ACHIEVEMENTS IN GREEN SAMPLE PREPARATION FOR THE GAS ... i… · CHROMATOGAPHIC DETERMINANTION OF...

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ACHIEVEMENTS IN GREEN SAMPLE PREPARATION FOR THE GAS

CHROMATOGAPHIC DETERMINANTION OF ORGANIC ENVIRONMENTAL

POLLUTANTS

Agata Spietelun1, Adam Kloskowski1, Michał Pilarczyk1, Jacek Namieśnik2

1Department of Physical Chemistry2Department of Analytical Chemistry

Faculty of ChemistryGdańsk University of Technology

G. Narutowicza Str. 11/1280-233 Gdańsk, Poland

Tel: (058) 347 1010E-mail: [email protected]

Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia

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FURTHER CHALLENGES OF ANALYTICAL CHEMISTRY

accurately monitoring the state of the environment andthe processes taking place in it

determining an wide range of analytes, often present intrace and ultratrace amounts in sample matrices withcomplex or variable compositions

need to introduce to analytical practice newmethodologies and equipment in order to comply withthe principles of sustainable development and greenchemistry


2003

1997

1996

1995

1991

Paul Anastas coined the term GREENCHEMISTRY in the ‘Green ChemistryProgram’, inaugurated by the US EPA in1991

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)


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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, G 73 (2001))

PRINCIPLES of GREEN CHEMICAL ENGINEERING(P.T. Anastas, J.B. Zimmerman, Design through the Twelve

Principles of Green Engineering, Environ. Sci.Technol., 37,

5, 94A-101A, (2003).)


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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)


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PUBLICATIONS ON GREEN ANALYTICAL CHEMISTRY

0

50

100

150

200

250

Cum

ulat

ive

num

ber o

f pub

licat

ions

1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2011

Year of publication

Our

est

imat

ion

Our

est

imat

ion


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solvent-free sample preparation techniques

reduced scale of analytical operations

reduced time delay in obtaining reliable

analytical information

green solvents and reagents

application of agents enhancing the efficiency

of specific operations

reduced professional exposure of analytical

chemists

GREEN ANALYTICAL CHEMISTRY- GAC


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EVALUATING THE 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, Brusselsand Pensacola, 1993.

2 Aken K., L. Strekowski, L. Patiny, EcoScale, a semi-quantitative tool to select an organic preparation based on economicaland ecological parameters, Beilstein J. Org. Chem. 2, 3, 2006.

3 “Home Sustainability Assessment”, http://www.ecocompass.com.au/


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DIFFERENT LEVELS OF EVALUATING THE GREEN CHARACTER OF ANALYTICAL ACTIVITIES

Comparative evaluation of the environmental impact of:solvents and reagents;agents enhancing efficiency of analytical work;analytical instruments and whole protocols used for

the same purposes;whole analytical laboratories of course working in

the same area.


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NO SAMPLE PRETREATMENT BEFORE ANALYSIS NECESSARY

AN IDEAL SOLUTION

BUT:• only a limited number of such techniques!

• new ones are not to be expected in the near future


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KNOWN TYPES OF DIRECT MEASUREMENT TECHNIQUES

Potentiometric techniques (ion-selective electrodes- ISE)

Flameless atomic absorption spectrometry (in a graphite cuvette)

Inductively coupled plasma emission spectrometry (ICP)

Neutron activation analysis (NAA)

X-ray fluorescence spectrometry (XRF)

Surface analysis techniques (AES, ESCA, SIMS, ISS)

Immunoassay (IMA)


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SOLVENTLESS (SOLVENT‐FREE) SAMPLE PREPARATION TECHNIQUES

preconcentration of an analyte to a level abovethe limit of detection of the measuring-monitoring instrument

removal of interferents, which may affectanalyte identification and determination

simplification of the sample matrix


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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 SFE

SOLVENT-FREE SAMPLE PREPARATION TECHNIQUES


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POSSIBLE APPLICATION OF SUBCRITICAL WATER AS AN EXTRACTANT

S.B. Hawthorne, A. Kubatowa, Hot (subcritical) water extraction, in: Sampling and sample preparation for field and laboratory collective work, edited by J. Pawliszyn), Elsevier, 2002, pp. 587-608

DIFFICULT NON-POLAR

EASY POLAR 100oC

280oCPCBPAH

Organohalogen pesticidesMonoterpenes

Triazines and organonitrogen pesticides

Explosives (HMX, RDX, TNT)Phenols, amines


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IONIC LIQUIDS – SOLVENTS OF THE 21ST CENTURY

IONIC LIQUIDS are salts containing:• an organic cation;• an anion (usually inorganic).

Terminology•room-temperature ionic liquid (RTIL);•non-aqueous ionic liquid;•molten salt;•liquid organic salt;•fused salt


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at room temperature these salts are liquids;

dissolve both inorganic and organic compounds;

are thermally stable: their boiling points are high, often > 350°C;

usually immiscible with water;

are non-volatile (very low vapour pressure at 25°C);

dissolve catalysts, especially complexes of transition metals;

without simultaneously damaging the walls of glass or steel reactors

INTERESTING AND PROMISING PROPERTIES OF IONIC LIQUIDS


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ANALYTICAL APPLICATION OF IONIC LIQUIDS

Extraction techniques A promising extraction medium

Gas chromatography stationary phases (independently or as an addition to silica beds)

Electrophoresis Non-aqueous solutions

Micellar Electrokinetic Chromatography Buffer solution modifier

Mass spectrometry (MALDI-MS, ESI-MS)

Spectroscopic techniques (UV,IR) solvents with good solvation properties for both polar and nonpolar compounds

Electrochemical techniques(sensors)

important properties:- high electrical conductance,- wide electrochemical window,- chemical and thermal stability,- low vapour pressure

Atomic spectroscopy (ICP-AES) Enhances sample nebulization


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SOLID‐PHASE DYNAMIC EXTRACTION (SPDE)

PRINCIPLE:analytes are accumulated in the polymer coating of the innerneedle wall by pulling in and pushing out a fixed volume of airto be sampled, through the gas-tight syringe for anappropriate number of times within a fixed time. The vapourpressure flowing over the accumulating phase layer iscontinuously renewed.The trapped analytes are recovered by thermal desorptionand analysed by GC or GC-MS

ADVANTAGES: Rapid and efficient sample enrichment Interfaces with any CombiPAL System, controlled by all

major GC/GC-MSGreen Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia

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INSIDE NEEDLE DYNAMIC EXTRACTION (INDEX)

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SOLID PHASE NANOEXTRACTION (SPNE)

PRINCIPLE:Makes use of the strong affinity of PAHs for gold nanoparticles

IMPLEMENTATION:Liquid samples (water) of volume ca 500 μl (!!!) are mixed with a colloidalsolution of gold. This is followed by the quantitative binding of PAH analytes tothe surface of gold nanoparticles, which are then removed in an ultracentrifuge

FINAL DETERMINATION TECHNIQUE:HPLC-FD (fluorescence detector)

DETERMINATION OF PAH ANALYTES IN WATER POSSIBLE AT THE PPB-PPT LEVEL

H.Wang, A.D. Campiglia, Anal. Chem., 80, 8202-8209 (2008)


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Construction:

1. Plunger2. Barrel3. Injection needle4. Inner needle5. Coated fused silica fibre

SOLID PHASE MICROEXTRACTION (SPME)


1. direct‐immersion SPME2. headspace‐SPME

Principles of SPME

Operation steps:

1. Imerison of the needel in the sample2. Exposition of the fiber3. Extraction of an analytes4. Retraction of the fiber5. Introduction of the fiber to injection port6. Desorption of analytes


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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 fibre. 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


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MAIN DIFFICULTIES WITH THE ISOLATION OF POLAR COMPOUNDS

low affinity of extraction coatings for polarcompounds

the polar coating may partially dissolve in thepolar sample matrix

limited number of commercially available fibrecoatings for the isolation of polar compounds


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THE CONCEPT OF M‐SPME

SPME:• simplicity• short extraction time• solventless• automation• GC compatible• in-situ sampling

Membrane techniques:• physical separation• selectivity• broad range of solvents

M-SPMEA. Kloskowski, M. Pilarczyk, J. Namieśnik, Anal. Chem., 81, 7363 (2009)


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SCHEME OF M‐SPME FIBRE

1) silica fibre

2) polar retaining medium (50μm coating of PEG)

3) non-polar membrane (90-100μm coating of PDMS)


anal

yte

conc

entr

atio

n

distance from rod axis [m]0 75

gl

as

s

r

od

sa

mp

le~175 ~200

KPEG/Water >> KPDMS/Water

po

ly

et

yl

en

eg

li

ko

le

PD

MS

me

mb

ra

ne


Principles of extraction in M‐SPME

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SORBENTS IN M‐SPME

PDMS PEG

‐ non‐polar ‐ polar

‐ gum‐like or liquid‐like state ‐ gum‐like or liquid‐like state

‐ thermostable to around 300°C ‐ thermally resistant

‐ chemically neutral ‐ low melting point

‐ flexible ‐ high value of dielectric constant

‐ known values of partition coefficients

‐ known values of partition coefficients


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ABSORPTION VS ADSORPTION

ADSORPTIONartefact formation incomplete desorption strong catalytic interactions of adsorbents

