New Generation Green Solvents for

Separation and Preconcentration of

Organic and Inorganic Species Soylak
Mustafa (Ed.)
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NEW GENERATION GREEN SOLVENTS FOR
SEPARATION AND PRECONCENTRATION
OF ORGANIC AND INORGANIC SPECIES
 NEW GENERATION
GREEN SOLVENTS FOR
SEPARATION AND
PRECONCENTRATION
OF ORGANIC AND
INORGANIC SPECIES
Edited by

Mustafa Soylak
Department of Analytical Chemistry, Faculty of Pharmacy, Near East University,
Nicosia, TRNC, Mersin, Turkey

Erkan Yilmaz
Department of Analytical Chemistry, Faculty of Pharmacy,
Erciyes University, Kayseri, Turkey
ERNAM—Erciyes University Nanotechnology Application and
Research Center, Kayseri, Turkey
Elsevier
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 Contents

List of contributors ix 4. New methodologies and equipment used

in new-generation separation and
1. Historical backgrounds, milestones in the preconcentration methods
field of development of separation and MOHAMMAD HOSSEIN AHMADI AZQHANDI,
preconcentration methods TAHERE KHEZELI, MEHRORANG GHAEDI AND
ALI DANESHFAR
ERKAN YILMAZ AND MUSTAFA SOYLAK
4.1 The historical development and overview of these
Abbreviations 1 preconcentration and separation
1.1 Introduction 2 methodologies 149
1.2 Historical development of separation and 4.2 Hyphenated and nonhyphenated chromatographic
preconcentration methods 3 techniques for extraction and/or separation of
1.3 Conclusions 36 target compounds 150
References 36 4.3 Ultrasound-assisted emulsification
microextraction 151
2. Historical background: milestones in the 4.4 Cloud point extraction 153
field of development of analytical 4.5 High-diffusion liquids 155
instrumentation 4.6 Pressurized liquid extraction 156
NASRULLAH SHAH, MUHAMMAD BALAL ARAIN AND
4.7 Microwave-assisted extraction 157
MUSTAFA SOYLAK 4.8 Vacuum microwave-assisted extraction 159
4.9 Supercritical fluid extraction 159
2.1 Introduction 45 4.10 Dispersive liquid liquid microextraction 160
2.2 Development in the field of chromatography 46 4.11 Solidified floating organic drop
2.3 Development in the field of spectroscopy 49 microextraction 164
2.4 Development of electroanalytical techniques 62 4.12 Modern techniques of isolation and/or
2.5 Hyphenated techniques 67 preconcentration 170
2.6 Advancement in sampling systems for analytical 4.13 The application of carbon nanotubes and
instruments 70 nanoparticles in separation 195
2.7 Conclusion 71 4.14 Conclusion 198
References 71 References 198

3. Type of new generation separation and 5. Type of green solvents used in separation
preconcentration methods and preconcentration methods
ERKAN YILMAZ AND MUSTAFA SOYLAK ERKAN YILMAZ AND MUSTAFA SOYLAK

3.1 Introduction 75 Abbreviations 207

3.2 Liquid phase microextraction 76 5.1 Introduction 208
3.3 New-generation solid phase extraction 5.2 Green analytical chemistry 209
methods 117 5.3 Switchable hydrophilicity solvents 251
References 138 References 258

v
vi CONTENTS

6. Ionic liquids in separation and 7.17 Temperature-assisted supramolecular solvent

preconcentration of organic and inorganic extraction 341
7.18 Trends 342
species
7.19 Conclusion 342
TAHERE KHEZELI, MEHRORANG GHAEDI,
Acknowledgment 343
ALI DANESHFAR, SONIA BAHRANI, ARASH ASFARAM AND
MUSTAFA SOYLAK References 343

6.1 Introduction 267 8. Switchable solvents in separation and

6.2 Physical properties of ionic liquids 270 preconcentration of organic and inorganic
6.3 Application of ionic liquids in extraction of
species
organic and inorganic compounds 274
USAMA ALSHANA, ERKAN YILMAZ AND MUSTAFA
6.4 Magnetic ionic liquids and theory application 300
SOYLAK
6.5 Conclusion 304
References 307 Abbreviations 347
8.1 Introduction 347
7. Supramolecular solvents in separation 8.2 Switchable-hydrophilicity solvents 348
and preconcentration of organic and 8.3 Synthesis and chemistry of switchable-hydrophilicity
inorganic species solvents 349
8.4 Applications of switchable-hydrophilicity
MUHAMMAD BALAL ARAIN AND MUSTAFA SOYLAK
solvents 353
Abbreviations 319 8.5 Switchable-hydrophilicity solvents in large-scale
7.1 Introduction 319 extractions 354
7.2 Background 322 8.6 Switchable-hydrophilicity solvents in
7.3 Solvent extraction system 325 microextractions 356
7.4 Preparation of supramolecular solvents 327 8.7 Future aspects 377
7.5 Formation mechanism of SUPRAS phase 329 References 377
7.6 Components of supramolecular solvents 331
7.7 Supramolecular solvents in separation and 9. Deep eutectic solvent in separation and
preconcentration methods 331 preconcentration of organic and inorganic
7.8 Efficiency 337 species
7.9 Thermodynamics 337
TAHERE KHEZELI, MEHRORANG GHAEDI, SONIA
7.10 Environment 338 BAHRANI, ALI DANESHFAR AND MUSTAFA SOYLAK
7.11 Types of SUPRAS molecular extraction 338
7.12 Supramolecular solvents in liquid liquid Abbreviations 381
microextraction 338 9.1 Introduction 381
7.13 Integrated use of supramolecular solvents with 9.2 Deep eutectic solvent (definition and
nanomaterials 339 preparation) 383
7.14 Ultrasonic-assisted supramolecular solvent 9.3 Physicochemical properties of deep eutectic
extraction 339 solvents 385
7.15 Microwave-assisted supramolecular solvent 9.4 Application of deep eutectic solvents in extraction
extraction 340 techniques 402
7.16 Vortex assisted supramolecular solvent 9.5 Conclusion 416
extraction 340 References 417
 CONTENTS vii
10. Supercritical fluid extraction in 10.3 Instrumentation 427
separation and preconcentration of organic 10.4 Mechanism and kinetic of supercritical fluid 429
10.5 Applications of supercritical fluid 430
and inorganic species
10.6 Conclusion 440
TAHERE KHEZELI, MEHRORANG GHAEDI, SONIA BAHRANI
References 447
AND ALI DANESHFAR
Index 453
Abbreviations 425
10.1 Introduction 425
10.2 Properties of supercritical fluid 426
 List of contributors

Usama Alshana Department of Analytical Tahere Khezeli Department of Chemistry, Faculty

Chemistry, Faculty of Pharmacy, Near East
University, Nicosia, TRNC, Mersin, Turkey
Muhammad Balal Arain Department of
Chemistry, University of Karachi, Karachi,
Pakistan
Arash Asfaram Medicinal Plants Research Center,
Yasuj University of Medical Sciences, Yasuj, Iran
Mohammad Hossein Ahmadi Azqhandi Applied
Chemistry Department, Faculty of Gas and
Petroleum (Gachsaran), Yasouj University,
Gachsaran, Iran
Sonia Bahrani Department of Chemistry, Yasouj
University, Yasouj, Iran
Ali Daneshfar Department of Chemistry, Faculty
of Sciences, Ilam University, Ilam, Iran
Mehrorang Ghaedi Department of Chemistry,
Yasouj University, Yasouj, Iran
of Sciences, Ilam University, Ilam, Iran
Nasrullah Shah Department of Chemistry, Abdul
Wali Khan University Mardan, Mardan, Pakistan
Mustafa Soylak Department of Chemistry, Faculty
of Sciences, Erciyes University, Kayseri, Turkey;
Technology Research & Application Center
(TAUM), Erciyes University, Kayseri, Turkey
Erkan Yilmaz Department of Analytical
Chemistry, Faculty of Pharmacy, Erciyes
University, Kayseri, Turkey; ERNAM—Erciyes
University Nanotechnology Application and
Research Center, Kayseri, Turkey; Technology
Research & Application Center (TAUM), Erciyes
University, Kayseri, Turkey

ix
 C H A P T E R

1
Historical backgrounds, milestones
in the field of development of separation
and preconcentration methods
Erkan Yilmaz1,2 and Mustafa Soylak3
1
Department of Analytical Chemistry, Faculty of Pharmacy, Erciyes University, Kayseri, Turkey
2
ERNAM—Erciyes University Nanotechnology Application and Research Center, Kayseri, Turkey
3
Department of Chemistry, Faculty of Sciences, Erciyes University, Kayseri, Turkey

