Application of green sample preparation techniques for the ... · techniques for the isolation,...
Transcript of Application of green sample preparation techniques for the ... · techniques for the isolation,...
Application of green sample preparation techniques for the isolation, preconcentration
and gas chromatographic determination of organic environmental pollutants
Spietelun Agata1, Marcinkowski Łukasz1, Kloskowski Adam1, Namieśnik Jacek2
1Department of Physical Chemistry, Chemical Faculty 2Department of Analytical Chemistry, Chemical Faculty
Gdańsk University of Technology, 80-233 Gdansk, 11/12 G. Narutowicza St., Poland
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
accurately monitoring the state of the environmentand the processes taking place in it
determining an wide range of analytes, often presentin trace and ultratrace amounts in sample matriceswith complex or variable compositions
need to introduce to analytical practice newmethodologies and equipment in order to complywith the principles of sustainable developmentand green chemistry
FURTHER CHALLENGES OF ANALYTICAL CHEMISTRY
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
2003
1997
1996
1995
1993
1991
1987
Office of Pollution Prevention and Toxicslaunched a research grants program called Alternative Synthetic Pathways for Pollution Prevention
Paul Anastas coined the term GREEN CHEMISTRY
an annual award was established for achievements in the application of GREEN CHEMISTRY principles
IUPAC Working Party on Green Chemistryfounded
the GREEN CHEMISTRY INSTITUTE (EPA)came into being in the USA. It fosters contactsbetween governmental agencies and industrialcorporations on the one hand, and universityresearch centres on the other
the first international GREEN CHEMISTRY symposium took place
the first national conference devoted to GREEN CHEMISTRY took place in Poland – EkoChemTech’03
GREEN CHEMISTRY (SHORT HISTORY)
Our Common Future, also known as theBrundtland Report, from the United NationsWorld Commission on Environment andDevelopment (WCED) was published
Green Chemistry Program was inauguratedby the US EPA
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
PRINCIPLES of GREEN CHEMISTRY(P.T. Anastas, J. Warner, Green Chemistry.Theory and Practice, Oxford University Press,New York, 1998, p. 30)
PRINCIPLES of GREEN CHEMICAL TECHNOLOGY(N. Winterton, Green Chem., 3 (2001) G73)
PRINCIPLES of GREEN CHEMICAL ENGINEERING(P.T. Anastas, J.B. Zimmerman, Environ. Sci.Technol., 37 (2003) 94A-101A.)
GREEN CHEMISTRY
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
GREEN CHEMISTRY
GREEN ANALYTICAL CHEMISTRY-GAC
‘The use of analytical chemistry techniques and methodologies that reduce or eliminate solvents, reagents, preservatives, and other
chemicals that are hazardous to human health or the environment and that also may enable faster and more energy efficient analyses
without compromising required performance criteria’
H. K. Lawrence, Green Analytical Methodology Curriculumhttp://www.chemistshelpingchemists.org/GreenAnalyticalMethodologyCurriculum.ppt#257,2,Curriculum
‘Green chemistry, is the invention, design and application of chemical products and processes to reduce or to eliminate the use and
generation of hazardous substances’
P. T. Anastas, J. C. Warner, Green Chemistry: Theory and Praktice. Oxford Science Publications, Oxford (1998)
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
Potentiometric techniques (ion-selective electrodes- ISE)
Flameless atomic absorption spectrometry (FAAS)
Inductively coupled plasma emission spectrometry (ICP)
Neutron activation analysis (NAA)
X-ray fluorescence spectrometry (XRF)
Surface analysis techniques (AES, ESCA, SIMS, ISS)
Immunoassay (IMA)
KNOWN TYPES OF DIRECT TECHNIQUES OF MEASUREMENT
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
1974 Development of flow injection analysis - FIA
1974 Development of purge-and-trap technique - PT
1976 Development of solid phase extraction - SPE
1978 Development of cloud point extraction - CPE
1985 Development of microwave-assisted extraction - MAE Development of supercritical fluid extraction - SFE
1987 The concept of ecological chemistry (H. Malissa)The concept of sustainable development
