separation and preconcentration methods in trace species...
TRANSCRIPT
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Separation and preconcentration methods in
trace species in environmental samples:
from solid phase extraction to microextraction
Mustafa Soylak
Erciyes University, Faculty of Science, Department of Chemistry, 38039,
Kayseri-Turkey
E-mail: [email protected]
Personal web page: www.soylak.net
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Trace Heavy Metals
Metals such as iron, copper, zinc and
manganese are essential metals since they
play an important role in biological systems.
The main roles of these elements can be
described as functional and structural.
Some trace metals like lead, cadmium,
arsenic, mercury are the heavy metals
playing toxic role human life.
1/11/2019
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Toxicity from dietary intake of arsenic—up to 60 µg/day daily—is relatively low. Intakes of higher amounts of arsenic on a chronic basis may cause hyperkeratosis, especially of the palms and soles, skin pigmentation, eczematous or follicular dermatitis, edema (especially of the eyelids),. Chronic-high arsenic ingestion has been associated with various cancers, such as basal cell carcinoma and bladder, liver and lung cancers. The nail changes associated with arsenic toxicity are known as Mees' lines or transverse striate leukonychia.
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Very Low Concentration of Analyte in Samples
Preconcentration of Analyte
Large Amount of Matrix Components in Samples
Separation of analtye
PROBLEM SOLUTION
PROBLEMS IN DIRECT DETERMINATION OF TRACE SPECIES
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PRECONCENTRATION-SEPARATION METHODS
Solid Phase Extraction and Solid Phase microextraction
Coprecipitation
Cloud Point Extraction
Solvent Extraction
Flotation
Electrochemical deposition
Atom traps
Microextraction techniques
Magnetic separations
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Flow Chart for SEPARATION-PRECONCENTRATIOM
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Trace Species
Directly or Convert into a suitable form
Separation-Preconcentration Stage
Determination by instrumental techniques
( HPLC, GC, MS, GC-MS …. AAS, ICP-OES, ICP-MS etc.)
It is a long story for me from solid phase extraction to microextraction for
30 years and with many experiences…
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Solid Phase Extraction
• Solid phase extraction is the one of the separation-preconcentration method for the traces analyte ions in the various materials including natural waters, ores, biological samples etc.
• Solid phase extraction has several advantages: • Sensitive • Fast • Economic • Large preconcentration factors • Simplicity of phase separation • Suitability for automation
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STRUCTURE OF AMBERLITE XAD RESIN SERIES
Polystyrene-divinyl benzene (PS-DVB)
Polyacrylic acid ester (PAA-E)
1988
M. Soylak, Master Thesis, 1990
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Adsorbent: Amberlite XAD -4
Ligand: APDC
Adsorbent Amount: 500 mg
Eluent: 1M HNO3 in acetone
Sample volume : 1000 ml
Eluent volume: 5 mL
Preconcentration Factor: 200
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• Adsorbent: Activted
carbon
• Ligand: pyrocatechol
violet
Adsorbent Amount: 500
mg
Eluent: 1M HNO3 in
acetone
Sample volume : 1000 ml
Eluent volume: 5 mL
Preconcentration Factor:
200
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Impregnation –physical interaction between
adsorbent and ligand
• Adsorbent: Ambersorb 563
• Ligand: PAN
• Adsorbent Amount: 500 mg
Eluent: 1M HNO3 in acetone
• Usage number of resin : 10 times
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Chelating resins.. chemical interaction between
adsorbent and ligand
Adsorbent: pyrocatechol violet- XAD-
1180
Eluent: 2 M HCl
Usage number of resin : >100 times
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Biosorption
Adsorbent: Bacillus sphaericus-Diaion
SP-850
Eluent: 1 M HCl
Usage number of resin : >50 times
After 50 times, microorganisms should
be
reloaded again to resin
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Speciation of Cr(III) and Cr(VI) by solid phase extraction
Natural Water
(Cr3+, Cr6+)
Cr3+ + ( excess) H2O2
Cr6+-DDTC Chelate (pH 2.5)
pH 2.5
Cr6+ - DDTC Chelate
Amberlite XAD–2010 Column Procedure
FAAS Total Cr
Natural Water
(Cr3+, Cr6+)
FAAS Cr6+
Total Chromium Conc. – Chromium(VI) = Chromium(VI)+
Amberlite XAD–2010 Column Procedure
V.N. Bulut, C.Duran, M.Tufekci, L.Elci, M.Soylak, J. of Hazardous Materials,143,1-2,112 (2007)
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SPE- Speciation
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Carbon nanotubes
Grafene and grafene oxide
Nanodiamond
Carbon based nanomaterials
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SPE- carbon nanotubes
• Adsorbent: Carbon nanotubes
• Ligand: APDC
• Adsorbent Amount: 300 mg
Eluent: 1M HNO3 in acetone
Sample volume : 400 ml
Eluent volume: 5 mL
Preconcentration Factor: 80
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• Adsorbent: Carbon nanotubes
• Ligand: TAR
• Adsorbent Amount: 200 mg
Eluent: 3M Acetic acid
• Sample volume : 75ml
Eluent volume: 3 mL
Preconcentration Factor: 80
• 40 times..
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• Nanocomposites are materials formed by the dispersion of
particle.s in a matrix at the nanometer scale
Nanocomposits
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• Adsorbent: PPY/CNT nano
composite
• Adsorbent Amount: 200 mg
Eluent: 3M nitric acid
• Sample volume : 200 ml
Eluent volume: 1 mL
Preconcentration Factor: 200
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Manyetik Nano materials
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• Adsorbent: magnetic carboxilated
nanodimons
• Analyte: Ziram
• Adsorbent Amount: 25 mg
Eluent: 0.25 M HNO3 in acetone
Sample volume : 40 ml
Eluent volume: 1 mL
Preconcentration Factor: 40
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Comparison SPE and SPME techniques
paramater Classical Solid phase
extraction
Solid phase
microextraction
Amount of adsorbent 500 mg 20-50 mg
Sample volume 100 ml 10 ml
Time At least 30-60 min per
sample
10 min per sample
Organic solvenrs Too much limited
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Green chemistry
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renewable materials
Safe solvents and auxiliary
reagents
Safe chemicals
The use of a safer method for the prevention of
accidents
Less harmful chemical processes
monitoring and analysis of the prevention of
pollution
Reduction of waste
Energy efficiency
design
Waste measures
The using of microsized methods
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New Generation Preconcentration
Methods
Liquid phase microextraction
New generation
solvents
Ionic liquids
Supra molecular solvents
Deep eutectic solvents
Switchable solvents
Apparatus
Ultrasonication
Vortex
Microwave
Magnetic stirring
Organic solvents
Solid phase microextraction
Magnetic solid phase extraction 42
New Generation Separation-Preconcentration Methods
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To use minumum amounts of solvents and reagents
Simplificty of steps
High preconcentration factors (from 20 ml to 100 microliter)
Green methods green chemistry (green solvents like ionic liquids)
Less harmful or harmless than a process with simple step
Lower cost
High yield
Time saving
Low risc
*
Why is Microextraction…?
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Model solution
Addition of microextraction
solvent
centrifuge
Cloudy phase
Phase separation
Extractant phase
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Microexstraction
-Classical Solvents -New generation solvents Ionic Liquids Supramolecular Solvents Deep eutectic solvents
Switchable solvents
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CCl4, CHCl3, CH2Cl2, CS2…. Advantage:
Phase stability
High preconcentration factor
Simple phase separation
High mass transfer
Disadvantage:
o Toxic
o Some of them are prohibited chemicals
o expensive
46
21
-05
-2016 , IV ESER AN
ALİZ KO
NG
RESİ
Classical Organic Solvents
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Ionic liquids refers to liquid organic salts which may be below the 100 0C . Simple ionic liquid consists of an anion and cation. Cations are usually found in larger and anions are the smaller alkyl chain.
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Ionic Liquids
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Benefits: Anions and cations of the ionic liquid can be changed by
forming properties can be synthesized in different ways and
for specific processing
Density, melting point, viscosity and so on. properties can
be achieved by changing the structure of the ions in a
suitable solvent to the process
Flammability and low vapor pressure
The solubilty of organic and inorganic components
Thermal stability
Phase stability
High preconcentration factor
Simple phase separation
High mass transfer
Disadvantage: Expensive
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THF
1-Decanol
Hydrogen bonding
1-Decanol-THF amphiphiles
formation
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Supramolecular solvents
Supramolecular
solvents is
obtained by mixing
have long carbon
chain such as
hydroxyl solvent
(OH) and
carboxylic acid
(COOH) with
tetrahydrofuran
and tetrabutyl
ammonium
species.
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Advantages of supramolecular solvents Supramolecular solvents in the extraction study are alternative
environment-friendly solvent to the resultant organic solvent.
Supramolecular solvents is obtained by changing some effect such as pH, temperature, and ionic strength and the resulting effects of the colloidal solution with surfactants, water immiscible solvent dispersed in a continuous phase.
In the extraction operation, i.e. amphiphilic supramolecular linking group of solvents consisting of high concentration, a very small volume (50 to 1000 µL) solution is obtained by adding high yield of extraction media
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Deep Eutectic Solvents
Deep eutectic solvents (DESs) show physical properties similar to ILs such as
tunable miscibility, low volatility, high conductivity and good thermal stability.
DESs eliminate the disadvantages of ILs such as dangers to health and the
environment and high price.
Some DESs are drinkable and are prepared by simply mixing two safe
components togethers, they are easily accessible, cheap, biodegradable,
renewable, non-flammable and nonvolatile.
The preparation facility of hydrophobic or hydrophilic DESs is the most
important property of DESs in extraction studies and provides a suitable
extraction medium for different polarity analytes
Formation of DESs.
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DES 's the most important aspect of having very low
freezing point and that they are liquid below 150 ° C.
DES 's is the most liquid at between room temperature
and 70 degrees.
Chlonine chloride (Vitamin B4) due to cheap, durable
and low toxicity, urea, glycerol as an organic salt is
usually used in the preparation of DES.
DES's eliminates the disadvantage of organic solvents
being expensive, flammable and toxic effects.
DES 's are inert to water, and they can be prepared
without requiring any special equipment or techniques in
laboratory conditions.
DES 's have been used in the field of organic chemistry,
biochemistry, electrochemistry, catalysis processes and
preparation of new materials.
Hundreds of different kinds of DES 's can be prepared
with different properties, such as pH, freezing point,
viscosity, conductivity and so on..
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Deep eutectic solvents Speciation- Microextraction
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Switchable Solvents
Switchable solvents have two form polar and non-polar form, which they show differences in terms of their physical properties.
A switchable polarity solvent (SPs) is a solvent that creates water-miscible hydrophilic form in the presence of an atmosphere of CO2 at 1 bar, however separates from water and creates hydrophobic form when CO2 is removed with a phase transition trigger such as bubbling air, argon, nitrogen or other inert gas under heating and addition of acids and bases.
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The formation of switchable solvents based on the protonation of apolar
secondary, and tertiary amines, with water in the presence of CO2 at 1
atmosphere pressure. The basis of this reaction is exothermic and is based
on the protonated amines involves an alkyl amine bicarbonate or
carbonate salts.
The reaction of ammonium bicarbonate or alkyl carbonate solvents
resulting switchable polar solvents form that is miscible with water.
However creates hydrophobic form when CO2 is removed with a phase
transition trigger such as bubbling air, argon, nitrogen or other inert gas
under heating and addition of acids and bases.
Besides being switchable in this reaction, all of the components react
readily available, they are not toxic and is cheaper to build Another
important advantage of the use of these solvents.
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Presence of C02
Removing of C02
Addition of acide or
base
Passing N2 or Ar gas
Heating
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Switchable Solvent Based Liquid Phase microextraction
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21
-05
-2016 , IV ESER AN
ALİZ KO
NG
RESİ
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Nowadays works and Future planning…
• Quantum dots in the solid phase extraction • Thin film preconcentration
• Novamene: A new class of carbon allotropes
• Mg/Al layered double hydroxide (LDH)
• Metal Organic Frameworks (MOF),
• Covalent Organic Frameworks (COF)
• Nanoextration and solid phase nanoextraction …
• Nanoengines…. Nano membrans, Microfactories ???
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Collaborations and thanks
• King Saud University- Suudi Arabistan • Sindh University Pakistan • University of Peshawer -Pakistan • Yasouj University- Iran • Baku State University - Azarbeycan • Universidade Federal da Bahia, Brezilya • National Research Centre , Mısır • University of Girona, Girona, Spain • University of Pavol Jozef Safárik, Slovakya
• Erciyes Üniversitesi • TUBITAK • Hacettepe Üniversitesi • Pamukkale Üniversitesi • Karadeniz Teknik Üniversitesi • Gaziosmanpaşa Üniversitesi • Nevşehir Hacı Bektaş Veli Üniversitesi • Niğde Üniversitesi • Gümüşhane Üniversitesi • Çanakkale 18 Mart Üniversitesi • Van Yüzüncü Yıl Üniversitesi • Siirt Üniversitesi • Cumhuriyet Üniversitesi
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Thanks for your attention
Soylak Research Group www.soylak.net
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Homemade Microsample Injection System (MIS) from ACA, 610 (2008) 135.
Teflon Huni
Mikro pipet
SisleştiriciKılcal boru
Micro
pipette
Teflon
funnel
Nebulizer
Capillary
Tubing
Microinjection system for Flame AAS
To get signal 50 or 100 microliter of sample is enough
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