbons in Water 2.1 Introduction 66 2.2 Experimental 71 2.2.1 Chemicals and Materials 71 2.2.2 Instrumentation 73 2.2.3 Extraction Procedures 75 2.3 Results and Discussion 76 2.3.1 Properties of Kevlar Fiber 76 2.3.2 Optimization of Extraction Procedures 78 2.3.3 Method Validation 82 2.3.4 Analysis of Genuine Samples 83 2.4 Conclusions 86 v Chapter Use of Commercial Polymeric Fiber for Solid-Phase 87 Microextraction Coupled with High-Performance Liquid Chromatography for the Analysis of Parabens in Water Samples 3.1 Introduction 87 3.2 Experimental 91 3.2.1 Chemicals and Materials 91 3.2.2 Instrumentation 94 3.2.3 Extraction Procedures 95 3.3 Results and Discussion 3.3.1 Optimization of Extraction Procedures 95 95 3.3.2 Method Validation 103 3.3.3 Analysis of Genuine Samples 107 3.4 Conclusions 107 Chapter Agitation-Assisted Dispersive Liquid-Liquid 109 Microextraction Combined with Hollow Fiber LiquidPhase Microextraction for the Determination of Bisphenol A in Environmental Water Samples 4.1 Introduction 109 4.2 Experimental 114 4.2.1 Chemicals and Materials 114 4.2.2 Instrumentation 116 4.2.3 Extraction Procedures 117 4.2.4 Injection Port Derivatization 118 4.3 Results and Discussion 4.3.1 Optimization of Extraction Procedures 119 119 vi 4.3.2 Method Validation 127 4.3.3 Analysis of Genuine Samples 129 4.4 Conclusions 131 Chapter Conclusions and Recommendations 133 5.1 Concluding Remarks 133 5.2 Future Outlook 135 References 138 List of Publications 184 vii Summary Sample preparation is the main bottleneck of the analytical process, especially when trace analysis is the purpose. The high demand for sustainable and more environmentally benign procedures in environmental analysis has driven the development of solventless microextraction techniques. The purpose of the this study was to develop novel SPME and LPME based microextraction techniques for the extraction and determination of trace organic pollutants in the environmental aqueous samples. Chapter briefly described the importance and necessity of sample preparation in environmental monitoring and analysis. It also included detailed discussion of conventional extraction techniques and solventless microextraction techniques, as well as their applications in environmental analysis. The advantages and disadvantages of each approach were depicted in table for comparison. Additionally, the niche of microextraction combined with derivatization in analytical chemistry was also discussed. Chapter and reported the development of a novel SPME based microextraction method making use of commercial polymer fiber as sorbent for the determination of polycyclic aromatic hydrocarbons and parabens in rainwater and wastewater samples, respectively. In this technique, the extraction device was simply a length of a strand of commercial polymeric Kevlar fiber, that was allowed to tumble freely in the aqueous sample during extraction. The extracted analytes were desorbed ultrasonically prior to HPLC analysis. Under the optimal conditions, the proposed viii method showed good linearity ranges, low limits of detection and satisfactory of precisions. The advantage of this polymeric fiber-based SPME method over classical SPME was the robustness of Kevlar fiber, thus it could be used as an extraction device directly without any fabricated device or supported apparatus. The cost- effectiveness of this method was proved by repeated use of a single fiber without deterioration in extraction capability and free of carryover problem. This method gave excellent recovery in various environmental water. In additionally, the good storage performance of the Kevlar fiber also demonstrated the portability of this novel technique for the on-site sampling. Chapter reported the possibility of using combination of two solvent microextraction approaches, i.e. agitation-assisted DLLME (AA-DLLME) and hollow fiber LPME (HF-LPME) for extracting and analyzing BPA in canal water, pond water and seawater samples. Initially, the AA-DLLME was performed using an extraction solvent with density lower than water, and subsequently followed by HF-LPME. After extraction, the extract within hollow fiber was injected together with derivatization reagent for GC-MS analysis. Under optimal conditions, linear range of four orders of magnitude, excellent limit of detection, good recovery and repeatability