1990 Development of solid-phase microextraction - SPMEDevelopment of micro total analysis system - µTAS
1993 Development of molecularly imprinted solid-phase extraction - MIMSPE
1995 The concept of environmentally friendly analytical chemistry (M. de la Guardia, J. Ruzicka)
1996 Development of presurized solvent extraction - PSE Development of liquid phase micro extraction - LPME Development of single drop microextration -SDME
1999 The concept of green chemistry (P.T. Anastas)The concept of clean analytical method ( M. de la Guardia)The concept of green analytical chemistry ( J. Namieśnik) Development of stir bar sorptive extraction- SBSE
MILESTONES IN GREEN ANALYTICAL CHEMISTRY
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
NEW EXTRACTION MEDIA GREEN SOLVENTS
Parameter Supercritical CO2 Supercritical H2O
Analyte solubility can be changed 10-100 times 50-1000000 times
Extractable analytes polar constituents non-polarconstituents
Easily extractable analytes non-polar constituents polar constituents
Analyte reactivity low low-average
Analyte preconcentration(after extraction) usually easy variable level of difficulty
Selectivity of extraction of analytes of different polarity average good
Selectivity of extraction from samples with a given matrix composition
(e.g. soils)good poor
Range of analyte polarity(ε) 1-2 10-80
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
NEW EXTRACTION MEDIA GREEN SOLVENTS
IONIC LIQUIDS – SOLVENTS OF THE 21ST CENTURY
IS are salts containing:• an organic cation• an anion (usually inorganic)
Terminology• Room-temperature ionic liquid• Task specific ionic liquid• Neoteric solvents• Non-aqueous ionic liquid• Molten organic salt• Fused salt
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
• at room temperature these salts are liquids
• dissolve organic and inorganic compounds
• thermally stable
• high viscosity
• usually immiscible with water
• non-volatile (very low vapour pressure at 25°C)
• high electrical conductance, wide electrochemical windows
• dissolve catalysts, especially complexes of transition metals without damaging the walls of glass or steel reactors
INTERESTING AND PROMISING PROPERTIES OF IONIC LIQUIDS
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
SOLVENT-FREE SAMPLE PREPARATION TECHNIQUES
preconcentration of the analytes to a level above the limit of detection of the measuring/monitoring instrument
isolating the analytes from the original sample matrix and/or matrix simplification
removal of interferents and elimination of sample constituents being strongly adsorbed in the chromatographic column and thus accelerating its consumption
Sample preparation - most critical step of the whole analytical protocoleNO SAMPLE PRETREATMENT BEFORE ANALYSIS NECESSARY
AN IDEAL SOLUTION BUT only a limited number of such techniques!
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
CLASSIFICATION OF SOLVENT-FREE SAMPLE PREPARATION TECHNIQUES
Application of stream of inert gas as extractant
Static Headspace analysis (S-HS)
Dynamic Headspace (D-HS)
Cryotrapping (CT)
Solid phase extraction techniqueswith thermal desorption:
Purge and Trap (PT)
Closed Loop Stripping Analysis (CLSA)
Gum-Phase Extraction (GPE)
Inside Needle Dynamic Extraction (INDEX)
Inside Needle Capillary Absorption Trap (INCAT)
Stir Bar Sorptive Extraction (SBSE)
Headspace Sorptive Extraction (HHSE)
Open-Tubular Trapping (OTT)
Coated Capillary Microextraction (CCME)
Thick Film Open Tabular Trap (TFOT)
Thick Film Capillary Trap (TFCT)
Solid-Phase Microextraction (SPME)
Membrane extraction techniques
Membrane Inlet Mass Spectrometry (MMS)
Membrane Extraction with Sorbent Interface (MESI)
Hollow Fibre Sampling Analysis (HFSA)
On-line Membrane Extraction Microtrap (OLMEM)
Membrane Purge and Trap (MPT)
Pulse Introduction Membrane Extraction (PIME)
Semi Permeable Membrane Devices (SPMD)
Thermal Membrane Desorption Application (TMDA)
Passive permeation dosimeters+thermal desorption
Supercritical Fluid Extraction
SOLVENT-FREE SAMPLE PREPARATION TECHNIQUES
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C. W. Huie, Anal. Bioanal. Chem. 373, (2002), 23.
