Mechanism of vortex assisted liquid liquid microextraction of strontium in water sample

THAI NGUYEN UNIVERSITY UNIVERSITY OF AGRICULTURE AND FORESTRY CHU NGUYEN THE STUDY MECHANISM OF VORTEX-ASSISTED LIQUID-LIQUID MICROEXTRACTION OF STRONTIUM IN WATER SAMPLE BACHELOR THESIS Study mode : Full-time Major : Environmental Science and Management Faculty : Advanced Education Program Office Batch : 2014 - 2018 Thai Nguyen 24/9/2018 DOCUMENTATION PAGE WITH ABSTRACT Thai Nguyen University of Agriculture and Forestry Degree Program Bachelor of Environmental Science and Management Student name Chu Nguyen Student ID DTN1453150016 Thesis Title Supervisors Mechanism of vortex-assisted liquid-liquid microextraction of Strontium in water sample - Prof Wu ,Chien-Hou - Prof Nguyen The Hung Supervisor’s Signature Abstract: A vortex-assisted liquid–liquid microextraction method was applied in many years ago, however the first time it was developed for the chromatographic determination of strontium (alkaline-earth) in aqueous samples in 2017 In the extraction , strontium was in aqua phase with the presence of tetraphenylborate as the counter anion, while organic phase (1- octanol was chosen) was complexed with 4′,4″(5″)-di-(tert-butylcyclohexano)-18-crown-6 (7:1 respectively ) Strontium from the organic phase was stripped with nitric acid back to aqueous solution and determined by ion chromatography By changing the concentration of 4′,4″(5″)-di-(tert-butylcyclohexano)-18-crown6 and tetraphenylborate, with standard conditions as vortex for 10s; centrifugation at 6000 rpm for min; stripping by 0.1 M nitric acid and lightproof condition, the result is that with [TPB]=0,003 M and [DtBuCH18C6]= 0,01 M, the extraction of Sr is i optimum with Recovery rate= 79% ,and distribution coefficient logD =1,22 Key words Strontium, tetra phenyl borate, ion chromatography, strontium, vortex-assisted liquid–liquid micro-extraction Number of pages 50 Date of Submission: 24/09/2018 ii ACKNOWLEDGEMENT To have completed this thesis, in addition to the ongoing efforts of myself, I would like to thank for teachers in Advanced Education Program Office as well as teachers in Thai Nguyen University of Agriculture and Forestry, who have dedicated teaching to me the valuable knowledge during study time in university and gave me a chance to my thesis oversea It is with immense gratitude that I acknowledge the support and help of Biomedical Engineering & Environmental Science Department, National Tsing Hua University for accepting me to working in this wonderful place Furthermore, express my sincere deepest gratitude to Prof Wu Chien Hou, from Biomedical Engineering & Environmental Science Department, National Tsing Hua University,who provided physical conditions in laboratory, documents and allowed me to trigger my experiments by myself, and Prof Nguyen The Hung from Thai Nguyen University of Agriculture and Forestry, who guided and created favorable conditions for me during the implementation of this thesis Next, i would like spend special thanks to Ms Pham Thi Hai Van - MSc student who suggested, directly guided to research my thesis, Ms Yang ziruo who teach me tips, principle and working-skills in the laboratory and usage of all devices used in my experiments Besides, they provided the information and data necessary for my implementation process and helped me finish this thesis Finally, I would like to sincerely thank my family, all of my friends who always beside me all the time, giving spiritual help for me complete the tasks assigned during learning and doing this thesis experiment iii In the process of implementing the project, my thesis might have inevitable shortcomings Therefore, I appreciate very much if I may receive the attention and feedback from teachers and friends for this thesis is more completion Sincerely, Chu Nguyen iv TABLE OF CONTENT DOCUMENTATION PAGE WITH ABSTRACT i ACKNOWLEDGEMENT iii TABLE OF CONTENT v LIST OF TABLES vii LIST OF FIGURES viii LIST OF ABBREVIATIONS ix PART I INTRODUCTION 1.1 Research rationale 1.2 Objectives