G graphene
Abbreviations GC gas chromatography
GCB graphitized carbon black
AµE adsorptive microextraction GC FID gas chromatography flame
APDC ammonium ionization detection
pyrrolidinedithiocarbamate GC MS/MS gas chromatography tandem mass
ASE accelerated solvent extraction spectrometer
C60 fullerenes GFAAS graphite furnace atomic absorption
CE capillary electrophoresis spectrometer
CF-SD-LPME continuous-flow microextraction/ GO graphene oxide
single-drop microextraction HGAAS hydride generation atomic absorption
CNTs carbon nanotubes spectrometry
CP coprecipitation HPLC high-performance liquid
CPE cloud-point extraction chromatography
CPT cloud-point temperature HR-CS-ETAAS high resolution continuum, source
DDTC diethyldithiocarbamate electrothermal atomic absorption
DESs deep eutectic solvents spectrometer
DI-SDME direct immersion single-drop HS-SDME head space single-drop
microextraction microextraction
EPA environmental protection agency ICP-AES inductively coupled plasma atomic
ETAAS electrothermal atomic absorption emission spectrometry
spectrometry ICP-OES inductively coupled plasma optical
FAAS flame atomic absorption spectrometer emission spectrometer
FIA flow injection analysis ILs ionic liquids
FIP international pharmaceutical ISO international organization for
federation standardization

New Generation Green Solvents for Separation and Preconcentration

DOI: https://doi.org/10.1016/B978-0-12-818569-8.00001-2 1 © 2020 Elsevier Inc. All rights reserved.
2 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods

LC-UV liquid chromatography ultraviolet The scientific community and the public have
spectrophotometer
LLE liquid liquid extraction
become aware of and concerned about the
LLLME liquid liquid liquid microextraction presence of organic trace species such as active
LPME liquid phase microextraction ingredients, pesticides, azo food additives, and
LSA liquid solid adsorption inorganic trace species such as heavy metal
LSE liquid solid extraction ions, metal compounds, anions, and nanoparti-
MAE microwave-assisted extraction
MALDI-MS matrix-assisted laser desorption/
cles in their working and living environments
ionization mass spectrometer and about the health impact of these sub-
MIPs molecularly imprinted polymers stances [3,4].
MISPE molecularly imprinted solid phase There is an increasing requirement to esti-
extraction mate the potential health risk of these trace
MOFs metal organic frameworks
PAHs polycyclic aromatic hydrocarbons
organic and inorganic species under the condi-
PGC porous graphitic carbon tions in which they are used. These species are
PLE pressurized liquid extraction found in biological, food, environmental sam-
PS-DVB polystyrene-divinylbenzene ples, and pharmaceutical products as naturally
PTFE polytetrafluoroethylene or synthetic at different concentrations, and
RAM restricted-access materials
RDSE rotating-disc sorbent extraction
they have been made for useful purposes; how-
SBSE stir-bar sorptive extraction ever, their prolonged use has become harmful.
SCSE stir-cake sorptive extraction Even if some of these species are useful for liv-
SDME single-drop microextraction ing cells to a certain extent, they have adverse
SFE supercritical fluid extraction effects on living cells in prolonged exposures
SFODME solidified floating organic drop
microextraction
[5 7].
SIA sequential flow injection analysis, When humans come into contact with or
solid phase microextraction consume these organic and inorganic species
SPE solid phase extraction in liquid, solid, and gaseous forms at different
SPME solid phase microextraction levels, these species can irritate and damage
SRSE stir-rod sorptive extraction
SSs switchable solvents
the skin, eyes, and respiratory tract; can dam-
SUPRAs supramolecular solvents age internal organs such as the nervous sys-
TAN 1-2-thiazolylazo-2-naphthol tem, liver, and kidneys; and especially can
WCED World Environment and cause specific diseases such as cancer [4 8].
Development Commission Worldwide foundations, organizations, admin-
TSP-MS-MS thermospray tandem mass
spectrometer
istrations, and environmental protection agen-
UAE ultrasound extraction cies such as the World Health Organization
UNWFP United Nations World Food (WHO), United Nations World Food
Programme Programme (UNWFP), World Pharmacy
WHO World Health Organization Council (WPC), International Pharmaceutical
WPC World Pharmacy Council
Federation (FIP), Environmental Protection
Agency (EPA) have set up organizations for
1.1 Introduction the long-term monitoring and identification of
organic and inorganic species in various bio-
In parallel with the development of technol- logical, food, environmental samples and phar-
ogy, there has been a significant increase in the maceutical products, including the effects at
amount of harmful trace organic, inorganic, different levels on living cells and the ecology.
and biological species in living areas, living Moreover, maximum permissible levels of the
organisms, and ecological environment [1,2]. organic and inorganic species in real samples

New Generation Green Solvents for Separation and Preconcentration

 1.2 Historical development of separation and preconcentration methods
Household
Foodanalysis Sewage
treatment
Energy Biotechnology
production
Trace
analysis
Environmental Pharmaceutical
analysis and andchemical
industry
monitoring
Transportation
Agriculture
are recommended by these organizations.
Hence the analysis of trace amounts of organic
and inorganic species in biological, food, and
environmental samples and in pharmaceutical
products have an important place in all envir-
onments containing living cells (Fig. 1.1).
1.2 Historical development of separation
and preconcentration methods
In the end of 19th century, Wilhelm Ostwald
described analytical chemistry as the art of sep-
arating, recognizing different substances, and
determining the constituents of a sample [9].
Taking the human health and environment
safety into consideration, the fast, accurate,
and sensitive determination of these organic
and inorganic species, especially at trace levels
in biological, food, and environmental samples
and pharmaceutical products, is always a sub-
ject of great interest, especially in the field of
analytical chemistry.
New Generation Green Solvents for Separation and Preconcentration
3
FIGURE 1.1 Subject areas that require trace or
ultratrace detection of the analytes.
In the age of classical analysis, while gravi-
metric and titrimetric methods were used for
the determination of the major and minor com-
ponents of materials such as rock and ores, the
proximity of the sum of components approach-
ing 100% was seen as a measure of the quality
of the analysis. Although it is known that trace
elements are present, however, they are not
considered to have a significant contribution to
clustering in very small amounts. An early
authority was Hillebrand [10], who published
his classic book Analysis of Silicate and Carbonate
Rocks in 1919 and used the word “trace” to
identify components below 0.01% or 0.02%
below the quantitative detection limit. In 1944
Sandell published Colorimetric Determination of
Traces of Metals. Sandell classified the major,
minor, and trace constituents as follows: Major
constituents of the fraction correspond to high-
er than 1% of the total sample amount; minor
constituents are those present in amounts
between 0.01% and 1%; and trace constituents
are those below 0.01% [11]. In a book Trace
4 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods

Analysis, published in 1965, reported the mod-
ern description of “trace” as more flexible [12].
This book contains beautiful and important
comments such as “The connotation of the
term ‘trace’ varies with the background or
interests of the reader” and “any sharp divi-
sion is, of course, superfluous, and will depend
on the nature of the sample to be analyzed,
the analytical technique employed, and the
analyst.” In that book, the upper limit of trace
level was considered to be about 100 ppm by
weight, and the term “ultratrace” was consid-
ered for constituents below 1 ppm.
The development of novel analysis methods
by analytical chemists allows for the determi-
nation of lower concentrations of analyte or
analytes in different sample matrices. A brief
history of analytical chemistry in terms of mile-
stones in detection limits is shown in Fig. 1.2.
For trace analysis to emerge as an area of
expertise in itself, two conditions had to be
met: special needs and applicable methods. In
general, qualitative methods appeared much
earlier than quantitative ones. There were a
few qualitative tests and even some quantita-
tive sensitivity methods before the beginning
of the century, but they did not cause much
curiosity until needed.
The 1940s created a new need for extraordi-
narily sensitive and difficult analytical proce-
dures. World War II had a very stimulating
influence on new needs, but it also suppressed
free publication for several years. This resulted
in the release for publication of a large amount
of previously classified information shortly
after the end of the war in 1945. The instru-
mentation and procedures built up to solve
specific war-related questions became available
for wider applications [12].
Analysis of trace levels of organic and inor-
ganic species in biological, food, and environ-
mental samples and in pharmaceutical
matrices is a difficult process. Generally, a
complete process of analysis of organic and
inorganic species in a sample takes five steps:
(1) collection of the sample, (2) conservation of
the sample, (3) preconcentration and separa-
tion of analyte/analytes from sample matrix,

FIGURE 1.2 Brief history of analytical chemistry in terms of milestones of detection limits.