Liquid phase microextraction techniques:• SDME (Single Drop Microextraction)• HF-LPME (Hollow Fibre Liquid-Phase Microextraction)• DLLME (Dispersive Liquid-Liquid Microextraction)• SM-LLME (Stir Membrane Liquid–Liquid Microextraction)
Solid phase microextraction techniques:• SBSE (Stir Bar Sorptive Extraction)• μSPE (Micro Solid-Phase Extraction)• AμE (Adsorptive μ-Extraction)• SCSE (Stir Cake Sorptive Extraction)• SPNE (Solid-Phase Nano-Extraction) • SPME (Solid-Phase Microextraction)
MICROEXTRACTION TECHNIQUES
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
C. W. Huie, Anal. Bioanal. Chem. 373, (2002), 23.
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
SINGLE DROP MICROEXTRACTION(SDME)
• High selectivity• Low detection limits• Simple, fast, and easy• Minimal sample preparation• Can be automated with commercially available equipment• Possible application for trace water analysis
HMIM PF 6
OMIM PF6
HMIM NTf 2
DI-SDME HS-SDMEn -Hexane n -Octane
EXTRACTING SOLVENTS FOR SDME
IL-SDMEBMIM PF 6
n -Octaneiso-Octane
Cyclohexanen -Hexadecane
n -DecaneTetradecane
Ethylene glycol
ButylacetateDiisopropyl ether
Tolueneo -Xylene1-Octanol
Drop volume
1 – 8L
G. Liu, P.K. Dasgupta, Anal. Chem. 68 (1996) 1817
Fig. D. Han, K. H. Row, Microchim. Acta,176 (2012) 1
HF-LPME may be accomplished in:• three-phase mode (a)• two-phase mode (b)
HOLLOW FIBER LIQUD-PHASE MICROEXTRACTION
(HF-LPME)
Inexpensive, simple, clean-upPossibility of automationCompatible with GC, HPLC, CEHigh versatility and selectivity Headspace/immersion modePossibility of n-situ derivatization
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S. Pedersen-Bjergaard, K.E. Rasmussen, Anal. Chem. 71 (1999) 2650.
ADVANCES IN HF-LPME TECHNIQUE
Hollow Fiber-Protected Ionic Liquid supported three-phase (Liquid–Liquid–Liquid) Microextraction (HFM-LLLME)
Hollow Fiber Solid–Liquid Phase Microextraction (HF-SLPME)
Solvent Stir Bar Microextraction (SSBME)
dynamic-HF-LPME
Solvent Cooling Assisted Dynamic HF-LPME (SC-DHF-LPME)
Electro Membrane Extraction (EME)
on-chip EME
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
CONTINOUS FLOW
LLLME DROP-TO-DROP
DI-SDME HS-SDME
SDME MODES
H.F. Wu, J.H. Yen, C.C. Chin, Anal. Chem., 78 (2006) 1707M. Ma, F.F. Cantwell, Anal. Chem., 70 (1998), p. 3912
W. Liu, H.K. Lee, Anal. Chem., 72 (2000), 4462 L. Xu, C. Basheer, H.K. Lee. J. Chromatog. A, 1152 (2007), 184
DROPLET-MEMBRANE-DROPLET-LPME (DMD-LPME)
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• Reasonably high selectivity• Cheap (commercial propylene membrane)• No gluing or clamping process• Simple and easy• Minimal sample preparation
T. Sikanen, S. Pedersen-Bjergaard, H. Jensen, R. Kostiainen, K. E. Rasmussen, T. Kotiaho,Anal. Chim. Acta 658 (2010) 133
SOLIDIFICATION OF FLOATING ORGANIC DROP MICROEXTRACTION
(SFOD/SFOME)
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
Physical and chemical properties of solvents for SFOME:
• immiscible with water• low volatility• low density• able to extract analytes
1,10-Dichlorodecane
13-1522-2417-18
1814-16
1-Undecanol1-Dodecanol2-Dodecanol
n-Hexadecane
Common used solvents in SFOMEOrganic solvent Melting point (oC)
M.R.K. Zanjani, Y. Yamini, S. Shariati, J.Å . Jönsson, Anal. Chim.Acta, 585 (2007) 286
ELECTRO MEMBRANE ISOLATION (EMI) ELECTRO MEMBRANE EXTRACTION (EME)