of the research 1.3 Research questions and hypothesis 1.4 Limitations of research PART II LITERATURE REVIEW 2.1 Strontium 2.1.1 The properties of strontium 2.1.2 The interaction of strontium with environment 2.1.3 Effects of Strontium to human‘s health 2.2 Method Review 11 2.2.1 Vortex-assisted liquid–liquid micro-extraction 11 2.2.1 a Vortex-assisted liquid–liquid micro-extraction concept and mechanism 11 2.2.1.b The factors affect to the vortex-assisted liquid-liquid microextraction 13 2.2.1.c Advantages of VALLME and applications 14 2.2.2 Crown ether- DtBuCH18C6 15 2.2.3 Sodium tetraphenylborate 18 2.2.4.Ion Chromatography 20 2.2.4.a Ion Chromatography mechanism 20 2.2.4.b Ion chromatography system 21 PART III METHODS 26 3.1 Material 26 v 3.1.1 Chemical materials 26 3.1.2 Instrumentation 26 3.2 Methods 27 3.2.1 Micro-extraction procedure 27 3.2.2 Analysis 28 PART IV RESULTS 29 4.1 The effect of DtBuCH18C6 and TPB concentration to result of Strontium extraction.29 4.2 Calibration Curve 33 PART V DISCUSSION AND CONCLUSION 34 5.1 DISCUSSION 34 5.2 CONCLUSION 34 REFERENCE 35 vi LIST OF TABLES Table 2.1 The properties of strontium Table 2.2 Properties of 4’,4’’(5’’)-di-tert-butyldicyclohexano 18-crown-6 (DtBuCH18C6) (12)( en.wikipedia.org) 18 Table 2.3 Properties of sodium tetraphenylboron (NaTPB)(13 ) ( en.wikipedia.org) 19 Table 2.4 Function of parts in an IC system 23 vii LIST OF FIGURES Figure.2.1 Applications of VALLME procedure in real samples (C Bosch Ojeda ,F Sánchez Rojas, 2014) 15 Figure 2.2 Ion Chromatography System Configuration 22 Figure 3.1 A vortex-assisted liquid–liquid microextraction process 27 Figure 4.1 The variance of Peak Area of Sr2+ when DtBuCH18C6 concentration is changed 29 Figure 4.2 The variance of Peak Area of Sr2+ when TPB concentration is changed 29 Figure 4.4 Effect of TPB concentration on the distribution coefficient of Sr 31 Figure 4.5 Effect of DtBuCH18C6 concentration on the distribution coefficient of Sr 31 Figure 4.6 Extraction of Sr as a function of DtBuCH18C6 concentration 32 Figure 4.7 Calibration Curve 33 viii LIST OF ABBREVIATIONS Aqueous Phase AP Distribution Coefficient D Aqueous Sample DP 4’,4’’(5’’)-Di-Tert-butyldicyclohexano 18-crown-6 DtBuCH18C6 Ion Chromatography IC Liquid–Liquid Microextraction LLE Strontium Sr Vortex-Assisted Liquid–Liquid Microextraction VALLME ix PART III METHODS 3.1 Material 3.1.1 Chemical materials o Deionized water (DIW) o Acid nitric (HNO3) o 1-octanol (99%) o Crown ether (90%) (4’,4”(5”)-di-tert-butyl-dicyclo-hexano 18-crown-6) o Sodium tetra-phenyl-borate (TPB) C24H20BNa o Strontium ion (Sr2+) o All solution were diluted by deionized water 3.1.2 Instrumentation o LABNET VX100 Vortex Mixer S0100 Rotator o Plastic tubes (vial-1.5ml and 2ml) o Glasses tubes (vial-2ml, 20ml,50ml and 100ml) o Beckman Coulter Microfuge 18 Centrifuge machine o Scale o Pipets o DX 120 Ion chromatography machine o Silver paper o Computer ( Excel and OriginPro applications ) 26 3.2 Methods 3.2.1 Micro-extraction procedure Figure 3.1 : A vortex-assisted liquid–liquid microextraction process The process is practiced in unlighted condition at room temperature Step 1: Tubes is covered by silver paper A 1.4 mL of sample solution containing strontium ppm and TPB (x) mM in water was delivered to 2.0 mL conical bottomed tube, then 200 μL of 1-octanol containing (y) mM DtBuCH18C6 were injected Step 2: The tube was sealed by a snap cap and shaken by hand for 10 s The mixture was then vigorously stirred using a vortex agitator (LABNET VX100 Vortex Mixer S0100 Rotator) at 3000 rpm for 10 s before it is separated to two phases by centrifuging (Coulter Microfuge 18 Centrifuge) at 6000rpm for 27 Step 3: The aqueous phase was removed so that 120 μL of organic phase could be withdrawn and transferred into a 1.5-mL Eppendorf Safe-Lock micro-centrifuge tube Step 4: Back-extraction (stripping) was accomplished by adding 60 μL of 0.1 M nitric acid into the organic phase The mixture was shaken by hand for 10 s and then vigorously stirred using a vortex agitator for