were achieved. The elimination of disperser solvent greatly reduced the solvent consumption and expanded the choice of solvents for solvent microextraction. Chapter concluded the present project, described the future prospect of the developed methods, and recommended the future works. ix List of Tables Table 1.1 Examples of ubiquitous water pollutants Table 1.2 Advantages and disadvantages of conventional extraction techniques 24 Table 1.3 Advantages and disadvantages of solventless microextraction techniques 59 Table 2.1 Optimized fluorescence detection program used for PAHs determination 74 Table 2.2 Quantitative results of PAHs extraction from water samples using Kevlar fiber 84 Table 2.3 Concentration of PAHs in rainwater samples 85 Table 3.1 Intraday and interday precision of the proposed method 103 Table 3.2 Quantitative results of parabens extraction from water samples using Kevlar fiber 104 Table 3.3 Extraction relative recoveries obtained by proposed method on spiked wastewater samples 106 Table 3.4 Concentration of parabens found in wastewater samples 107 Table 4.1 Quantitative results and experimental parameters of the proposed method and other solventless techniques for BPA extraction in water samples 128 Table 4.2 Concentration of BPA found in environmental water samples 130 Table 4.3 Relative recovery obtained by proposed technique on spiked environmental water samples 130 170 [390] P.D. 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Bodour, Prioritizing research for trace pollutants and emerging contaminants in the freshwater environment, Environ. Pollut., 158 (2010) 3462. 184 List of Publications Journal Paper 1. C. Basheer, H.G. Chong, T.M. Hii, H.K. Lee, Application of porous membrane-protected micro-solid-phase extraction combined with HPLC for the analysis of acidic drugs in wastewater, Anal. Chem., 79 (2007) 6845. 2. T.M. Hii, C. Basheer, H.K. Lee, Commercial polymeric fiber as sorbent for solid-phase microextraction combined with high-performance liquid chromatography for the determination of polycyclic aromatic hydrocarbons in water, J. Chromatogr. A, 1216 (2009) 7520. 3. T.M. Hii, C. Basheer, H.K. Lee, Use of Commercial Polymeric Fiber for Solid-Phase Microextraction Coupled with High-Performance Liquid Chromatography for the Analysis of Parabens in Water Samples. (Manuscript in preparation) T.M. H.K. Hii, Lee, Agitation-Assisted Dispersive Liquid-Liquid Microextraction Combined with Hollow Fiber Liquid-Phase Microextraction for the Determination of Bisphenol A in Environmental Water Samples. (Manuscript in preparation) Book Chapter 1. T.M. Hii, H.K. Lee, Liquid-liquid extraction in environmental analysis, in J. Pawliszyn, H.L. Lord (Eds.), Handbook of Sample Preparation, Wiley, New Jersey, 2010, p. 39-51. Conference Paper 1. T.M. Hii, C. Basheer, H.K. Lee, Commercial polymeric fiber as sorbent for solid-phase microextraction combined with high-performance liquid chromatography for the determination of polycyclic aromatic hydrocarbons in water, ExTech 2007 Ninth International Symposium on Advances in Extraction Technologies, Alesund, Norway, Jun 3-6, 2007. 2. T.M. Hii, C. Basheer, H.K. Lee, Commercial polymeric fiber as sorbent for solid-phase microextraction combined with high-performance liquid 185 chromatography for the determination of polycyclic aromatic hydrocarbon in water, 3rd Mathematics & Physical Science Graduate Congress, Kuala Lumpur, Malaysia, Dec 12-14, 2007. 3. T.M. Hii, C. Basheer, H.K. Lee, Application of commercial polymeric fiber as sorbent for solid-phase microextraction combined with high-performance liquid chromatography for the determination of parabens in water samples, Singapore International Chemistry Conference 5, Singapore, Dec 16-19, 2007 4. T.M. Hii, C. Basheer, H.K. Lee, Use of commercial polymeric fiber for solid-phase microextraction coupled with high-performance liquid chromatography for the analysis of parabens in water samples, 235th ACS National Meeting & Exposition, New Orleans, LA, USA, Apr 6-10, 2008. [...]