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On chip- EME
M. D. Ramos Payán, H. Jensen, N. J. Petersen, S. H. Hansen, S. Pedersen-Bjergaard, Anal. Chim. Acta, 735 (2012) 46
S. Pedersen-Bjergaard, K.E. Rasmussen, J. Chromatogr., A 1109 (2006) 183.
DISPERSIVE LIQUD-LIQUID MICROEXTRACTION
(DLLME)
Fig. A. V. Herrera-Herrera, M. Asensio-Ramos, J. Hernández-Borges, M. Á. Rodríguez-Delgado, Trends Anal. Chem., 29 (2010) 728
Inexpensive, simple, fastEasy to operatePossibility of automation Enormous contact area between acceptor phase and sampleCompatible with GC, HPLC, CE, UV-vis spectrometryFast extraction kineticsHigh enrichment factor obtained
M. Rezaee, Y. Assadi, M.R.M. Hosseini, E. Aghaee, F. Ahmadi, S. Berijani, J. Chromatogr., A 1116 (2006) 1.
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
ADVANCES IN DLLME TECHNIQUE
SOLVENT DEMULSIFICATION DLLME
NEW EXTRACTION SOLVENTS
SOLVENT TERMINATED- DLLME
EXTRACTION SOLVENT LIGHTER THAN WATER
IONIC LIQUID
SPECIAL HOME-MADE EXTRACTION DEVICES
DLLME BASED ON THE SOLIDIFICATION OF A FLOATING ORGANIC DROP
COLD- INDUCED AGGREGATION MICROEXTRACTION (CIAME)
IN SITU SOLVENT-FORMATION MICROEXTRACTION (ISFME)
TEMPERATURE-CONTROLLED IONIC LIQUIDEXHAUSTIVELY DLLME (TILDLME)
SEQUENTIAL INJECTION–DLLME
LOW-DENSITY SOLVENT-BASED SOLVENT DEMULSIFICATION-DLLME
SURFACTANT-ASSISTED DLLME
COACERVATES AND REVERSE MICELLES
ULTRASOUND ASSISTED DLLME
VORTEX-ASSISTED DLLME
STIR BAR SORTPIVE EXTRACTION (SBSE)
Advances in SBSE technique: Application of poliurethane foams, PPESK,
alkyl-diolsilica RAM, silica materials, molecularly imprinted coatings, monoliths and sol-gel technique to prepare of stir bar coatings
Double-phase stir bar coatings
Rapid, simple, solvent-freeSensitive and effective extractionCompatible with GC, HPLC, CEHeadspace and immersion modesHigh thermal and chemical stability of stir bar coatings
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E. Baltussen, H. G. Janssen, P. Sandra, C. A. Cramers, J. High. Resolut. Chromatogr., 20 (1997) 385
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STIR „CAKE” SORPTIVE EXTRACTION (SCSE)
Combines the advantages of stirring with the high absorption capacity of the monolithic material
high availabilitypreparation simplicity low cost excellent longevity of monolithic cakes (lifetime more than 1000h)very versatile approach, broad applicabilitygood extraction results
Fig. X. Huang, L. Chen, F Lin, D. Yuan, J. Sep. Sci., 34 (2011) 2145
MICRO SOLID-PHASE EXTRACTION (µSPE)
Advances in (µSPE) technique: Application of mulberry paper bag, electrospun
composite of polyaniline-nylon-6 (PANI-N6) and electrospun composite of polypyrrole-polyamide (PP-PA) as sorbent sheet
Inexpensive, simple, clean-upConveniently applicableEasy to be manipulatedCompatible with GC, HPLCHeadspace and immersion modesSufficient sensitivity, Good reproducibilityExcellent enrichment
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C. Basheer, A. A. Alnedhary,B. S. M. Rao, S. Valliyaveettil, H. K. Lee, Anal. Chem., 78 (2006) 2853
ADSORPTIVE μ-EXTRACTION (AμE)
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Modes:•bar adsorptive μ- extraction (BaμE) •multi-spheres adsorptive μ-extraction (MSAμE)
cost-effectiveeasy to work-updevices are easy to prepare robustness and good μ-extraction efficiencydemonstrating to be a remarkable analytical tool for trace analysis presents the advantage to tune the most suitable sorbent
to each specific type of applicationN.R. Neng, A.R.M. Silva, J.M.F. Nogueira, J. Chromatogr. A, 1217 (2010) 7303