Step 5: The two phases were separated by centrifuging the mixture at 6000 rpm for Step 6: The aqueous phase containing strontium was collected with 50 μL and diluted to 200 μL with water before analysis Value x,y, are changed at each detail sample 3.2.2 Analysis Quantification of strontium was conducted with a DionexDX120 IC (Thermo Scientific, Sunnyvale, CA) The analytical columns were adopted in this study: and a Dionex Ion Pac CS16 (250 mM × mM) for waters sample analysis Both were operated at 25◦C under isocratic conditions with 30 mM methanesulfonic acid (CH3SO3H) as mobile phase The flow rate was set at 1.0 mL/min On chromatography analysis, peak area of strontium was illustrated last, the reason is that strontium has the biggest between 13rd -14th minute with: a Dionex Ion-Pac CS12A (250 mM × mM) and 23rd – 26 th with Dionex Ion Pac CS16 (250 mM × mM) Because size of CS 16 is bigger than CS 12A, the machine need more time to determine strontium when uses the Dionex IonPac CS16 28 PART IV RESULTS 4.1 The effect of DtBuCH18C6 and TPB concentration to result of Strontium extraction Figure 4.1 : The variance of Peak Area of Sr2+ when DtBuCH18C6 concentration is changed Figure 4.2: The variance of Peak Area of Sr2+ when TPB concentration is changed 29 Base on the figure 4.1, it is clear that the value of Peak Area received when the concentration of TPB is mM always is higher than that when the concentration of TPB is 5mM at all sample with different DtBuCH18C6 concentration Moreover, with the both TPB concentration, Peak Area has the highest value when the DtBuCH18C6 concentration in the rang from 1mM to 10 mM Base on the figure 4.3, with Log[ TPB]= - 4,25 and [DtBuCH18C6]= 0,01 M in aqua phase and organic phase respectively, the Recovery of Sr extraction reach the highest percentage at 79% what is calculated by formula : Rate = 100 [DtBuCH18C6] 0.01M 60 40 Extraction of Sr, % 80 20 -5.50 -5.25 -5.00 -4.75 -4.50 -4.25 -4.00 -3.75 Log[TPB] Figure 4.3 Extraction of Sr as a function of TPB concentration 30 1.4 [DtBuCH18C6] 0.01M 1.2 1.0 Log DSr 0.8 0.6 0.4 0.2 0.0 -5.4 -5.2 -5.0 -4.8 -4.6 -4.4 -4.2 Log [TPB] Figure 4.4 Effect of TPB concentration on the distribution coefficient of Sr According to the figure 4.4, LogD versus log[TPB] at a fix of concentration of DtBuCH18C6 = 0,01M give the slope=1,02 And the distribution coefficient reach the highest value at LogD=1,22 commensurate with log[TPB]= -4,26 100 [TPB] 0.003M 60 40 Extraction of Sr, % 80 20 -4.5 -4.0 -3.5 -3.0 -2.5 -2.0 -1.5 -1.0 Log [DtBuCH18C6] Figure 4.5 Extraction of Sr as a function of DtBuCH18C6 concentration 31 Simultaneous, according to the figure 4.5, with Log[DtBuCH18C6]= - 2,6 and [TPB]= 0,003 M in aqua phase and organic phase respectively, the Recovery of Sr extraction reach the highest percentage at 79% From figure 4.3 and figure 4.5, in this method, [DtBuCH18C6] =0,01 M and [TPB] = 0,003 in aqua phase and organic phase respectively is optimal concentration to obtain the highest recovery of Sr Extraction That is reason why we choose this concentration to study the mechanism of VALLME method of strontium 0.5 [TPB] 0.003M Log DSr 0.0 -0.5 -1.0 -1.5 -4.5 -4.0 -3.5 -3.0 -2.5 -2.0 Log [DtBuCH18C6] Figure 4.6: Effect of DtBuCH18C6 concentration on the distribution coefficient of Sr According to the figure 4.6, LogD versus log[DtBuCH18C6] at a fix of concentration of [TPB]= 0,003M give the slope=0,67 And the distribution coefficient reach the highest value at LogD=0,32 commensurate with log[DtBuCH18C6]= -2,66 32 4.2 Calibration Curve 90 With VALLME Without VALLME 80 y = 75.14x - 0.9875 R² = 0.9723 Peak Area (S x Sec) 70 60 50 40 30 y = 29.579x + 0.2138 R² = 0.9996 20 10 0 500 1000 Sr 2+ 1500 2000 Concentration (ppb) Figure 4.7 Calibration Curve Base on the figure 4.7, a calibration Curve of signal which is applied VALLME method is and correlation coefficient R2 = 0,9723 and a calibration Curve of signal which is not applied VALLME method is and correlation coefficient R2 =0,9996 Compare the slope of the curve and correlation coefficient of this method, the result of relative error at signal with VALLME and without VALLME respectively 2.27% and 0.04% Both of that are suitable to extract Sr in water sample However to support of VALLME and it’s advantages we need prepare more experiment with other concentration of Sr and developed that with some technique to analysis the result 33 PART V DISCUSSION AND CONCLUSION 5.1 DISCUSSIONS In this study, Vortex-assisted liquid–liquid micro-extraction is proved that it is the efficient method to extract Sr in water sample, according to figure 4.7 Moreover using this method with the ratio between organic phase and aqua phase 1:7 and the optimum conditions is [DtBuCH18C6]= 10mM and [TPB] =3 mM, the result is sensitive with the recovery = 79, % and the relative error = 2,27% The experiments should be implement with more concentration of TPB and DtBuCH18C6 to discover the accurate optimum conditions for the extraction By comparing the Calibration Curve between with VALLME and without VALLME and result of relative error from the two treatment, VALLME is totally dominant method although it is having higher relative error 5.2 CONCLUSION As the result, Vortex-assisted liquid–liquid micro-extraction is the efficient method to extract Sr in water sample experiment this method with the ratio between organic phase and aqua phase :7 The optimum conditions is [DtBuCH18C6]= 10mM and [TPB] =3 mM with the Recovery = 79,00 % and the relative error = 2,27% 34 REFERENCE Agency for toxic substances and disease registry (ATSDR) Toxicological profile for strontium: U.S Department of Health and Human Services, Public Health Service, Atlanta, GA 2000 Agency for toxic substances and disease registry (ATSDR) Toxicological profile for strontium: U.S Department of Health and Human Services, Public Health Service, Atlanta, GA 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A1, Yap HF2, Saad B3 Vortex-assisted liquid-liquid-liquid microextraction (VALLLME) technique: A new microextraction approach for direct liquid chromatography and capillary electrophoresis analysis 2015 Oct 1;143:394-401 R M Washburn, F A Billig, "Tetraarylboron Compounds"US Patent 3,311,662 Ulrich Behrens, Frank Hoffmann, and Falk Olbrich (2012) "Solid-State Structures of Base-Free Lithium and Sodium Tetraphenylborates at Room and Low Temperature: Comparison with the Higher Homologues MB(C6H5)4 (M = K, Rb, Cs)" Organometallics, volume 31, p 905−913 Ying R Extraction and Analysis of Strontium in Water Sample Using a Sr2+Selective Polymer as the Absorbent Phase International Journal of Analytical Chemistry (2015) 37 Internet source https://www.lenntech.com/periodic/elements/sr.htm accessed on 27/07/2018 https://en.wikipedia.org/wiki/Sodium_tetraphenylborate(accessed on 20/07/2018) https://slideplayer.com/slide/6819607/ accessed on 15/08/2018 https://slideplayer.com/slide/6819607/ 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422546 40 190972,8 280601,7 39 Change the concentration of DtBuCH18C6in Organic phase Average Peak Area Average Peak Area Concentration of (mS x Sec) Standard (mS x Sec) with Standard Crown Ether with 5mM TPB Deviation 3mM TPB Deviation 0,01 389230,7 127657,5 467178,9 0,05 462375,8 534562,1 0,1 571283,6 580368,7 110984 601537,1 557839,4 636677,6 103535,1 578791,2 513539,2 537038,9 70419 10 651566,5 700006,4 72919,66 20 427343,6 752950,6 587511,3 91811,73 50 287021,8 463133,6 100 162804,3 207463,7 337224,9 55956,05 40 ... part of the strontium found in water is from the settling of strontium dust out of the air Some strontium is suspended in water Typically, the amount of strontium that has been measured in drinking... vortex- assisted liquid- liquid microextraction of Strontium in water sample - Prof Wu ,Chien-Hou - Prof Nguyen The Hung Supervisor’s Signature Abstract: A vortex- assisted liquid? ? ?liquid microextraction. .. primarily from the settling of 90Sr dust out of the air Some 90Sr is suspended in water In general, the amount of 90Sr that has been measured in drinking water in different parts of the United States