New Generation Green Solvents for Separation and Preconcentration

 1.2 Historical development of separation and preconcentration methods
(4) instrumental analysis, and (5) data proces-
sing. A survey carried out in 1991 declared
that sample preparation can account for
around two-thirds (61%) of the effort of the
typical analytical chemist, and 92% of the
respondents considered sample preparation as
very important or moderately important [13].
No doubt it should be stated that, in the
last 50 years, analytical chemists have been
able to present many developments in their
work, as well as cost- and time-saving meth-
odology. And hence the classic gravimetric
and titrimetric analysis methods, which allow
the analysis of a single or at most two ana-
lytes, are now in most cases replaced by
instrumental detection techniques that can
provide two- and multidimensional informa-
tion at quantities of a few nanograms, picto-
grams, or even femtograms [14].
Though most modern instrumental detec-
tion systems provide excellent detection limits,
combined methods, consisting of several stages
such as sampling, decomposition, preconcen-
tration, separation, and determination, bring
important improvements in relative detection
limits, as well as in the accuracy and precision
of the analytical results [15]. The other impor-
tant advantages of such combinations are illus-
trated in Table 1.1.
Though the importance of sample prepara-
tion is often overlooked, it must be recognized
that the most important and critical stage in
this process is the separation and preconcentra-
tion step due to the complexity of sample
matrices and lower levels of these species at
trace levels and even lower than the detection
limits of the available measurement system
(from ng L21 to mg L21 or from ng kg21 to
mg kg21). In this way, analyte concentration is
increased above the detection limit of the mea-
surement system, interference effects of the
matrix species is decreased or eliminated, and
the analyte in sample matrix is converted into
a more suitable form for detection, which can
New Generation Green Solvents for Separation and Preconcentration
5
promote the loss of analytes or contamination
of sample.
A wide range of separation and preconcen-
tration techniques have been developed over
the last 100 years. While development was
slow until the 1990s, the developments in this
field have gained momentum in the last two
decades because scientists continue to explore
accurate, sensitive, simple, cheap, and widely
available sample preparation procedures with
reasonable detection limits.
Solid phase extraction (SPE), liquid liquid
extraction (LLE), cloud-point extraction (CPE)
and coprecipitation (CP) applications were the
conventional and more used sample treatment
techniques until 2000s. However, the produc-
tion of the new extraction mediums, such as
nanosized sorbents and new-generation sol-
vents, and the advent of new extraction equip-
ment, such as minisized extraction columns,
minisized extraction tubes, microinjection sys-
tems, ultrasonic and microwave vibration sha-
kers, vortex mixer equipment, and so on, have
led to an important transition from macroscale
separation and preconcentration methods to
microscale ones. Microscale separation and
preconcentration methods may become more
simple and rapid without causing deterioration
in the analytical accuracy and precision. The
microscale new-generation separation and pre-
concentration methods have come to be known
as solid phase microextraction (SPME) and liq-
uid phase microextraction methods (LPME) for
30 years.
When the literature studies are examined, it
is seen that while separation and preconcentra-
tion procedures, especially coprecipitation,
liquid liquid extraction and solid phase
extraction for the extraction of the major com-
ponents in real samples, have been used over
the last 100 years, they have been frequently
used for extraction and preconcentration of
trace organic, inorganic, and bioactive analytes
for 70 years [16 84].
6 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods
TABLE 1.1 Comparison of the direct instrumental analysis and combined methods with instrumental techniques for
trace organic and inorganic analyte analysis.
Items Direct analysis with instrumental techniques
Interferences Strong matrix effects interferences may occur
Detectability Detection limits depend on the sensitivity of the
detector and the signal generation area of the
instrumental technique
Calibration Reference materials are used
Systematic Loss of analytes, contamination, and blank problems
errors are minimal level
Economical Simultaneous analysis of analytes are simple and
aspects rapid
The coprecipitation method is one of the
first separation and preconcentration applica-
tions for trace analytes, followed by
liquid liquid extraction and solid phase
extraction methods.
1.2.1 Historical development of
coprecipitation methods
In the coprecipitation method, a precipitat-
ing agent is used for the reliable isolation of
the analyte precipitates in optimum conditions.
The precipitates are isolated from the sample
solution with centrifugation or filtration with
membrane filters. Isolated analyte precipitates
are dissolved in a suitable solvent such as dif-
ferent concentrations of HNO3, H2SO4, HCl,
and the like. Then analyte concentration in the
last phase is analyzed by means of a
suitable detection technique.
The mechanism of the coprecipitation
method was explained for first time by Shapiro
and Kolthoff in 1896 [16]. They explained the
New Generation Green Solvents for Separation and Preconcentration
Combined methods with instrumental techniques
Matrix interferences can be eliminated by separating
trace analytes from the sample matrix
Trace analytes in the sample are completely
concentrated into a small volume, which lead to a
strong increase in the detection limit
Calibration can be done readily by applying the
standard solutions
Contamination, volatilization hazards and blank
problems are more common
However, these drawbacks can be eliminated by
careful operations
Expert person, capability, time, and more apparatus
are generally required, but the methods can also be
carried out rapidly and simply by using well
designed techniques and apparatus
precipitation of silver bromide with the copre-
cipitation mechanism. After this report, many
studies were carried out to explain the copreci-
pitation mechanisms for different species. For
example, in 1924 McCandless and Burton pro-
posed the coprecipitation mechanism for the
determination of phosphoric acid by the
molybdate-magnesia method [17]. In a differ-
ent study, in 1934 a benzoate method was
developed by Kolthoff and coworkers to sepa-
rate the iron, aluminum, and chromium from
other ions of the third group and alkaline earth
ions [18]. This study may be the first work to
report on the separation and analysis of the
metals with the coprecipitation method.
Currently, the search for new precipitating
agents for the quantitative precipitation and
determination of metal ions is ongoing. Mover
and Remington provided magnesium and 8-
hydroxyquinoline precipitation as a coprecipi-
tation agent for zinc in 1938. Moreover, they
explained the importance of the pH of the sam-
ple solution phase on coprecipitation efficiency
and reported that the separation of ferric iron
 1.2 Historical development of separation and preconcentration methods
and aluminum is possible within in same con-
ditions with zinc ions [19]. In 1939 a report
was declared by Kolthoff and Overholser on
the coprecipitation of divalent zinc, nickel,
cobalt, magnesium, calcium, and manganese
ions. They used ferric hydroxide as the copre-
cipitation agent and checked the influence of
the concentration of ammonia and ammo-
nium chloride on the coprecipitation effi-
ciency of the metal ions. They found that
coprecipitation efficiencies of cobalt, nickel,
and zinc ions decrease with increasing con-
centrations of ammonia and ammonium chlo-
ride, while those of calcium, manganese, and
magnesium decrease with increasing concen-
trations of ammonium chloride but increase
with increasing concentrations of ammonia
[20]. In 1941 Louis Waldbauer and coworkers
used barium sulfate as a coprecipitation agent
for the coprecipitation of nickel, chromium,
cobalt, iron, and manganese ions and used
lead sulfate as the coprecipitation agent for
the coprecipitation of copper and zinc ions.
They found that chromium, manganese, and
iron could be coprecipitated with barium sul-
fate, while nickel and cobalt did not copreci-
pitate with barium sulfate. Zinc and copper
were coprecipitated with lead sulfate [21].
Witte provided a coprecipitation method for
the determination of tungsten as BaWO4 in
1943 [22].
The first known study for the separation
and analysis of small amounts of arsenic, anti-
mony, and tin in lead and lead alloys by copre-
cipitation method was performed by Luke in
1943. In this study, Luke used manganese diox-
ide as the coprecipitation agent [23]. The turn-
ing point in this area took place in 1948 with
the first study on the analysis of the trace level
of metal ions reported by Kolthoff and Carr.
They used magnesium ammonium phosphate
as the coprecipitation agent for the accumula-
tion of traces of arsenate. In this method,
150 μg L21 of arsenic can be analyzed with an
accuracy of 2%. They used an excess of tartrate
New Generation Green Solvents for Separation and Preconcentration
7
to prevent the precipitation of other metal ions
in the ammonia medium. They suggested that
the developed coprecipitation method can be
successfully used for the determination of arse-
nic in steel samples that contains more than
0.01% of arsenic [24].
Almost at the same time, investigation vari-
ous organic and inorganic precipitating agents
for coprecipitation methods has been stepped
up. In 1950 West and Conrad reported in an
extensive work titled “A Comparison Study of
the Coprecipitation of Cations by Organic and
Inorganic Precipitants.” They carried out the
experiments on the typical classes of inorga-
nic organic precipitation reactions in relation
to their tendency to coprecipitate foreign
cations. They found that organic coprecipita-
tion agents tend to coprecipitate cations to a
greater extent than inorganic ones. The possi-
ble mechanisms in this sort of precipitation
include the formation of coagulated colloidal