APPLICATION OF NANOPARTICLES IN NANOEXTRACTION TECHNIQUES
VARIANT I VARIANT II
Solid-phase nanoextraction(SPNE)
WATER SAMPLE MICRO-PLANE GLASS WITH Au NPs
SHAKING AND CENTRIFUGATION
COLLECT PRECIPITATE
SOLVENT ADDITION
SHAKING AND CENTRIFUGATION
SUPERNATANT COLLECTION
HPLC LETRESS
H. Wang, A. D. Campiglia, Anal. Chem., 80 (2008) 8202 Y. Zhu, S. Zhang, Y. Tang, M. Guo, C. Jin, T. Qi, J Solid State Electrochem, 14 (2010) 1609.
SOLID PHASE MICROEXTRACTION (SPME)
1. Plunger2. Barrel3. Injection needle4. Inner needle5. Coated fused silica fiber
simplicity of operation short extraction and desorption time solvent-free operation small size (convenient for designing portable devices) possibility of full automation direct linkup with a GC possibility to in-situ and in-vivo sampling
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C. L. Arthur, J. Pawliszyn, Anal. Chem., 62 (1990) 2145
1. direct-immersion SPME2. headspace-SPME
PRINCIPLES OF SPME
Operation steps:
1. Immersion of the needle in the sample
2. Exposition of the fiber
3. Extraction of an analytes
4. Retraction of the fiber
5. Introduction of the fiber to injection port
6. Desorption of analytes
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
MILESTONES IN THE DEVELOPMENT OF SPME
SOLID PHASE MICROEXTRACTION (SPME) first paper on concept of SPME 1990
HEADSPACE SPME (HS-SPME) - Analytes are sampled from headspace above the sample, particularly useful for analysing the composition of solid samples or samples containing matrix constituents and in the extraction of very volatile analytes
1993
COOLED COATED FIBRE SPME (CCF-SPME) - approach improving extraction efficiency byheating the sample and simultaneously cooling the SPME fiber. The temperature is easily controlled by cooling the fibre coating from the inside with a coolant and by altering the core diameter of the arrangement
1995
IN-TUBE SPME - the extraction phase is immobilized as the inner coating of the needle or part of the chromatographic column. Analytes are retained in the extraction medium during a few draw/eject cycles of the sample, or extraction takes place following a one-off filling of the needle
1997
FIBRE-IN-TUBE SPME - polymer core is inserted into the capillary of the in-tube SPME arrangement. The core reduces the capillary volume, but the surface area of the sorbent is not reduced
2000
SOLID-PHASE AROMA CONCENTRATE EXTRACTION (SPACE) - the SPACE rod is fabricated from stainless steel coated with an adsorbent mixture (mainly of graphite carbon) fixed on the head of a closed flask, where it adsorbs the aroma for a given time
2004
MEMBRANE-SPME (M-SPME) - physical separation of the two phases with a membrane impermeable to both of them or by immobilization of the extracting agent in the membrane pores
2009
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
ADVANCES IN SPME TECHNIQUE
AUTOMATION
NEW EXTRACTION PHASE
NEW DEVICES AND MODIFICATIONS
IONIC LIQUIDS
CARBON NANOTUBES AND GRAPHEN
SILICA MICROSTRUCTURES
MEMBRANE-SPME
LIQUID-LIQUID-SOLID MICROEXTRACTION
ELECTROSORPTION ENHANCED-SPME
COMMERCIAL SPME FIBERS
limited choice high cost poor selectivity for polar analytes some fiber coating have active adsorption centers-
possibility of competing of the matrix compounds with the analytes for available adsorbent sites need to high temperatures to be used to desorb the less
volatile compounds- can lead to degradation of the analytes, adsorbent materials and promote catalytic breakdown of the trapped analytes
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
