Title: Slajd 1
1Application of green sample preparation
techniques for the isolation, preconcentration
and gas chromatographic determination of organic
environmental pollutants
Spietelun Agata1, Marcinkowski Lukasz1,
Kloskowski Adam1, Namiesnik Jacek2 1Department
of Physical Chemistry, Chemical Faculty
2Department of Analytical Chemistry, Chemical
Faculty Gdansk University of Technology, 80-233
Gdansk, 11/12 G. Narutowicza St.,
Poland chemanal_at_pg.gda.pl
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
2FURTHER CHALLENGES OF ANALYTICAL CHEMISTRY
accurately monitoring the state of the
environment and the processes taking place in
it determining an wide range of analytes, often
present in trace and ultratrace amounts in
sample matrices with complex or variable
compositions need to introduce to analytical
practice new methodologies and equipment in order
to comply with the principles of sustainable
development and green chemistry
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
3(SHORT HISTORY)
GREEN CHEMISTRY
2003 1997 1996 1995 1993 1991 1987
the first national conference devoted to GREEN
CHEMISTRY took place in Poland EkoChemTech03
the GREEN CHEMISTRY INSTITUTE (EPA) came into
being in the USA. It fosters contacts between
governmental agencies and industrial corporations
on the one hand, and university research centres
on the other
the first international GREEN CHEMISTRY symposium
took place
IUPAC Working Party on Green Chemistry founded
an annual award was established for achievements
in the application of GREEN CHEMISTRY principles
Office of Pollution Prevention and Toxics
launched a research grants program called
Alternative Synthetic Pathways for Pollution
Prevention Paul Anastas coined the term GREEN
CHEMISTRY
Green Chemistry Program was inaugurated by the US
EPA
Our Common Future, also known as the Brundtland
Report, from the United Nations World Commission
on Environment and Development (WCED) was
published
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
4GREEN CHEMISTRY
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.)
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
5GREEN CHEMISTRY
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)
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
Curriculum http//www.chemistshelpingchemists.org/
GreenAnalyticalMethodologyCurriculum.ppt257,2,Cur
riculum
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
6 6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
7KNOWN TYPES OF DIRECT TECHNIQUES OF MEASUREMENT
- 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)
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
8MILESTONES IN GREEN ANALYTICAL CHEMISTRY
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 - SPME Development 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. Namiesnik) Development of stir bar sorptive extraction- SBSE
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
9NEW 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-polar constituents
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(e) 1-2 10-80
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
10NEW 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
11INTERESTING AND PROMISING PROPERTIES OF IONIC
LIQUIDS
- 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 25C)
- high electrical conductance, wide
electrochemical windows - dissolve catalysts, especially complexes of
transition metals without damaging the walls of
glass or steel reactors
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
12SOLVENT-FREE SAMPLE PREPARATION TECHNIQUES
- Sample preparation - most critical step of the
whole analytical protocole - NO SAMPLE PRETREATMENT BEFORE ANALYSIS NECESSARY
- AN IDEAL SOLUTION
- BUT only a limited number of such techniques!
preconcentration of the analytes to a level above
the limit of detection of the measuring/monitorin
g 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
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
13CLASSIFICATION OF SOLVENT-FREE SAMPLE PREPARATION
TECHNIQUES
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 techniques with 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 dosimetersthermal
desorption
Supercritical Fluid Extraction
C. W. Huie, Anal. Bioanal. Chem. 373, (2002), 23.
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
14MICROEXTRACTION TECHNIQUES
- Liquid phase microextraction techniques
- SDME (Single Drop Microextraction)
- HF-LPME (Hollow Fibre Liquid-Phase
Microextraction) - DLLME (Dispersive Liquid-Liquid Microextraction)
- SM-LLME (Stir Membrane LiquidLiquid
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)
C. W. Huie, Anal. Bioanal. Chem. 373, (2002), 23.
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
15SINGLE DROP MICROEXTRACTION (SDME)
Drop volume 1 8mL
- 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
G. Liu, P.K. Dasgupta, Anal. Chem. 68 (1996) 1817
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
16HOLLOW FIBER LIQUD-PHASE MICROEXTRACTION
(HF-LPME)
- Inexpensive, simple, clean-up
- Possibility of automation
- Compatible with GC, HPLC, CE
- High versatility and selectivity
- Headspace/immersion mode
- Possibility of n-situ derivatization
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)
S. Pedersen-Bjergaard, K.E. Rasmussen, Anal.
Chem. 71 (1999) 2650.