particles under the action of the electrolytes
present at the time of the reaction. Trivalent
cations have very suitable flocculation values,
and as a result the precipitation will be at the
highest level [25].
In the 1950s, it was possible to measure the
analytes in lower concentrations in parallel
with the developments in instrumental mea-
surement techniques, and the studies in this
field gained speed. In 1951 Garrison and Gile
developed a method for the radiochemical
analysis of At211 in fat, bone, skin, and muscle
of rats using a coprecipitation method.
According to our best knowledge, the devel-
oped method may be the first report on the
analysis in biological samples. They used the
metallic tellurium as coprecipitation agent and
analyzed At211 with an alpha-particle-X-ray
counting method [26]. Fr223 has a half-life of
21 min; hence it is imperative to use a very fast
method for analysis of Fr223. Based on this
requirement, Hyde, who was a researcher at
the University of California, used silicotungstic
acid as coprecipitation agent for the
8 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods
precipitation and isolation of francium-87 from
bombarded thorium targets [27].
The important advancements on the copreci-
pitation method has been lived after 1950s
with the application of new analytical instru-
ments and combined separation methods, such
as ion exchange, adsorption, and liquid liquid
extraction for trace analysis.
Some of important coprecipitation applica-
tions to date are described here.
In 1963 Girardi and Pietra found that the
separation of trace species from the matrix
environment prior to isotope analysis was a
very important stage. They used ion exchange,
isotopic exchange, and coprecipitation meth-
ods for the separation of 13 trace impurities in
aluminum prior to neutron-activation analysis.
The carrier free coprecipitation step provided
the simpler and faster final separation of indi-
vidual rare earths [28]. Though the photometric
determination of tin with the phenylfluoron
method provides an improved sensitivity,
matrix ions show adverse effects on accurate
determination. Shimizu and Ogata developed a
coprecipitation method based on the formation
of ferric hydroxide at pH 6B7, which led to
the collection of tin in the sample solution.
After this step, the precipitate was dissolved
and adsorbed on an anion-exchange column.
Zirconium, selenium, germanium, titanium,
and antimony were removed by elution with
0.5 N hydrochloric acid. Mercury and bismuth
were removed in a hydrochloric acid sulfuric
acid solution by using isobutyl ketone as a liq-
uid phase extraction medium. The obtained
results showed that as little as 1 μg kg21 of tin
in common salt, seawater, and bittern could be
analyzed with satisfactory results [19].
In 1966 Abdel-Rassoul and coworkers pre-
ferred a combined use of separation methods
consisting of adsorption on silica gel,
liquid liquid extraction, and coprecipitation
for the simultaneous determination of iron,
chromium zinc, and cobalt in metallic ura-
nium, uranium oxides samples, and uranium
New Generation Green Solvents for Separation and Preconcentration
concentrates prior to neutron-activation analy-
sis. They used aluminum chloride as a copreci-
pitation agent. In last step, they used ion-
exchange chromatography for the fractional
separation of the elements. The method devel-
oped allowed the determination of iron, chro-
mium zinc, and cobalt at parts per million
levels with a reproducibility of 10% 15% [30].
In 1967 a combined method designed as
coprecipitation with alkaline earth salts, fol-
lowed by solvent extraction of transition metal
dithiocarbamates, was developed by Joyner
and others for the separation and preconcen-
tration of nickel, manganese, iron, cobalt, zinc,
lead, and copper at trace levels in seawater
samples. They were able to recovery more than
90% for these elements prior to atomic absorp-
tion or flame emission analysis [31].
Fujinaga et al. developed a preconcentration
method based on organic coprecipitation for
trace levels of zinc, copper, vanadium, molyb-
denum, aluminum, and uranium in natural
water samples prior to neutron-activation anal-
ysis. The soluble ions were converted to oxine
chelates at pH 5.2, followed by extraction with
o-phenylphenol above 56 C and solidification
at room temperature. The solid particles were
accumulated on a filter, dried, and wrapped
up in a polyethylene sheet. In last step,
amounts of analytes were measured by
neutron-activation analysis at the parts per
billion level [32]. In 1975 a combined
coprecipitation X-ray fluorescence method
was developed by Bruninx and Van Meyl for
the preconcentration and determination of zinc
and lead between the 10 and 100 μg L21 levels
in surface waters. Zinc and lead in surface
waters were precipitated by formation of iron
hydroxide precipitants [33]. In the same year,
Rollier and Ryan searched the applicability of
solid-state fluorescence analysis for trace
elements by using aluminum as the example
element. They precipitated the aluminum as
aluminum oxinate with a high amount of oxine
and measured the luminescence of the
 1.2 Historical development of separation and preconcentration methods
aluminum oxinate precipitate (λex, 385 nm: λex,
524 nm). The developed method allows the
analysis of the parts per billion level of alumi-
num. In the 1970s, the importance of separation
and preconcentration methods in determining
trace elements was understood by scientists,
and interest in this field increased day by day.
An important research on the coprecipitation,
ion exchange, and solvent extraction was car-
ried out by Okochi in 1975. Okochi developed
eight kinds of coprecipitation, three kinds of
ion exchange, and three kinds of solvent
extraction methods for the separation and pre-
concentration of trace elements in metals.
Okochi investigated the possibility of the sepa-
ration and preconcentration of smaller
amounts of elements than in the conventional
methods, which led to the creation of new
ideas [34]. From the literature, it is seen that
iron hydroxide is one of the most used of
coprecipitation agents. In 1975 Bruninx used
ferric hydroxide as a coprecipitation agent for
the precipitation of trace amounts of Zn, Cd,
and Hg [35]. One of the most comprehensive
coprecipitation methods for trace elements was
carried out by Nagatsuka and Tanizaki in 1976.
They developed a coprecipitation method
based on the formation of Fe(OH)3 and PbS
precipitants for the separation and preconcen-
tration of Ca, Al, Mg, Dy, V, Ti, As, Ag, Cr, Co,
Cu, Cs, Fe, Eu, Lu, Na, Rb, La, Sc, Se, Sb, W,
Zn, and Sm prior to neutron-activation analy-
sis. They applied this developed method for
analysis of these trace elements in river waters
[36].
Takemoto and coworkers suggested a
coprecipitation X-ray fluorescence analysis
procedure for microgram levels of Pb(II), Fe
(III), Cu(II), Zn(II), Mn(II), Cd(II), Cr(III), Sb(III),
and As(III) in industrial wastewater and river
water samples. They used model solutions
including diethyldithiocarbamate (DDTC) or
ammonium pyrrolidinedithiocarbamate
(APDC) as complexing agents at pH 5.0 5.5.
The metal chelate complex formed was
New Generation Green Solvents for Separation and Preconcentration
9
precipitated by the addition of dibenzylidene-
D-sorbitol. The precipitates were collected on a
filter paper, dried, and analyzed by X-ray fluo-
rescence spectrometer. The obtained analytical
results were in good agreement with those
obtained by the atomic absorption method [37].
Ueda and Yamazaki developed a coprecipi-
tation procedure for trace amounts of cadmium
prior to flameless atomic absorption spectro-
metric and the differential-pulse polarographic
determinations in 1986. Cadmium changing
from 0.01 μg to at least 1000 μg amounts in
50 400 cm3 of a sample solution was precipi-
tated quantitatively by using a hafnium
hydroxide coprecipitation agent. They success-
fully used these methods for the determination
of trace amounts of cadmium in river water
samples [38].
A combined sequential separation/precon-
centration method, consisting of coprecipita-
tion with iron hydroxide and bismuth
phosphate, ion exchange, electrodeposition,
and counting by alpha spectrometry, was pro-
vided by Pu and Am at trace levels in environ-
mental samples. To determine Th in a chicken
bone sample, a combined sequential separa-
tion/preconcentration method was used as fol-
lows: oxalate precipitation, ion exchange,
electrodeposition, and alpha spectrometry [39].
In 1989 Eller et al. used Se as a coprecipita-
tion agent for gold, platinum, palladium, and
rhodium at the nanogram and picogram levels
in natural water, geological and biological stan-
dards, and manganese crust. They achieved
the quantitative isolation for these elements
prior to Zeeman graphite furnace atomic
absorption spectrometry and total reflection X-
ray spectrometry analysis [40]. In the same
year, Kurata et al. suggested an easy and rapid
procedure consisting of coprecipitation and X-
ray fluorescence for the analysis of As, Sb, Bi,
Sn, Fe, and Pb at trace levels in copper. In the
procedure, they solved a copper sample rang-
ing from 0.2 to 2.0 g in 20 mL of 8 M HNO3 by
heating. After cooling, 1 mL from 1 mg mL21
10 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods
of Zr solution was put in sample solution, and
the pH was adjusted to 9.4 9.5. The volume of
the sample solution was increased to 70 mL
with pure water and left to sit for 1 h to com-
plete the precipitation, and precipitates were
collected on the 1.0 μm membrane filter. The
precipitate on the filter was dried prior to X-
ray analysis. Three percent of relative standard
deviation (RSD) was obtained for analysis of
20 μg of all elements. They applied their
method for analysis of certified reference mate-
rials (CRMs). The obtained results were in
good agreement with the certified values [41].
In 1990 McLaren et al. used the isotope dilu-
tion ICP-MS for multielement trace determina-
tion in seawater and the nondefatted lobster
hepatopancreas tissue certified reference mate-
rials and HPLC-ICP-MS for determination of
tributyltin and dibutyltin in the harbor sedi-
ment reference material. While the elements in
seawater were separated from the matrix
medium by using either adsorption on immo-
bilized 8-hydroxyquinoline or by reductive
coprecipitation with iron and palladium, butyl-