ABSORPTION VS ADSORPTION
ADSORPTIONartefact formation incomplete desorption strong catalytic interactions
of trapped analytes with adsorbents
ABSORTIONanalytes are retained by dissolutionanalytes can be desorbed at moderate temperatures analyte decomposition can be ruled outnon-specific interactions between analyte and sorbent
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
LIQUID–LIQUID–SOLID MICROEXTRACTION (LLSME)
simpleexciting low-cost environment-friendly negligible organic solvent consumption enhanced efficiencyhigh selective and sensitive pretreatment
Y. Hu, Y. Wang, Y. Hu, G. Li, J. Chromatogr. A, 1216 (2009) 8304
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
ELECTROSORPTION ENHANCED SPME (EE-SPME)
simple, fast, sensitivegood performance short adsorption timewide linear rangelow detection limithigh recoveries
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
X. Chai, Y. He, D. Ying, J. Jia, T. Sun, J. Chromatogr. A, 1165 (2007) 26 Q. Li, Y. Ding, D. Yuan, Talanta 85 (2011) 1148
MEMBRANE-SPME (M-SPME)
1) silica fiber 2) coating of polyethylene glycol (PEG)3) coating of polydimethylsiloxane (PDMS)
Inner coating Outer coating
Absorbent material PEG PDMSAverage thickness of coating 40-50μm 100-110μmLength of sorbent coating 1cm 1,2 cm
The role of sorbent coating very polar retaining medium
hydrophobic, nonpolar membrane
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
A. Kloskowski, M. Pilarczyk, J. Namieśnik, Anal. Chem., 81 (2009) 7363.
M-SPME ADVANTAGES
low cost of fiber preparation
high thermal stability (PDMS is stable up to 300oC)
short extraction and desorption time
lack of water sorption (due to the presence of hydrophobic membrane)
high affinity to polar analytes
At the extraction temperature PEG of low molecular weight behaves as an immobilised liquid (viscous liquid polymer)
Analytes are retained by dissolution in the sorbent layer
absorption nature of the retentionpartitioning mechanism of the extraction
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
A. Kloskowski, M. Pilarczyk, J. Namieśnik, Anal. Chem., 81 (2009) 7363
Determination of phenols using M-SPME and GC
Compound Linearity range (µg/L) R2
LOD (µg/L)
M-SPME PA
4-Chloro-3-methylphenol 15-1500 0.9953 7 50
2-Chlorophenol 3-300 0.9936 43 530
2,4-Dichlorophenol 3-300 0.9987 15 120
2,4-Dimethylphenol 3-300 0.9921 9 110
2,4-Dinitrophenol 10-1000 0.9963 110 950
2-Methyl-4,6-dinitrophenol 15-1500 0.9898 81 680
2-Nitrophenol 3-300 0.9945 9 60
4-Nitrophenol 15-1500 0.9937 150 1800
Pentachlorophenol 15-1500 0.9914 83 740
2,4,6-Trichlorophenol 10-1000 0.9932 61 440
Compound
R2 LOD (mg/L) RSD (%)
M-SPME DVB/CAR/PDMS M-SPME DVB/CAR
/PDMS M-SPMEDVB/CA
R/PDMS
chlorobenzene 0.997 0.994 0.031 0.016 11 9p-xylene 0.992 0.986 0.022 0.015 9 6o-xylene 0.986 0.994 0.018 0.014 12 7
isopropylbenzene 0.994 0.995 0.015 0.018 12 8n-propylbenzene 0.998 0.997 0.013 0.017 14 102-chlorotoluene 0.997 0.993 0.016 0.019 8 64-chlorotoluene 0.995 0.995 0.017 0.018 10 6t-butylbenzene 0.997 0.985 0.011 0.021 12 8
sec-butylbenzene 0.987 0.992 0.011 0.021 11 81,3-dichlorobenzene 0.989 0.998 0.017 0.017 14 101,4-dichlorobenzene 0.994 0.987 0.017 0.023 13 71,2-dichlorobenzene 0.986 0.988 0.016 0.028 13 7
Determination of VOCs using M-SPME and GC
M-SPME conclusionpartitioning mechanism of the extraction, which is characterized by significantly higher linearity range when compared to commercial fibre
enabling highly polar sorbents to be used without the risk of dissolving in polar sample matrix