ABSORTIONanalytes are retained by dissolutionanalytes can be desorbed at moderate temperatures analyte decomposition can be ruled outnon-specific interactions between analyte and sorbent


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PRELIMINARY RESULTS ‐ phenoles

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. Namieśnik, Anal. Chem., 81, 7363 (2009)


PRELIMINARY RESULTS – VOC’s

LOD (ng/l) COMPOUNDS PEG/PDMS DVB/CAR/PDMS

obenzene (CB) 0.23 0.41 p‐xylene (p‐X) 0.16 0.33 o‐xylene (o‐X) 0.13 0.24 isopropylbenzene (isoPB) 0.11 0.27 n‐propylbenzene (n‐PB) 0.10 0.27 2‐chlorotoluene (2‐CT) 0.12 0.31 4‐chlorotoluene (4‐CT) 0.13 0.35 t‐butylbenzene (t‐BB) 0.08 0.23 sec‐butylbenzene (sec‐BB) 0.08 0.12 1.3‐dichlorobenzene (1.3‐DCB) 0.12 0.37 1.4‐dichlorobenzene (1.4‐DCB) 0.13 0.37


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Outlook:Possibility of utilizing highly polar materials as sorbents

Opportunity to overcome the difficulties with extracting polar analytes from polar media

ADVANTAGES OF M‐SPME Low cost; Good mechanical properties, extremely stable thermally; Improved extraction efficiency; Possibility of adjusting selectivity of sorption based on high dielectric

constant of PEG; Analytes retained by dissolution; Analytes can be desorbed at moderate temperatures; Extraction time is considerably shorter than that required with a solid

polymer


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RECENT PUBLICATIONS ON GREEN ANALYTICAL CHEMISTRY

M. Tobiszewski, A. Mechlińska, B. Zygmunt, J. Namieśnik, Green analytical chemistryin sample preparation for determination of trace organic pollutants, Trends Anal.Chem., 28 (2009) 943.

A. Kloskowski, M. Pilarczyk, J. Namieśnik, Membrane solid-phase microextraction –a new concept of sorbent preparation, Analytical Chemistry, 81 (2009) 7363.

M. Tobiszewski, A. Mechlińska, J. Namieśnik, Green analytical chemistry : theory andpractice, Chem. Soc. Rev., 39 (2010) 2869.

A. Spietelun, M. Pilarczyk, A. Kloskowski, J. Namieśnik, Current trends in solid- phasemicroextraction (SPME) fibre coatings, Chem. Soc. Rev., 39 (2010), 4524.

M. Urbanowicz, B. Zabiegała, J. Namieśnik, Solventless sample preparationtechniques based on solid- and vapour-phase extraction, Anal. Bioanal. Chem., 399(2011) 277.


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DEPARTMENT OF ANALYTICAL CHEMISTRYCHEMICAL 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


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EUROPEAN MASTER IN QUALITY IN ANALYTICAL LABORATORIES‐ EMQAL

http://eacea.ec.europa.eu/erasmus_mundus/


The exploitation of white cabbage for phytoremediation and biofumigation of soils (AGROBIOKAP)

01.07.2007‐01.07.2013Project deadline:3 391 950,00 PLNRecommended subsidy:

1.3.1. Development projectsSub‐action:

1.3. Support for R+D projects carried out by scientific institutions on behalf of industrial companies

Action:

1. Research and development of novel technologies Priority axis:

Project co-financed by European Union from European Regional Development Fund in a framework of the Innovative Economy Operational Programme 2007-2013

CONTACTGdansk University of Technology, Chemical Faculty

G. Narutowicza 11/12 Str., 80-233 Gdańskphone/fax: 0048 58 347 26 25

e-mail: [email protected]://www.chem.pg.gda.pl/agrobiokap/


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MEMBERS OF MY RESEARCH GROUP


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THANK YOU FOR YOUR ATTENTION!


ACHIEVEMENTS IN GREEN SAMPLE PREPARATION FOR THE GAS ... i… · CHROMATOGAPHIC DETERMINANTION OF...

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