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
of Analytical Chemistry, Chemical Faculty
Gdańsk University of Technology,
80-233 Gdansk, 11/12 G. Narutowicza St., Poland
*[email protected]
2Department
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
FURTHER 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
(SHORT HISTORY)
GREEN CHEMISTRY
2003
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
IUPAC Working Party on Green Chemistry
founded
1997
Our Common Future, also known as the
Brundtland Report, from the United Nations
World Commission on Environment and
Development (WCED) was published
the first international GREEN CHEMISTRY
symposium took place
1996
1995
Green Chemistry Program was inaugurated
by the US EPA
the first national conference devoted to
GREEN CHEMISTRY took place in Poland
– EkoChemTech’03
an annual award was established for
achievements in the application of GREEN
CHEMISTRY principles
1991
Office of Pollution Prevention and Toxics
launched a research grants program called
Alternative Synthetic Pathways for Pollution
Prevention
1987
Paul Anastas coined the term
GREEN CHEMISTRY
1993
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
GREEN 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
GREEN 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.ppt#257,2,Curriculum
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
KNOWN 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
MILESTONES 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. Namieśnik)
Development of stir bar sorptive extraction- SBSE
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-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(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
INTERESTING 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 25°C)
• 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
SOLVENT-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/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
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
CLASSIFICATION OF SOLVENT-FREE
SAMPLE PREPARATION TECHNIQUES
SOLVENT-FREE SAMPLE PREPARATION TECHNIQUES
Application of stream
of inert gas as extractant
Solid phase extraction techniques
with thermal desorption:
Static Headspace analysis (S-HS)
Purge and Trap (PT)
Membrane Inlet Mass Spectrometry (MMS)
Dynamic Headspace (D-HS)
Closed Loop Stripping Analysis (CLSA)
Membrane Extraction with Sorbent Interface (MESI)
Cryotrapping (CT)
Gum-Phase Extraction (GPE)
Hollow Fibre Sampling Analysis (HFSA)
Inside Needle Dynamic Extraction (INDEX)
On-line Membrane Extraction Microtrap (OLMEM)
Inside Needle Capillary Absorption Trap (INCAT)
Membrane Purge and Trap (MPT)
Stir Bar Sorptive Extraction (SBSE)
Pulse Introduction Membrane Extraction (PIME)
Headspace Sorptive Extraction (HHSE)
Semi Permeable Membrane Devices (SPMD)
Open-Tubular Trapping (OTT)
Thermal Membrane Desorption Application (TMDA)
Coated Capillary Microextraction (CCME)
Passive permeation dosimeters+thermal desorption
Supercritical Fluid
Extraction
Membrane extraction techniques
Thick Film Open Tabular Trap (TFOT)
Thick Film Capillary Trap (TFCT)
Solid-Phase Microextraction (SPME)
C. W. Huie, Anal. Bioanal. Chem. 373, (2002), 23.
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
MICROEXTRACTION 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 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)
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)
EXTRACTING SOLVENTS FOR SDME
DI-SDME
HS-SDME
IL-SDME
n -Hexane
n -Octane
iso-Octane
Cyclohexane
n -Hexadecane
Butylacetate
Diisopropyl ether
n -Octane
n -Decane
Tetradecane
Ethylene glycol
Toluene
o -Xylene
1-Octanol
BMIM PF 6
HMIM PF 6
OMIM PF6
HMIM NTf 2
Drop volume
1 – 8L
• 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
HOLLOW 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
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
SDME MODES
CONTINOUS FLOW
W. Liu, H.K. Lee, Anal. Chem., 72 (2000), 4462
LLLME
M. Ma, F.F. Cantwell, Anal. Chem., 70 (1998), p. 3912
DI-SDME
HS-SDME
L. Xu, C. Basheer, H.K. Lee. J. Chromatog. A, 1152 (2007), 184
DROP-TO-DROP
H.F. Wu, J.H. Yen, C.C. Chin, Anal. Chem., 78 (2006) 1707
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
DROPLET-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
SOLIDIFICATION 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
Common used solvents in SFOME
o
Organic solvent
Melting point ( C)
1-Undecanol
13-15
1-Dodecanol
22-24
2-Dodecanol
17-18
n-Hexadecane
18
1,10-Dichlorodecane
14-16
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
ELECTRO 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
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, 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 Analytical Chemistry, 16-18.10.2012, Shanghai
ADVANCES IN DLLME TECHNIQUE
ULTRASOUND ASSISTED DLLME
VORTEX-ASSISTED DLLME
SURFACTANT-ASSISTED DLLME
SOLVENT DEMULSIFICATION DLLME
SOLVENT TERMINATED- DLLME
LOW-DENSITY SOLVENT-BASED SOLVENT
DEMULSIFICATION-DLLME
SEQUENTIAL INJECTION–DLLME
NEW EXTRACTION SOLVENTS
EXTRACTION SOLVENT
LIGHTER THAN WATER
SPECIAL HOME-MADE
EXTRACTION DEVICES
DLLME BASED ON THE SOLIDIFICATION OF A
FLOATING ORGANIC DROP
IONIC LIQUID
COLD- INDUCED AGGREGATION
MICROEXTRACTION (CIAME)
IN SITU SOLVENT-FORMATION
MICROEXTRACTION (ISFME)
TEMPERATURE-CONTROLLED IONIC LIQUID
EXHAUSTIVELY DLLME (TILDLME)
COACERVATES AND REVERSE MICELLES
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
STIR 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
STIR „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
MICRO 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
ADSORPTIVE 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
APPLICATION OF NANOPARTICLES
IN NANOEXTRACTION TECHNIQUES
MICRO-PLANE GLASS
WITH Au NPs
WATER SAMPLE
SHAKING AND
CENTRIFUGATION
COLLECT PRECIPITATE
SOLVENT ADDITION
SHAKING AND
CENTRIFUGATION
SUPERNATANT
COLLECTION
HPLC
LETRESS
VARIANT I
H. Wang, A. D. Campiglia, Anal. Chem., 80 (2008) 8202
VARIANT II
Y. Zhu, S. Zhang, Y. Tang, M. Guo, C. Jin, T. Qi,
J Solid State Electrochem, 14 (2010) 1609.
Solid-phase nanoextraction(SPNE)
SOLID 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
C. L. Arthur, J. Pawliszyn, Anal. Chem., 62 (1990) 2145
1.
2.
3.
4.
5.
Plunger
Barrel
Injection needle
Inner needle
Coated fused silica fiber
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
PRINCIPLES OF SPME
1. direct-immersion SPME
2. headspace-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 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
ADVANCES IN SPME
TECHNIQUE
AUTOMATION
NEW EXTRACTION PHASE
IONIC LIQUIDS
CARBON NANOTUBES AND GRAPHEN
SILICA MICROSTRUCTURES
NEW DEVICES AND MODIFICATIONS
MEMBRANE-SPME
LIQUID-LIQUID-SOLID
MICROEXTRACTION
ELECTROSORPTION ENHANCED-SPME
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
COMMERCIAL SPME FIBERS
 limited choice
 high cost
 poor selectivity for polar analytes
 some fiber coating have active adsorption centerspossibility 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
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
LIQUID–LIQUID–SOLID 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
ELECTROSORPTION 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
MEMBRANE-SPME (M-SPME)
1) silica fiber
2) coating of polyethylene glycol (PEG)
3) coating of polydimethylsiloxane (PDMS)
Inner coating
Outer coating
PEG
PDMS
40-50μm
100-110μm
Length of sorbent coating
1cm
1,2 cm
The role of sorbent coating
very polar
retaining medium
hydrophobic,
nonpolar membrane
Absorbent material
Average thickness of coating
A. Kloskowski, M. Pilarczyk, J. Namieśnik, Anal. Chem., 81 (2009) 7363.
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
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 retention
partitioning mechanism of the extraction
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
Determination of phenols
using M-SPME and GC
Linearity
range (µg/L)
R2
15-1500
2-Chlorophenol
Compound
LOD (µg/L)
M-SPME
PA
0.9953
7
50
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
4-Chloro-3-methylphenol
A. Kloskowski, M. Pilarczyk, J. Namieśnik, Anal. Chem., 81 (2009) 7363
Determination of VOCs
using M-SPME and GC
LOD (mg/L)
R2
Compound
M-SPME
DVB/CAR
/PDMS
M-SPME
DVB/CAR
/PDMS
chlorobenzene
p-xylene
o-xylene
isopropylbenzene
n-propylbenzene
2-chlorotoluene
4-chlorotoluene
t-butylbenzene
sec-butylbenzene
1,3-dichlorobenzene
1,4-dichlorobenzene
0.997
0.992
0.986
0.994
0.998
0.997
0.995
0.997
0.987
0.989
0.994
0.994
0.986
0.994
0.995
0.997
0.993
0.995
0.985
0.992
0.998
0.987
0.031
0.022
0.018
0.015
0.013
0.016
0.017
0.011
0.011
0.017
0.017
0.016
0.015
0.014
0.018
0.017
0.019
0.018
0.021
0.021
0.017
0.023
1,2-dichlorobenzene
0.986
0.988
0.016
0.028
RSD (%)
DVB/CA
M-SPME
R
/PDMS
11
9
9
6
12
7
12
8
14
10
8
6
10
6
12
8
11
8
14
10
13
7
13
7
M-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
EVALUATION OF ENVIRONMENTAL
IMPACT OF ANALYTICAL PROCEDURES
TOOLS:
Life Cycle Assessment (LCA)1
Eco- Scale2
Eco-Compass3
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.
1
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.
2
3 “Home
Sustainability Assessment”, http://www.ecocompass.com.au/
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
ANALYTICAL 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:
>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.
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
THE PENALTY POINTS (PPS) TO CALCULATE ANALYTICAL ECO-SCALE
REAGENTS
Amount
Hazard (physical,
environmental,
health)
<10 mL (g)
10-100 mL (g)
>100 mL (g)
None
Less severe hazard
More severe hazard
Subtotal PP
1
2
3
0
1
2
Total PP
Amount
PPHazard
PP
INSTRUMENTS
Energy
Occupational
hazard
Waste
≤0.1 kWh per sample
0
≤1.5 kWh per sample
1
>1.5 kWh per sample
2
Analytical process hermetization
0
Emission of vapors and gases to the air
3
None
0
<1 mL (g)
1
1-10 mL (g)
3
>10 mL (g)
5
Recycling
Degradation
Passivation
No treatment
0
1
2
3
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
DEPARTMENT OF ANALYTICAL CHEMISTRY
CHEMICAL FACULTY
GDANSK UNIVERSITY OF TECHNOLOGY
Department of
Analytical Chemistry
This lecture can also be found on the homepage
of 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/
6th Shanghai International Symposium on Analytical Chemistry, 16-18.10.2012, Shanghai
47
48
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