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
17ADVANCES IN HF-LPME TECHNIQUE
- Hollow Fiber-Protected Ionic Liquid supported
three-phase - (LiquidLiquidLiquid) Microextraction
(HFM-LLLME) - Hollow Fiber SolidLiquid 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
18SDME MODES
CONTINOUS FLOW
DI-SDME HS-SDME
W. Liu, H.K. Lee, Anal. Chem., 72 (2000), 4462
L. Xu, C. Basheer, H.K. Lee. J. Chromatog. A,
1152 (2007), 184
LLLME
DROP-TO-DROP
H.F. Wu, J.H. Yen, C.C. Chin, Anal. Chem., 78
(2006) 1707
M. Ma, F.F. Cantwell, Anal. Chem., 70 (1998), p.
3912
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
19DROPLET-MEMBRANE-DROPLET-LPME (DMD-LPME)
- 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
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
20SOLIDIFICATION OF FLOATING ORGANIC DROP
MICROEXTRACTION (SFOD/SFOME)
- Physical and chemical properties
- of solvents for SFOME
- immiscible with water
- low volatility
- low density
- able to extract analytes
M.R.K. Zanjani, Y. Yamini, S. Shariati, J.Å .
Jönsson, Anal. Chim.Acta, 585 (2007) 286
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
21ELECTRO MEMBRANE ISOLATION (EMI) ELECTRO MEMBRANE
EXTRACTION (EME)
On chip- EME
S. Pedersen-Bjergaard, K.E. Rasmussen, J.
Chromatogr., A 1109 (2006) 183.
M. D. Ramos Payán, H. Jensen, N. J. Petersen, S.
H. Hansen, S. Pedersen-Bjergaard, Anal. Chim.
Acta, 735 (2012) 46
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
22DISPERSIVE 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, fast
- Easy to operate
- Possibility of automation
- Enormous contact area between acceptor phase and
sample - Compatible with GC, HPLC, CE, UV-vis
spectrometry - Fast extraction kinetics
- High 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
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23 6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
24STIR BAR SORTPIVE EXTRACTION (SBSE)
- Rapid, simple, solvent-free
- Sensitive and effective extraction
- Compatible with GC, HPLC, CE
- Headspace and immersion modes
- High thermal and chemical stability of stir bar
coatings
- 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
-
E. Baltussen, H. G. Janssen, P. Sandra, C. A.
Cramers, J. High. Resolut. Chromatogr., 20 (1997)
385
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
25STIR CAKE SORPTIVE EXTRACTION (SCSE)
Fig. X. Huang, L. Chen, F Lin, D. Yuan, J. Sep.
Sci., 34 (2011) 2145
- Combines the advantages of stirring with the high
absorption capacity - of the monolithic material
-
- high availability
- preparation simplicity
- low cost
- excellent longevity of monolithic cakes
(lifetime more than 1000h) - very versatile approach, broad applicability
- good extraction results
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
26MICRO SOLID-PHASE EXTRACTION (µSPE)
- Inexpensive, simple, clean-up
- Conveniently applicable
- Easy to be manipulated
- Compatible with GC, HPLC
- Headspace and immersion modes
- Sufficient sensitivity,
- Good reproducibility
- Excellent enrichment
- 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 -
C. Basheer, A. A. Alnedhary,B. S. M. Rao, S.
Valliyaveettil, H. K. Lee, Anal. Chem., 78 (2006)
2853
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
27ADSORPTIVE µ-EXTRACTION (AµE)
- Modes
- bar adsorptive µ- extraction (BaµE)
- multi-spheres adsorptive µ-extraction (MSAµE)
- cost-effective
- easy to work-up
- devices are easy to prepare
- robustness and good µ-extraction efficiency
- demonstrating to be a remarkable analytical tool
for trace analysis - presents the advantage to tune the most suitable
sorbent - to each specific type of application
N.R. Neng, A.R.M. Silva, J.M.F. Nogueira, J.
Chromatogr. A, 1217 (2010) 7303
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
28APPLICATION OF NANOPARTICLES IN NANOEXTRACTION
TECHNIQUES
VARIANT I VARIANT II Solid-phase
nanoextraction(SPNE)
Y. Zhu, S. Zhang, Y. Tang, M. Guo, C. Jin, T. Qi,
J Solid State Electrochem, 14 (2010) 1609.
H. Wang, A. D. Campiglia, Anal. Chem., 80 (2008)
8202
29SOLID PHASE MICROEXTRACTION (SPME)
- 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
- Plunger
- Barrel
- Injection needle
- Inner needle
- Coated fused silica fiber
C. L. Arthur, J. Pawliszyn, Anal. Chem., 62
(1990) 2145
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
30PRINCIPLES OF SPME
1. direct-immersion SPME 2. headspace-SPME
- Operation steps
- Immersion of the needle in the sample
- Exposition of the fiber
- Extraction of an analytes
- Retraction of the fiber
- Introduction of the fiber to injection port
- Desorption of analytes
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
31MILESTONES 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 by heating 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
32 6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
33COMMERCIAL 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
34ABSORPTION VS ADSORPTION
- ADSORPTION
- artefact formation
- incomplete desorption
- strong catalytic interactions
- of trapped analytes with adsorbents
- ABSORTION
- analytes are retained by dissolution
- analytes can be desorbed at moderate temperatures
- analyte decomposition can be ruled out
- non-specific interactions between analyte and
sorbent
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
35LIQUIDLIQUIDSOLID MICROEXTRACTION (LLSME)
- simple
- exciting low-cost
- environment-friendly
- negligible organic solvent consumption
- enhanced efficiency
- high 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
36ELECTROSORPTION ENHANCED SPME (EE-SPME)
- simple, fast, sensitive
- good performance
- short adsorption time
- wide linear range
- low detection limit
- high recoveries
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
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
37MEMBRANE-SPME (M-SPME)
1) silica fiber 2) coating of polyethylene
glycol (PEG) 3) coating of polydimethylsiloxane
(PDMS)
Inner coating Outer coating
Absorbent material PEG PDMS
Average thickness of coating 40-50µm 100-110µm
Length of sorbent coating 1cm 1,2 cm
The role of sorbent coating very polar retaining medium hydrophobic, nonpolar membrane
A. Kloskowski, M. Pilarczyk, J. Namiesnik, Anal.
Chem., 81 (2009) 7363.
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
38M-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 retention partitioning
mechanism of the extraction
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
39Determination of phenols using M-SPME and GC
Compound Linearity range (µg/L) R2 LOD (µg/L) LOD (µg/L)
Compound Linearity range (µg/L) R2 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
A. Kloskowski, M. Pilarczyk, J. Namiesnik, Anal.
Chem., 81 (2009) 7363
40Determination of VOCs using M-SPME and GC
Compound R2 R2 LOD (mg/L) LOD (mg/L) RSD () RSD ()
Compound M-SPME DVB/CAR /PDMS M-SPME DVB/CAR /PDMS M-SPME DVB/CAR /PDMS
chlorobenzene 0.997 0.994 0.031 0.016 11 9
p-xylene 0.992 0.986 0.022 0.015 9 6
o-xylene 0.986 0.994 0.018 0.014 12 7
isopropylbenzene 0.994 0.995 0.015 0.018 12 8
n-propylbenzene 0.998 0.997 0.013 0.017 14 10
2-chlorotoluene 0.997 0.993 0.016 0.019 8 6
4-chlorotoluene 0.995 0.995 0.017 0.018 10 6
t-butylbenzene 0.997 0.985 0.011 0.021 12 8
sec-butylbenzene 0.987 0.992 0.011 0.021 11 8
1,3-dichlorobenzene 0.989 0.998 0.017 0.017 14 10
1,4-dichlorobenzene 0.994 0.987 0.017 0.023 13 7
1,2-dichlorobenzene 0.986 0.988 0.016 0.028 13 7
41M-SPME conclusion
partitioning 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 final quantitative
determination of analytes on the ppb level
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
42evaluation of environmental impact of analytical
procedures
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/
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
43Analytical Eco-Scale
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 gt75 excellent green
analysis gt50 acceptable green analysis lt50
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 Galuszka A.,
Konieczka P., Migaszewski Z.M., Namiesnik J.
2012. Analytical Eco-Scale for assessing the
greenness of analytical procedures. Trends in
Analytical Chemistry 37, 6172.
6th Shanghai International Symposium on
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44The penalty points (PPs) to calculate analytical
Eco-Scale
REAGENTS REAGENTS REAGENTS REAGENTS REAGENTS
Subtotal PP Subtotal PP Total PP
Amount lt10 mL (g) 1 1 Amount PP?Hazard PP
Amount 10-100 mL (g) 2 2 Amount PP?Hazard PP
Amount gt100 mL (g) 3 3 Amount PP?Hazard PP
Hazard (physical, environmental, health) None 0 0 Amount PP?Hazard PP
Hazard (physical, environmental, health) Less severe hazard 1 1 Amount PP?Hazard PP
Hazard (physical, environmental, health) More severe hazard 2 2 Amount PP?Hazard PP
INSTRUMENTS INSTRUMENTS INSTRUMENTS INSTRUMENTS INSTRUMENTS
Energy 0.1 kWh per sample 0.1 kWh per sample 0
Energy 1.5 kWh per sample 1.5 kWh per sample 1
Energy gt1.5 kWh per sample gt1.5 kWh per sample 2
Occupational hazard Analytical process hermetization Analytical process hermetization 0
Occupational hazard Emission of vapors and gases to the air Emission of vapors and gases to the air 3
Waste None None 0
Waste lt1 mL (g) lt1 mL (g) 1
Waste 1-10 mL (g) 1-10 mL (g) 3
Waste gt10 mL (g) gt10 mL (g) 5
Waste Recycling Degradation Passivation No treatment Recycling Degradation Passivation No treatment 0 1 2 3
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
45DEPARTMENT OF ANALYTICAL CHEMISTRY CHEMICAL
FACULTYGDANSK UNIVERSITY OF TECHNOLOGY
This lecture can also be found on the homepage
of the Department of Analytical
Chemistry http//www.pg.gda.pl/chem/Katedry/Analit
yczna/analit.html
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
46EUROPEAN MASTER IN QUALITY IN ANALYTICAL
LABORATORIES- EMQAL
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
47MODAS
- 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/
47
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
48(No Transcript)
49MEMBERS OF MY RESEARCH GROUP
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai
50THANK YOU FOR YOUR ATTENTION!
6th Shanghai International Symposium on
Analytical Chemistry, 16-18.10.2012, Shanghai