tin compounds in the harbor sediment refer-
ence material were separated from the matrix
medium by cation-exchange high performance
liquid chromatography (HPLC). Detection lim-
its for tributyltin and dibutyltin were found as
5 and 12 ng Sn g21, respectively [42]. A differ-
ent usage of coprecipitation and ICP-MS proce-
dure was reported by Nakamura and Fukuda
to determine Sb, As, Bi, Pb, and Sn traces in
high-purity copper. They dissolved 1.0 g of
copper sample in 8 mL of 7 M HNO3 and
added 10 mg of La to the solution. As, Sb, Bi,
Sn, and Pb ions were coprecipitated with lan-
thanum ions as their hydroxides by adjusting
the pH of the sample solution between 9 and
10. The precipitate was collected on a filter and
dissolved with acidic solution, and concentra-
tions of Sb, As, Bi, Pb, and Sn were determined
by ICP-MS. The respective detection limits
were found between 0.01 and 0.08 ng mL21
New Generation Green Solvents for Separation and Preconcentration
with the RSD less than 2.5% for 100 ng of ana-
lytes [43].
Niskavaara and Kontas suggested a reduc-
tive coprecipitation method to separate Pd, Au,
Rh, Pt, Se, Ag, and Te traces from geological
samples. In this method, while mercury was
used as a collector, tin(II) was used as a reduc-
tant. After the coprecipitation step, graphite
furnace atomic absorption spectrometer
(GFAAS) was used to measure the concentra-
tion of analytes. The accuracy of the developed
method was checked on the analysis of geo-
chemical reference samples [44]. In a different
application, lanthanum hydroxide as a copreci-
pitation agent was used for the separation of
hydride-forming Bi(III), As(V), Sb(V), Te(IV),
and Se(IV) trace elements in a Mo matrix prior
to analysis with continuous hydride generation
and inductively coupled plasma atomic emis-
sion spectrometry. Detection limits for As, Bi,
Sb, Se, and Te were found as 0.2, 0.7, 2, 0.5,
and 2 μg g21, respectively [45].
The transition from macroscale coprecipita-
tion methods needing large sample amounts
and reagents to the microsized minimum sam-
ple amounts and reagents has gained impor-
tance in recent years. The most important step
in the development of microsized coprecipita-
tion techniques is the solving of precipitates in
microliter levels of final solvents before the
detection step. The improvements have led to
high preconcentration factors and reach to low-
ered detection limits. An example application
was carried out by Agaki and Haraguchi in
1990. They used coprecipitation and induc-
tively coupled plasma atomic emission spec-
trometry (ICP-AES) for preconcentration and
determination of Cr, TI, Al, Fe, Mn, Ni, Co, Zn,
Cu, Pb, and Y traces in seawater. They precipi-
tated trace elements with gallium hydroxide
and dissolved the precipitate with 50 μL of
nitric acid. A cross-flow nebulizer was used to
introduce the 50 μL of solution into the plasma.
The detection limits of these elements were
found to be 10 500 ng L21 with about 10%
 1.2 Historical development of separation and preconcentration methods
precision. In this analytical method, about 50
samples of 10 mL volume could be enriched
and analyzed within 1 h. The low sample vol-
ume needed and the speed of the method were
the most important advantages [46].
Takeda et al. used the coprecipitation
method for the preconcentration of trace
amounts of tin before electrothermal atomic
absorption spectrometry (ETAAS). They used
yttrium hydroxide for the precipitation of tin at
pH 9.5 11.2. A linear calibration graph
between 0.004 and 0.12 μg mL21 was obtained.
They used this developed coprecipitation-
electrothermal atomic absorption spectrometry
(ETAAS) procedure for the determination of
tin in zinc metal [47]. Hiraide et al. developed
a coprecipitation method based on the forma-
tion of indium hydroxide at pH 9.5 for parts
per billion levels of Cu(II), Cr(III), and Mn(II).
After the preconcentration step, the precipitate
was dissolved in 0.5 M hydrobromic acid and
determined with GFAAS. They applied this
developed method to water samples [48].
The transition metals have different oxida-
tion steps because the oxidation steps for each
element have different health effects on living
cells. Therefore in a sample, the analysis of the
species with the correct oxidation steps is more
important than the total quantification of the
relevant element. In 1991 Wengi et al. provided
a chelate coprecipitation graphite furnace
AAS procedure to determine parts per billion
levels of Cr(III) and (VI) in natural water and
human urine samples. They checked several
metal ion chelating agent coprecipitation car-
riers: Co(II)-l-nitroso-2-naphthol, Co(II)-dithi-
zone, Ni-dimethylglyoxime, Ni(II)-dithizone,
Co(II)-pyrrolidinedithiocarbamate, Fe(II)-dithi-
zone, Fe(III)-diethyldithiocarbamate (DDTC),
Zn(II)-APDC(APDC), Mn(II)-DDTC, and Cu
(II)-DDTC. They found that Mn(II)-DDTC was
the most suitable chelate carriers for the sepa-
ration of Cr(III) and Cr(VI) at suitable pH.
While the recovery values for Cr(III) were
changing from 87.4% to 105.3%, the recoveries
New Generation Green Solvents for Separation and Preconcentration
11
for Cr(VI) were changing from 85.4% to 108.2%
[49].
In another study, Zhang et al. suggested a
coprecipitation method for the determination
of arsenic(III) and arsenic(V) traces in water
samples. In this study, As(III) was coprecipi-
tated quantitatively with a Ni-ammonium
APDC complex at the pH between 2 and 3,
but, in the same experiment conditions, arsenic
(V) was not coprecipitated with the Ni-PDC
complex. So the developed method was based
on the precipitation of As(III). The amount of
As(III) in the precipitate was measured by
solid sampling ETAAS. As(V) was converted
to As(III) by using sodium thiosulfate and
potassium iodide, and the total As concentra-
tion was analyzed. The detection limit was
found as 0.02 ng mL21 for 500 mL portions of
water samples [50].
Currently, the prospect of developing online
preconcentration and analysis methods, which
enables automatic analysis in a short time, has
created excitement in the scientific community.
In 1992 Fand and Dong suggested an online
flow injection coprecipitation system coupled
to an electrothermal atomic absorption
spectrometer for the determination of heavy
metal traces in whole blood digests. They
used the iron(II)-hexamethylenedithiocarbamate
(HMDTC) complex to collect nickel and cad-
mium on the walls of a knotted reactor. The
precipitate was dissolved in 60 μL of isobutyl
methyl ketone and introduced onto a graphite
furnace platform of atomic absorption spec-
trometer. The precipitate collection times were
20 40 s, and sample flow rates of 2 mL min21
for Ni and 3 mL min21 for Cd were applied.
The detection limits for cadmium and nickel
were found as 0.003 and 0.02 μg L21, respec-
tively [51]. In another study, Dong and Fang
designed a flow injection technique including
an online coprecipitation and flame atomic
absorption spectrometer determination for
trace amounts of cadmium, nickel, and cobalt.
Metal ions were coprecipitated with APDC-Fe
12 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods
complex on a knotted reactor (KR). The precip-
itate was dissolved in MIBK and directly
injected into flame atomic absorption spec-
trometer (FAAS). The enhancement factors for
Ni, Cd, and Co were 30, 33, and 42, respec-
tively. They applied the developed method for
the analysis of bovine liver (NBS1577a) and
urine (GBWO9103) standard reference materi-
als with good agreement [52]. A different flow
injection online preconcentration procedure
was developed for silver at trace level in geo-
logical samples. The separation and preconcen-
tration of silver ions were accomplished by
using an online coprecipitation with iron(II)-
diethyldithiocarbamate complex in the pres-
ence of 1,10-phenanthroline in a flow injection
system. A knotted reactor was used to collect
the precipitate. The precipitate, dissolved in iso-
butyl methyl ketone, was injected into the neb-
ulizer of an atomic absorption spectrometer.
High concentrations of iron(II) were masked
with 1,10-phenanthroline. Enhancement factor,
detection limit (3σ), concentration efficiency,
coprecipitation time, and sampling frequency
were found as 26, 0.5 μg L21, 28 min21, 45 s,
and 62 h21, respectively [53].
Nielsen et al. combined hydride generation
atomic absorption spectrometry (HGAAS) with
online coprecipitation. The developed flow
injection procedure was used for analysis of
ultratrace amounts of selenium(IV). The sug-
gested application provided an online addition
of the coprecipitant to the time-based aspirated
sample. In this system, the sample solution and
lanthanum nitrate as the coprecipitating agent
were mixed online and merged with an ammo-
nium buffer solution of pH 9.1, which led to
precipitation and quantitative collection on the
walls of the microline reactor. Afterward, the
precipitate was dissolved in hydrochloric acid
and analyzed with hydride generation atomic
absorption spectrometry (HGAAS) [54]. In
1998 Mao et al. designed a flow injection online
coprecipitation preconcentration, combined
with FAAS for the accurate analysis of trace
New Generation Green Solvents for Separation and Preconcentration
silver. Copper-diethyldithiocarbamate (DDTC)
chelate was used as the coprecipitation agent.
The detection limit for silver was 0.6 μg L21 for
a loading time of 30 s. The scientists success-
fully analyzed trace amounts of silver in
geological samples [55]. Liu et al. used Ni(II)-
diethyldithiocarbamate (DDTC) coprecipitation
agent in the flow injection online coprecipita-
tion system for preconcentrations of trace lead,
copper, iron, and cadmium in environmental
and biological samples. They also used a knot-
ted reactor to collect the precipitate prior to
FAAS determination. While enhancement fac-
tors for iron, lead, cadmium, and copper were
59, 58, 65, and 60, the detection limits for iron,
lead, cadmium, and copper were 2.5, 2.7, 0.2,
and 0.5 μg L21, respectively [56].
Divrikli and Elci provided a cerium(IV)
hydroxide coprecipitation method to separate
and preconcentrate Co, Cu, Pb, Ni, and Cd
traces prior to FAAS determination. They used
this method for accurate determination of the
trace metals in aqueous solutions, water, and
sediment samples [57].
Usage of coprecipitation methods, together
with the electroanalytical techniques, has an
important place in the literature. Sekharan
et al. developed a coprecipitation method for
the separation of the antimony in impure
zinc sulfate electrolyte, followed by its
voltammetric determination in 1996 [58].
Hydrous manganese dioxide was used as the
coprecipitation agent [58]. In a different
method, Kirgöz et al. designed a voltam-
metric cell allowing direct measurement of
precipitates without any need for dissolution
or filtration steps. They successfully used this
system on the preconcentration of Pb(II)
traces in aqueous solution by using Al(OH)3
as the coprecipitation agent. The obtained
peak currents from voltammetric determina-
tion were found to be much higher than those
without applying centrifugation. The detec-
tion limit of the developed method was
2.2 3 1029 M [59].
 1.2 Historical development of separation and preconcentration methods
Soylak and Balgunes provided a gadolinium
hydroxide coprecipitation-atomic absorption
spectrometry system to determine trace
amounts of cobalt(II), lead(II), copper(II), and
manganese(II). The pH of the sample solution
was adjusted to 11 to obtain gadolinium(III)
hydroxide from gadolinium(III) salt. At this
stage, cobalt(II), lead(II), copper(II), and man-
ganese(II) ions were precipitated. The precipi-
tate was dissolved in 1 mL of 1 mol L21 HNO3
and analyzed by FAAS. The detection limits of
the analytes were found between 0.52 and
12.0 μg L21 [60].
A important microprecipitation method
based on the formation of Cd(II) 1-(2-thiazoly-
lazo)-2-naphthol (TAN) microprecipitate was
provided by ALOthman et al. for the precon-
centration of cadmium traces. In this system,
microvolume of the last phase was injected into
a flame atomic absorption spectrometer using a
microinjection system. The optimum precipita-
tion medium was obtained at pH 8. The limit of
detection, limit of quantification, and relative
standard deviation were found 0.25 μg L21,
0.83 μg L21, and 5.5%, respectively. They
applied the developed microprecipitation-
microsampling FAAS procedure to the analysis
of cadmium in food samples [61].
1.2.2 Historical development of liquid
phase extraction/microextraction methods
Liquid liquid extraction (solvent extrac-
tion) has been one of the best processes known
for two centuries for separating the compo-
nents of a liquid (the feed) by contact with a
second liquid phase (the solvent). The basis of
the process is based on the dispersion rates of
the components between two essentially
immiscible liquids. When the relevant ana-
lytes/analytes in the sample solution are trans-
ferred to the other phase, the matrix
components remain in the sample solution or
vice versa. In this way, extraction of the
New Generation Green Solvents for Separation and Preconcentration
13
analyte/analytes from the matrix environment
is carried out successfully. In other words, the
transfer of the components from one phase
(the feed) to the other is guided by a deviation
from the thermodynamic equilibrium, and the
equilibrium state depends on the interactions
between the two phases [31,62 95]. The foun-
dations of solvent extraction are probably
based on the studies conducted by Buchoz in
1805 [62,63]. He discovered that uranyl nitrate
is freely soluble in diethyl ether. The first
known application of liquid liquid extraction
(LLE) was by E. Peligot [64]. In 1842 uranyl
nitrate was extracted from nitric acid solution
to the ether phase in this study. Nearly 100
years later, nuclear energy, of great interest
during World War II, was used in the extrac-
tion and enrichment of large amounts of ura-
nium from the matrix environment. In 1867
Skey suggested the extraction of various metal
ions as thiocyanate forms into the ether phase,
a method that is still popular, but did not use
this method himself. He provided ether-based
thiocyanate extraction for the separation of
gold from platinum, iron from the alkaline
earths aluminum, chromium, manganese, ura-
nium, platinum and nickel, and cobalt from
nickel [65]. Ether extraction was becoming
increasingly popular, and in 1892 Rothe suc-
ceeded in extracting ferric chloride present in
concentrated nitric acid into the ether phase.
These applications continued rapidly up to the
ether extraction of gallium trichloride in 1924
[66]. One of the most important milestones in
the history of solvent extraction is the synthe-
sis and use of organic chelating agents that
form organic soluble complexes with various
metal ions. A very important application in
this field was carried out by Fischer.
Dithizone, a versatile chelating agent, was
used in the extraction and quantitative deter-
mination of various metal ions in his study
[66,67]. In order to perform the desired extrac-
tion and analysis, the effects of pH and the use
of masking agent variables that are important
14 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods
in extraction studies were investigated. Then
different organic chelating reagents such as
β-diketones, dimethylglyoxime, and 8-
hydroxyquinoline were successfully used in
LLE procedures. In the 19th century, LLE was
a popular procedure to extract and obtain
valuable ingredients, such as perfume and
paint, from different plant sources.
In the 1800s three research studies con-
ducted by Berthelot and Jungfleisch, Nernst,
and Gibbs were introduced to explain the the-
ory of phase equilibrium, the dissolution rates
of solutes dissolving between two unmixed
liquids, and presented data describing the sci-
entific facts of liquid liquid extraction [68,69].
These and other advances have made signifi-
cant contributions to the development of the
chemical industry.
In 1883 Goering developed a countercurrent
extraction process using ethyl acetate to recover
acetic acid from “pyrolytic acid” produced by
the pyrolysis of wood [70]. In the late 1890s, the
emergence of the chemical engineering profes-
sion paved the way for further consideration of
process designs and quantitative foundations in
process development. Most of the pathway
recorded in distillation and absorption studies
was readily adapted to liquid liquid extraction
due to its similarity with another diffusion-
based operation. The use of liquid liquid
extraction studies in the chemical industry
increased day by day and became one of the
most popular methods in the 1930s. Many of
the liquid liquid extraction methods still used
today in the chemical industry are the result of
innovations and developments made between
1920 and 1970.
For example, in the 1940s, the Dow
Chemical and Universal Oil Products
Companies introduced a well-known com-
mercial Udex procedure. In this procedure,
aromatic compounds were separated from
hydrocarbon mixtures by using diethylene
glycol.
New Generation Green Solvents for Separation and Preconcentration
The 1920s 1940s are considered important
milestones in the progress of liquid liquid
extraction methods since the production of
new solvents and innovative apparatus, such
as centrifugal extruders, mixer-settling equip-
ment, and mechanically agitated extraction
columns, were starting to be used in extrac-
tion procedures. At the end of the 1920s, oil
refineries and chemical companies were able
to produce different alcohol, ketone, ester and
chlorinated hydrocarbon derivatives in large
volumes by using petroleum-refining pro-
cesses or natural gas products. After these
developments, many specialty solvents such
as sulfolane (tetrahydrothiophene-1,1-diox-
ane) and NMP (N-methyl-2-pyrrolidinone)
were provided to extract aromatics from
hydrocarbons in the same years. Moreover,
special organophosphorous extraction sol-
vents were also utilized for extraction and
recovery of metals dissolved in aqueous
solutions.
After the 1950s, liquid liquid extraction
methods began to gain popularity for separa-
tion and preconcentration of trace amounts of
organic and inorganic analytes due to the
accessibility of new extraction solvents and
detection systems. Although the LLE methods
were frequently used in the separation and
enrichment of the organic and inorganic spe-
cies at the trace level between 1950s and
1990s, in this 40-year period, the main impor-
tant developments came about in the analysis
step, combined with the LLE extraction meth-
ods, and no significant further improvement
was made in LLE extraction. Major develop-
ments and innovations were experienced
with the introduction of green chemistry,
new-generation extraction solvents, and
microextraction methods in the 1990s.
Therefore LLE can be explained in two parts,
before and after 1990. Developments up to the
1990s are explained in the some literature
studies.
 1.2 Historical development of separation and preconcentration methods
1.2.2.1 Classification of liquid liquid
extraction systems
Extraction can be classified on the basis of the
• nature of extracted species and
• process of extraction.
On the basis of nature of extracted species, there
are two types
1. chelate extraction and
2. ion association
Classification based on the basis of process of
extraction, there are four types
1. extraction by chelation or chelate formation,
2. extraction by ion pair formation,
3. extraction by salvation, and
4. synergistic extraction.
The organic extraction solvents commonly
used until the 1990s for the extraction of ana-
lytes from aqueous phase to organic phase in
the LLE are as follows:
Carbon-based solvents: Carbon tetrachloride
(CCl4), chloroform (CHCl3), dichlromethane
(CH2Cl2), carbon disulfide (CS2), N-hexane.
Acid-based solvents: Carboxylic acids
(naphthenic acids, Versatic acids, decanoic acid,
pentanoic acid, hexanoic acid, heptanoic acid, octa-
noic acid), alkyl phosphoric acids [Di2-
ethylhexyl phosphoric acid (DEHPA)].
Amine-based solvents: Primary amines, sec-
ondary amines, tertiary amines, quaternary
amines (N,N-dimethyl cyclohexylamine, N,N-
dimethyloctylamine, triethylamine, primene JMT,
Adogen 283, Alamine 336, Adogen 381).
Alcohol-based solvents: Decanol, undecanol,
heptanol.
Cyclic structure solvents: Cyclohexane,
cyclohexanone.
In 1951 Andrews and Lloyd developed an
LLE method for the separation of zinc traces
prior to its colorimetric determination. Zn com-
plexed with di-beta-naphthylthiocarbazone
gives a cherry-red soluble complex in carbon
tetrachloride. Other metals, which show
interference effect upon determination, were
New Generation Green Solvents for Separation and Preconcentration
15
eliminated by applying a preliminary extrac-
tion as diethyl-dithiocarbamates. The method
was developed and used for analysis of 0.01
ppm zinc in liquid or 0.05 ppm in solid sam-
ples [71]. In 1953 Garner and Hale researched
the effect of surface-active materials on LLE
procedures. As a model application, they
researched the effect of Teepol added in the
water phase on the rate of extraction of diethy-
lamine from toluene drops by water. Results
showed that extraction efficiency was reduced
to 45% with the addition of only 0.015% of
surface-active material (Teepol) [72].
Pijck et al. developed a different LLE
method for the separation of radioactive trace
analytes. They used isoamylacetate for extrac-
tion of chromium traces from iron matrix with
high amounts. Cuproine in isoamylalcohol as
the extraction solvent phase was used to sepa-
rate copper at trace levels from zinc matrix
[73]. In 1962 Attaway et al. developed a proce-
dure for LLE and the gas-liquid chromatogra-
phy fraction of trace amounts of carbonyl
components in orange essence. Carbonyl com-
ponents were converted to their dinitrophenyl-
hydrazones by reactions of carbonyl with 2,4-
dinitrophenylhydrazine sulfate in ethanol and
analyzed as dinitrophenylhydrazones. The car-
bonyl components identified include hexanal,
hexenal (two isomers), acetaldehyde, octenal,
octanal, neral, furfural, carvone and geranial
[74].
In 1965 Brooks checked the usability of
extraction solvents lighter than water. He
developed a new method to separate and ana-
lyze trace elements in silicate rocks. The
method was based on the extraction of ele-
ments as chloro complexes into methyl isobutyl
ketone phase and subsequent spectrographic
analysis. The results showed that trace ele-
ments in silicate rock could be extracted from
the main matrix medium and could be
fractionated from each other. The method
developed provided fast, flexible, relatively
free extraction and simple analysis with
16 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods
quantitative results. Authors claimed that the
method developed was applicable for separa-
tion radioactive species and different oxidation
states of the same element, for example, anti-
mony(III) from antimony(V) [75].
In 1967 Joyner et al. introduced a simple
separation and preconcentration procedure for
metal traces. The procedure consists of copreci-
pitation with alkaline earth salts, followed by
liquid liquid extraction of transition metal
dithiocarbamates prior to flame emission or
atomic absorption determinations. The method
developed was applied to the quantitative
analysis of iron, manganese, cobalt, nickel, lead
copper and zinc at trace levels [31].
In 1968 Campbell developed a liquid liquid
extraction for the separation of rhodium and
palladium from waste solutions. They used tri-
capryl monomethyl ammonium chloride as
extraction solvent. They used flame photome-
try to determine rhodium and palladium in the
last phase. The method developed provided
0.05 μg mL21 of detection limit [76]. Mirza sug-
gested an LLE for 115Cd and 89,90Sr as fission
products. They succeed the extraction of these
elements with 1-phenyl-3-methyl-4-caprylpyra-
zolone-5. The LLE method provided extraction
efficiency of more than 80% for 89,90Sr and 90%
for 115Cd [77].
In a different study, Farrar et al. used 2-
thenoyltrifluoroacetone-xylene as the extrac-
tion solvent phase for liquid liquid extraction
of 249Bk. They used the beta counting system
for analysis of 249Bk [78].
In 1971 Bonsack developed an LLE method
for the separation of trace levels of niobium
from industrial titanium sulfate solutions.
Cyclohexanone and diisobutyl carbinol were
used as extraction solvents in acidic extraction
medium. Niobium was separated from the
matrix medium with a high extraction effi-
ciency (92% 98%) [79]. In 1972 Barratt et al.
introduced an LLE method for separation and
preconcentration of trace amounts of nickel
prior to gas-liquid chromatography analysis.
New Generation Green Solvents for Separation and Preconcentration
Ni(II) in aqueous phase at pH 4.5 5.0 was
extracted to the extraction phase consisting of
monothiotrifluoroacetylacetone and n-hexane.
The LLE method applied for determination of
trace amounts of nickel in fat and tea samples
[80].
Yatirajam and Ram introduced an LLE
method for the separation of molybdenum
from a hard matrix medium including alumi-
num, uranium manganese, chromium, zirco-
nium, iron, nickel, cobalt, and titanium.
Molybdenum was turned to phosphomolybde-
num blue complex in acidic medium and
extracted to isobutyl ketone phase.
Concentration of molybdenum in the last
phase was determined by cerimetry or other
standard methods [81]. Tinsley and Iddon used
a liquid ion exchanger Amberlite LA 2 in thio-
cyanate form as the extraction phase for the
separation and extraction of copper prior to
atomic absorption determination [82].
Generally LLE methods are used in the
extraction of analytes in the aqueous phase
into the organic phase. However, in some stud-
ies, an opposite application has been made. For
example, Lamey and Maloy used sulfuric acid
as a selective extraction solvent for extraction
of anthracene traces from cyclohexane solu-
tions of phenanthrene. In this method, anthra-
cene was removed, and high amounts of
ultrapure phenanthrene were easily obtained
[83].
In 1970s in order to find the optimum and
best separation-preconcentration procedure,
the scientists started to make comparison stud-
ies between extraction methods for trace ana-
lytes. Mieure et al. developed three different
extraction methods, which were liquid liquid
extraction, preconcentration of analytes in a
porous polymer resin column, and preconcen-
tration of analytes in porous polymer resin col-
umn. They selected organic components as
trace analytes. It was reported that detection
limits of 0.01 0.1 ppm were obtained with
these methods [84].
 1.2 Historical development of separation and preconcentration methods
As a result of the fact that the methods of
trace analysis have become important and a
lot of studies have been made in this field, a
literature data source was formed. Scientists
have begun to write review studies in this
area by using these resources. One of the most
important developments in extraction meth-
ods was to collect all information about
extraction in reviews. In 1975 Eisenbrand
wrote a review titled “Recent Developments
in Trace Analysis of Volatile Nitrosamines: A
Brief Review.” In this review, many extraction
and detection techniques up to the 1970s were
discussed [85]. As in other sample preparation
methods, online extraction applications in
LLE started to attract attention at this time. In
1976 Wu and Suffet designed new continuous
LLE devices, which paved the way to the
design and construction of new online extrac-
tion apparatus. The main part of this device
was a helical Teflon mixing coil. The continu-
ous delivery of the sample solution and the
extraction solvent to the extraction medium
was provided by a dual-channel micropump.
Separation of the extraction phase from the
aqueous sample phase was accomplished by a
glass column phase separator and a continu-
ous solvent evaporator concentrator. In this
way, the extraction solvent separated was pre-
pared for recycling. The developed apparatus
had a simple and cheap modular concept that
provide greater analytical flexibility and was
capable of recycling the extraction solvent.
The developed apparatus was used for analy-
sis of organophosphate pesticides in water
samples. Moreover, the authors claimed that
this continuous LLE apparatus is applicable
for the extraction and analysis of any trace
organic molecules [86]. Nord and Karlberg
also introduced an automated liquid liquid
extraction system for the separation and pre-
concentration of trace amounts of metal ions
prior to flame atomic absorption spectrometer
determination [87]. Coello et al. introduced a
continuous-flow LLE combined with flame
New Generation Green Solvents for Separation and Preconcentration
17
atomic absorption spectrometer for extraction
and analysis of indium. In this procedure,
indium traces in diluted nitric acid solution
were extracted into bis(2-ethylhexyl)phospho-
ric acid phase dissolved in 4-methylpentane-
2-one. The continuous-flow LLE system was
connected to online flame spectrometry to use
a fully mechanized system. The detection
limit, relative standard deviation, and sample
throughput of the developed method were
0.03 mg L21, 1.5%, and 60 h21, respectively
[88].
Oliver and Bothen combined the LLE
method with a capillary gas chromatogra-
phy electron capture detection system for the
separation, preconcentration and analysis of
trace amounts of 12 chlorobenzenes in water
samples. They used pentane as the extraction
solvent in the LLE method. They achieved a
preconcentration factor of 1000 2000 and
detection limits of 0.01 500 ng L21 (ppt) for
chlorobenzenes [89]. In a different application,
trace levels of herbicides and nitro derivatives
were extracted with CH2Cl2 and analyzed by
gas chromatography and capture electron
detector [90]. In 1983 Vahtila compared the
applicability and analytical performance values
of different preconcentration methods, such as
liquid liquid extraction, solid phase extrac-
tion, ion exchange, and the like, for analysis of
trace metals in seawater, biological materials,
and marine sediments [91]. Agostiano et al.
applied a different LLE method for separation
and preconcentration of some trace pesticides
(carbamates, chlorinated, carbonates phospho-
rated) in water samples. GC (gas chromatogra-
phy) and HPTLC were used in the
measurement stage [92].
In 1987 Petrov and Zhivopistsev used anti-
pyrine and diantipyrylmethane salts instead of
organic solvents for extraction of trace ele-
ments prior to spectrochemical analysis [93].
Hamann and Kettrup combined LLE and SPE
methods for the separation and preconcentra-
tion of phenoxy acid herbicides in water
18 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods
samples. Analyses were conducted by HPLC-
UV [94]. In a different application, LLE and
SPE methods was used together for the separa-
tion and preconcentration of trace metals [95].
As the world population increases, the
needs of people and production required to
meet these needs have increased rapidly. In
parallel, there has been a linear increase in
the amount of chemical activities in both
research laboratories and industry in order to
meet production needs. Chemical activities in