povides opportunity of application of quite new kinds of materials, which due to low melting temperatures or solubility in water have not been taken into consideration so far in this kind of applications
high extraction efficiency of phenols and VOCs obtainable with M-SPME fibres, comparable and better than the extraction efficiency using commercially available fibres
M-SPME combined with determination by GC may become a powerful, environmentally friendly tool for sampling, isolation and preconcentration of organic pollutants
• applicable on the sample preparation step prior to the finalquantitative determination of analytes on the ppb level
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
TOOLS:
Life Cycle Assessment (LCA)1
Eco- Scale2
Eco-Compass3
1 Consoli, F., D. Allen, R. Weston, I. Boustead, J. Fava, W. Franklin, A. Jensen, N. de Oude, R. Parrish, R. Perriman, D. Postlethwaite, B. Quay, J. Séguin and B. Vigon., ‘Guidelines for life cycle assessment: A ‘Code of practice’, SETAC, Brussels and Pensacola, 1993.
2 Aken K., L. Strekowski, L. Patiny, EcoScale, a semi-quantitative tool to select an organic preparation based on economical and ecological parameters, Beilstein J. Org. Chem. 2, 3, 2006.
3 “Home Sustainability Assessment”, http://www.ecocompass.com.au/
EVALUATION OF ENVIRONMENTALIMPACT OF ANALYTICAL PROCEDURES
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
A new tool for evaluation of the greenness of analytical methodology
Eco-Scale = 100 – total penalty points
The result is ranked on the following scale:>75 – excellent green analysis>50 – acceptable green analysis<50 – inadequate green analysis
Penalty points are assigned for amount of reagents, hazards (physical, environmental, health and occupational), energy used and waste generated in the analytical procedure
Gałuszka A., Konieczka P., Migaszewski Z.M., Namieśnik J. 2012. Analytical Eco-Scale for assessing the greenness of analytical procedures. Trends in Analytical Chemistry 37, 61–72.
ANALYTICAL ECO-SCALE
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
REAGENTSSubtotal PP Total PP
Amount<10 mL (g) 1
Amount PPHazard
PP
10-100 mL (g) 2>100 mL (g) 3
Hazard (physical, environmental, health)
None 0Less severe hazard 1More severe hazard 2
INSTRUMENTS
Energy≤0.1 kWh per sample 0
≤1.5 kWh per sample 1
>1.5 kWh per sample 2
Occupational hazard
Analytical process hermetization 0
Emission of vapors and gases to the air 3
Waste
None 0
<1 mL (g) 1
1-10 mL (g) 3
>10 mL (g) 5
RecyclingDegradation PassivationNo treatment
0123
THE PENALTY POINTS (PPS) TO CALCULATE ANALYTICAL ECO-SCALE
DEPARTMENT OF ANALYTICAL CHEMISTRYCHEMICAL FACULTY
GDANSK UNIVERSITY OF TECHNOLOGY
Department of Analytical Chemistry
This lecture can also be found on the homepageof the Department of Analytical Chemistry
http://www.pg.gda.pl/chem/Katedry/Analityczna/analit.html
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
EUROPEAN MASTER IN QUALITY IN ANALYTICAL LABORATORIES- EMQAL
http://eacea.ec.europa.eu/erasmus_mundus/
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
MODAS
„Production and attestation of new types of reference materials crucial for achieving
European accreditation for polish industrial laboratories ‐MODAS”
http://www.pg.gda.pl/chem/modas/
476th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
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MEMBERS OF MY RESEARCH GROUP
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
THANK YOU FOR YOUR ATTENTION!
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai