New and Emerging Sample Preparation Techniques For Water Analysis

New and emerging
sample preparation
techniques for water
analysis.
Dr S. D. M. Chinthaka
Department of Chemistry
University of Sri Jayewardenepura
Liquid-Liquid Extraction
❑ Historically the first sample preparation technique used in
analytical chemistry.
❑ A substance distributes between contacting immiscible liquids
❑ Distribution behavior is put to analytical use in concentrating

the substance into a small volume of the organic liquid.
❑ The ratio of its solubility in each phase is considered
❑ The analyte does not react with either phase or no chemical

change in both phases.
Liquid –liquid extraction with secondary equilibrium

Liquid –liquid extraction with secondary equilibrium
Solvent extraction of metal ions
❖ Hydrated inorganic salts

❖ Strong electrolytes
❖ More soluble in water than in organic solvents
To extract to the organic phase

❖ Neutralize their charge
Forming neutral metal chelation complex
Ion association
Organic species with an acidic group (-OH, -SH) and basic group (=N-, =O etc)
can easily replace the coordinated water molecules
½ Cu2+
H+
Liquid –liquid extraction of metal ions
Factors affecting the stability the metal ion complexes
❖ Basic strength of the chelating group

❖ Nature of the donor atom (soft base forms stable complexes
with smaller metal atoms)
❖ Ring size
❖ Resonance and steric effect
Influence of the acidity on the extraction of metal chelates

M n+ + n(HA) org → (MAn)org + nH +
If the concentration of metal cheated species (MAn) and M(OH)p species
in aqueous phase can be neglected
E vs pH
pH1/2
p
H
E vs pH
Problems with Liquid –liquid extraction
❑ Use of large amount of organic solvents
❑ Use of toxic organic solvents
❑ Expensive (ultra pure solvents required)
❑ Emulsion formation
❑ Time consuming
❑ Difficult automation
❑ Less green
Solutions for the drawbacks of Liquid –liquid extraction
❑ Micro liquid-liquid extraction
❑ Solid phase extractions
❑ Solid phase micro extractions

Micro –liquid-liquid
extraction
Diethyl ether
[AA] (non polar)
[AA] Water (polar)
Because small solvent volume mass transfer is

New and emerging micro-solvent extraction

techniques
❖ Hollow fiber liquid/liquid micro extraction
❖ Dispersive liquid/liquid micro extraction
❖ Cloud point micro extraction
❖ Floating drop liquid/liquid microextraction
❖ Single drop liquid/liquid microextraction

❖ Micro syringe hollow fiber liquid/liquid micro extraction
Two phase extraction

Extraction from aqueous to organic solvent
❑ Two phase hollow fiber liquid/liquid micro extraction
❖ Highly selective
❖ Rather clean extract
❖ High degree of enrichment
❖ On-line connection with analytical instruments (GC/HPLC)
❖ Suitable for compounds with large distribution ratio
❖ Suitable for moderately and highly hydrophobic analytes

❖ On-line connection with analytical instruments (GC/HPLC)
❖ Three-phase hollow fiber liquid/liquid micro extraction
❖ Three-phase hollow fiber liquid/liquid micro extraction
❖ Adjustment of the composition of donor/acceptor phases is critical
❖ Extraction from organic phase to aqueous phase
❖ Back extraction to the donor phase is prevented
❖ Can extract low K org/d compounds (high K a/org)
❖ Ionisable compounds having low Korg/d can be extracted just
by shifting two phase to three phase system
2,4-Dichlorophenoxyacitic acid (2,4 DPA)

Applications of HPLLME
Determination of drugs and residues in water and in bio

fluids
Environmental and food analysis

Endocrine disruptive chemicals
Reduced matrix interferences in dirty samples
Pesticides and drug residues in food/water/soil
Single drop liquid/liquid microextraction (SDME)
Head phase
Direct immersion
Advantages
❖ Simplicity
❖ Ease of implementation
❖ Insignificant startup cost,
❖ SDME is accessible to virtually all laboratories.
Advantages/disadvantages of HS-
SDME
❖ Rapid stirring is not possible
❖ Good for volatile and semi-volatile analytes
❖ low non-volatile matrix interferences
❖ Aqueous phase mass transfer step is critical
low vapor pressure solvents must be selected
Dynamic liquid/liquid microextraction
(SDME)
Continuous flow Single drop liquid/liquid microextraction (SDME)
Disadvantages of single drop liquid/liquid microextraction

(SDME)
❖ Careful and elaborate manual operation
❖ Complex matrixes reduces the stability of the solvent drop
❖ Sensitivity and the precision of SDME methods need further

improvement.
❖ Online preconcentration is not compatible.

Floating drop liquid/liquid microextraction
Dispersive liquid/liquid micro extraction (DLLME)
❑ Very fast micro extraction technique
❑ Ternary component solvent extraction system.
❑ Consists of an extraction solvent, a disperser solvent and aqueous

sample
❑ Appropriate mixture of extraction solvent and disperser solvent are

rapidly injected to aqueous sample
❑ A cloudy solution is formed and sedimented phase is collected for

further analysis after the centrifugation.
❑ Factors such as pH. extraction solvent and the volume, disperser

solvent and the volume, and the ionic strength of the sample effects
the DLLME.
Dispersive liquid/liquid micro extraction (DLLME)
Cloud point liquid extraction(CLE)
❑ Utilizes the two phase formation in non ionic surfactants
❑ The above the CMC and above the cloud point temperature,
the surfactant forms surfactant rich phase(micells) and
surfactant poor phase.
❑ The analyte is distributed between these two phases
❑ A very fast technique
❑ No shaking is necessary and centrifugation is only needed.

Cloud point liquid extraction(CLE)
Surfactant poor
phase
Surfactant rich
phase
Cloud point 25 at 1% aq soln °C Cloud point 68 °C in 1 % aq soln

Solvent free Extractions
Solvent free extraction techniques
❑ Purge and trap methods (P & T)
❑ Solid phase extraction (SPE)
❑ Solid phase microextraction (SPME)

Purge and trap methods (P &

T)
❑ Use for isolation of highly volatile analytes
❑ Compounds are extracted (purged) from water by bubbling an

inert gas.
❑ Purged sample components are trapped suitable solid sorbent

materials
❑ Sorbent is heated and back-flushed with inert gas to thermally

desorb trapped sample components onto gas chromatography
Purge and trap methods (P &
T)
Solid phase
❑ extraction(SPE)
A frontal chromatographic analysis
❑ A form of liquid column chromatography
❑ Development of hydrophobic silica columns facilitate SPE
❑ The aqueous sample run trough the sorbent bed
❑ The non polar or moderately polar analytes are adsorbed on

the hydrophobic sorbent bed.
❑ The bed need to be conditioned for better wetting and analyte

contact
❑ The adsorbed analytes are desorbed by suitable polarity

matched solvent.
❖ Use to isolate less strongly retained trace components

from major components
❖ Quantification is difficult
❖ Column is contaminated by sample
❖ Basis for solid phase extraction techniques
How Solid phase extraction(SPE) works
Analyte partition into the surface monolayer from aqueous

sample
Interaction of analyte with

sorbant
An equilibrium constant, KL, can be defined in terms of the mole

fraction of adsorbed sites, XA–S, the mole fraction of unadsorbed
sites, XS, and the mole fraction of analyte in equilibrium
A fractional coverage, θ, the fraction of analyte
occupied in sorbent surface
1
How Solid phase extraction(SPE)

performed

performed
performed
performed
How Solid phase extraction(SPE) performed-sequential extraction ,
cleanup, drying
Questions before
SPE
Factors to be considered for SPE
❑ Polarity of analyte
❑ Polarity of the sorbent
❑ Polarity of eluting solvent
❑ Sample cleanup sorbent
❑ Solubility of analyte in water(Ko/w)values

Dispersive SPE
❑ The sorbent is distributed in the sample matrix and separated

after extraction
❑ Quicker than conventional SPE
❑ Widely used for sample cleanup and extraction

QuEChERS Quick, Easy, Cheap, Effective, Rugged, and Safe, - A
dispersive SPE technique
❑ Removal of polar matrix components (organic acids,
polar pigments, carbohydrates)
❑ Acidification for some analytes and degradation of

others
❑ Dehydration
❑ Extraction
Advantages:
❑ Isolation and clean - up in one step
❑ Time and solvents saving
❑ Quick and EChERS

QuEChERS Quick, Easy, Cheap, Effective, Rugged, and Safe, - A
dispersive SPE technique

New and Emerging Sample Preparation Techniques For Water Analysis

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New and emerging

❑ A substance distributes between contacting immiscible liquids

❑ Distribution behavior is put to analytical use in concentrating

❑ The ratio of its solubility in each phase is considered

❑ The analyte does not react with either phase or no chemical

Liquid –liquid extraction with secondary equilibrium

❖ Hydrated inorganic salts

To extract to the organic phase

❖ Basic strength of the chelating group

Influence of the acidity on the extraction of metal chelates

❑ Use of large amount of organic solvents

❑ Use of toxic organic solvents

❑ Expensive (ultra pure solvents required)

❑ Micro liquid-liquid extraction

❑ Solid phase extractions

❑ Solid phase micro extractions

[AA] Water (polar)

Because small solvent volume mass transfer is

New and emerging micro-solvent extraction

❖ Dispersive liquid/liquid micro extraction

❖ Cloud point micro extraction

❖ Floating drop liquid/liquid microextraction

❖ Single drop liquid/liquid microextraction

Two phase extraction

❖ Rather clean extract

❖ High degree of enrichment

❖ On-line connection with analytical instruments (GC/HPLC)

❖ Suitable for compounds with large distribution ratio

❖ Suitable for moderately and highly hydrophobic analytes

❖ Adjustment of the composition of donor/acceptor phases is critical

❖ Extraction from organic phase to aqueous phase

❖ Back extraction to the donor phase is prevented

❖ Can extract low K org/d compounds (high K a/org)

❖ Ionisable compounds having low Korg/d can be extracted just

by shifting two phase to three phase system

2,4-Dichlorophenoxyacitic acid (2,4 DPA)

Determination of drugs and residues in water and in bio

Environmental and food analysis

❖ Insignificant startup cost,

❖ SDME is accessible to virtually all laboratories.

Disadvantages of single drop liquid/liquid microextraction

❖ Complex matrixes reduces the stability of the solvent drop

❖ Sensitivity and the precision of SDME methods need further

❖ Online preconcentration is not compatible.

❑ Very fast micro extraction technique

❑ Ternary component solvent extraction system.

❑ Consists of an extraction solvent, a disperser solvent and aqueous

❑ Appropriate mixture of extraction solvent and disperser solvent are

❑ A cloudy solution is formed and sedimented phase is collected for

❑ Factors such as pH. extraction solvent and the volume, disperser

❑ The analyte is distributed between these two phases

❑ A very fast technique

❑ No shaking is necessary and centrifugation is only needed.

Cloud point 25 at 1% aq soln °C Cloud point 68 °C in 1 % aq soln

❑ Purge and trap methods (P & T)

❑ Solid phase extraction (SPE)

❑ Solid phase microextraction (SPME)

Purge and trap methods (P &

❑ Compounds are extracted (purged) from water by bubbling an

❑ Purged sample components are trapped suitable solid sorbent

❑ Sorbent is heated and back-flushed with inert gas to thermally

❑ A form of liquid column chromatography

❑ Development of hydrophobic silica columns facilitate SPE