... Transformation products Metabolites from all above Metabolites of perfluorinated compounds Chloroacetanilide herbicide metabolites environmental pollutants was continuously a formidable challenge for analytical chemist Despite the unprecedented progress made in measurement techniques and analytical tools over the last few decades, the simple approach of “dilute and shoot” is usually incompatible with environmental. .. suitable form for separation and detection Chemical modification of the target analytes could be involved for an easy isolation, and facile later separation and detection [8] Unfortunately, analysts are seldom recommended or even permitted to inject samples without any sample preparation Usually, as a procedure, several sample preparation steps are necessary between sampling and the instrumental analysis For. .. developed extraction techniques during 2002 and 2005, with an inclusion of some novel applications Recently, Chen et al [8] composed a panorama of sample preparation with a focus on some fast developed promising methods Some criteria for evaluating a sample preparation method have also been proposed for reference 1.3 Conventional Extraction Techniques There is a wide range of extraction techniques available,... extraction techniques 1.3.1 Liquid-Liquid Extraction LLE, also known as solvent extraction, is the simplest and most commonly used approach for extraction of nonvolatile and semivolatile organic analytes from aqueous samples Historically, LLE was the first sample preparation used in analytical chemistry Organic chemists have used LLE for over 150 years for isolating organic substances from aqueous solutions... provided an overview and diverse aspects of sample preparation techniques in chemical, biological, pharmaceutical, environmental and material sciences Nollet [16] discussed the important theoretical and practical 7 aspects of sample preparation techniques, separation methods and detection modes in the chromatographic analysis of different environmental compartments Pawliszyn [10] summarized the fundamental... species, including humans for their survival Therefore, ensuring adequate water supplies is crucial for human well-being Although water exists plentifully on Earth, yet, only about 2.5% is freshwater And, because most of the freshwater is stored as glaciers or deep groundwater, it leaves only about one-third of freshwater readily available for human use [3,4] Clean water is vital for basic human needs,... It therefore comes without a surprise that this key environmental problem has been noticeably increasing public awareness to protect and safeguard living environmental, both locally and globally Hence, in order to better assess water quality and evaluate the freshwater's environmental impact, there is a need to monitor the sources and fate of freshwater in the aquatic ecosystem 1.2 Environment Analysis. .. sample for between 6 and 48 hours The completed extraction produces a large volume, dilute and dirty extract that require solvent evaporation and extensive cleanup prior to analysis As a rugged and wellestablished technique, Soxhlet is often used as the benchmark method for evaluating new extraction techniques Commercially available automatic Soxhlet system (e.g 10 Soxtec) is capable of performing... properly conducted [76] For instance, the solvent volume must be sufficient to completely immerse the sample to prevent electrical arcing [79] For safety precautions, it is highly recommended that only approved equipment and specifically operating procedures are used for MAE application [76] Today MAE has matured and mainly used for the extraction of organic pollutants from environmental samples [69,73,75,76,80]... common sample preparation techniques pharmaceutical, food and natural product analyses [90] in environmental, clinical, 18 SPE was initially developed as a complement or replacement for LLE Conventional LLE is laborious, time consuming, high solvent consumption, difficult to automate, and frequently plagued by emulsion formation In addition, LLE often suffers from poor recoveries for many polar analytes . NOVEL MICROEXTRACTION TECHNIQUES FOR AQUEOUS ENVIRONMENTAL ANALYSIS HII TOH MING (M.Sc., University of Technology Malaysia) A THESIS SUBMITTED FOR THE DEGREE. trace analysis is the purpose. The high demand for sustainable and more environmentally benign procedures in environmental analysis has driven the development of solventless microextraction techniques. . this study was to develop novel SPME and LPME based microextraction techniques for the extraction and determination of trace organic pollutants in the environmental aqueous samples. Chapter