the laboratory and industry can negatively
affect living cells and the natural environment
and may lead to a decrease in the quality of
life.
Perhaps environmental awareness for most
of us started with the book Silent Spring pub-
lished by Rachel Carson in 1962 [96]. One of
Carson’s alarming observations was the envi-
ronmental pollution caused by pesticides such
as DDT, leading to the death of millions of
birds. During this time, the industry was striv-
ing to protect the nearby environmental zones
by building long chimneys. But it could not
account for serious environmental problems in
the long run. After 20 years, the UN
Conference on Environment and Development
(the Earth Summit) was organized, and many
reports were published. In 1987 The World
Environment and Development Commission
(WCED) published a report called “Our
Common Future.” In this report, for the first
time, the concept of sustainable development
was mentioned [97]. In 1993 a technical com-
mittee, coded as 207, was founded by the
International Organization for Standardization
(ISO) for environmental management. ISO/TC
207 was established as an umbrella committee
under ISO 14,000 environmental management
standards. Environmental management sys-
tems, life cycle assessment, environmental
labeling, greenhouse gas management, and
similar activities are evaluated by this commit-
tee. These studies, published reports, and
books, as well as organized meetings, are the
New Generation Green Solvents for Separation and Preconcentration
most important milestones in creating a more
sustainable future.
Awareness of life and of the need for envi-
ronmental protection has led chemists to recon-
sider the techniques, processes, chemicals, and
therefore all chemical events and to develop
environmentally friendly processes. In 1991 the
term “green chemistry” was introduced with
the 12 principles agreed upon by different key
individuals, scientists, and institutions
[98 101].
The main rules of green chemistry are
related to the developments of the “greening of
methodologies” by applying lower consump-
tions of energy, atom economy, eliminating
hazardous chemical processes and the use of
toxic chemicals and materials and reducing
waste.
Seven principles that can be applied to green
analytical chemistry, taken from the 12 princi-
ples of green chemistry accepted by all
branches of chemistry and industry, must be
considered [99 101]:
1. Prevention of wastes that may occur after
the process or minimizing them as much as
possible, for example, by using smaller
extraction systems in solid phase or liquid
phase extraction systems or smaller inner
diameter columns in chromatography.
2. Use of nontoxic environmentally friendly or
as little toxic chemicals and solvents as
possible.
3. Design and use of minimal energy-
consuming analytical systems and methods
to ensure energy efficiency.
4. Avoiding the use of chemical catalysts,
derivatization reagents, and other auxiliaries
avoided as much as possible.
5. Use of catalysts instead of stoichiometric
reactions.
6. Use of in situ analysis instead of offline
analysis.
7. Use of safer chemistry to prevent accidents
such as explosions and fires.
 1.2 Historical development of separation and preconcentration methods
Analytical chemists, who have taken on the
seven foundations of green analytical chemis-
try as their own, have demonstrated the impor-
tance in developing methods of sample
preparation methods that fulfill most of the
requirements of green chemistry. They have
used new-generation sample digestion systems
such as microwave ovens, ultrasonic irritation,
and the like. They have developed simpler,
environmentally friendly, and cheaper separa-
tion and preconcentration procedures, such as
SPME, membrane extraction, liquid phase
microextraction (LPME), accelerated solvent
extraction (ASE), microwave-assisted extrac-
tion (MAE), ultrasound extraction, among
others. And they have produced more green
solvents such as ionic liquids (ILs), deep eutec-
tic solvents (DESs), supramolecular solvents
(SUPRAs), switchable solvents (SSs), and
supercritical solvents for analytical applica-
tions and have used automated analysis sys-
tems such as flow injection analysis (FIA),
sequential flow injection analysis (SIA), and
multicommutation flow systems [100 104].
Several review articles [99 104], as well as a
few books [105,106], describing the area of green
analytical chemistry. For instance, Armenta et al.
[98] described the timeline and concepts for
many of the analytical techniques identified as
being green, including microwave-assisted
extraction (MAE), supercritical fluid extraction
(SFE), pressurized liquid extraction (PLE), solid
phase microextraction (SPME), stir-bar sorptive
extraction (SBSE), single-drop microextraction
(SDME), and liquid liquid liquid microextrac-
tion (LLLME), among others. The focus has been
on sample preparation, since this part of the
analytical chain is well recognized as the least
green, mainly due to the large consumption of
solvents.
Although liquid liquid extraction (LLE) is a
method that can be classified as a very effective
prescription method on both a laboratory scale
and an industrial scale, the most important dis-
advantages of this method are the use of
New Generation Green Solvents for Separation and Preconcentration
19
expensive and toxic chemicals, the application
of time-consuming and multistage extraction
steps, and the use of high-volume laboratory
equipment.
These disadvantages rapidly removed
liquid liquid extraction from green analytical
chemistry and restricted its use in sample
preparation. This situation has pushed analyti-
cal chemists to research faster, less costly, eas-
ier, and more environmentally friendly—
green—analytical sample preparation techni-
ques. They first predicted that the amount of
solvents used in liquid liquid extraction meth-
ods could be reduced. In this sense, the first
applications were reported by two different
research groups.
In 1996 Liu et al. reported the first applica-
tion of microsized liquid liquid extraction
called as LPME. Scientists have taken the first
steps in the transition from macrosized extrac-
tion solvents or systems to a microdrop extrac-
tion system SDME [107,108].
The basis of this LPME method, SDME, is
essentially the same as with conventional
liquid liquid extraction. However, the most
important difference in this method is to
extract the analytes in the aqueous phase into
the microvolume of the hydrophobic extraction
phase.
Liu and Dasgupta used this method for the
separation and preconcentration of sodium
dodecyl sulfate (a methylene blue active sub-
stance) prior to analysis with a light-emitting
diode based absorbance detector. In this
SDME application, they suspended B1.3 μL of
extraction solvent drop (chloroform) inside a
flowing aqueous sample solution, and a multi-
tube assembly was used to obtain a drop-in-
drop system. The aqueous sample solution
containing the ion pair of analyte is continu-
ously sent to the outer drop and aspirated
from the meniscus of the drop. Then, by wash-
ing this organic drop with a wash solution, a
clean extraction phase was obtained. In the last
stage, the concentration of analyte was
20 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods
measured by using a light-emitting dio-
de based absorbance detector. This important
SDME system as a kind of LPME provided
easy and flexible extraction, use of only
microliter-level extraction solvent, and combi-
nation with other detection systems [107].
Jeannot and Cantwell accomplished the
extraction of 4-methylacetophenone from aque-
ous phase into 8 μL of the n-octane phase by
using a different mode of single-drop microex-
traction. In this procedure, 8 μL of n-octane
drop as extraction phase was located at the
end of a Teflon rod, and the single-drop Teflon
rod apparatus was immersed in the sample
solution on the magnetic stirrer. The solution
was stirred for a certain time, and the single-
drop Teflon rod apparatus was taken out of
the sample solution. The organic drop was
sampled by using a microsyringe, and the con-
centration of 4-methylacetophenone in the last
phase was analyzed with GC [108]. The
method developed is a static LPME and is
called direct immersion single-drop microex-
traction (DI-SDME).
The main drawbacks of this method were
the use of a microsyringe for GC sampling
after completion of the extraction process and
the instability of extraction drop. In order to
solve these problems, conventional a GC
microsyringe as a micro separation funnel was
used by He and Lee in 1997 [109]. The authors
referred to the procedure as dynamic LPME. In
this method, the configuration of the extractant
phase is in the form of a plug rather than a
drop. This method has been developed to solve
the instability of extraction drop, which is a
significant problem in SDME extraction meth-
ods. To speed up the extraction process, the
sample phase is repeatedly drawn into the
syringe and removed again [109].
The introduction of these applications into
the literature has been an important milestone
for the future of liquid liquid extra-
ction based methods, and different modes of
SDME were introduced to the literature in a
New Generation Green Solvents for Separation and Preconcentration
very short period of time. These SDME meth-
ods can be classified by considering the appli-
cation of extractor phase as follows:
Three-phase SDME: In 1999 Ma and Cantwell
introduced three-phase SDME as a new mode
of LPME for cleanup and preconcentration of
trace analytes [110]. In this method, the 30 μL
n-octane liquid membrane was held inside the
a Teflon ring above the 1.60 mL of sample solu-
tion. A microdrop of receiving aqueous phase
is left suspended inside the organic liquid
membrane by using a microsyringe, and sam-
ple solution is stirred for extraction of analytes
from the sample solution into the organic
membrane phase and back-extracted simulta-
neously into the microdrop. After extracting
for a certain time, a syringe needle was used to
take back the microdrop and put it into an
HPLC for quantification. Scientists used this
new method for analysis of trace amounts of
methamphetamine, methoxyphenamine, 2-
phenylethylamine and mephentermine. As the
method provided a 160-fold enrichment factor
for 2-phenylethylamine and 500-fold for meth-
amphetamine, mephentermine, and methoxy-
phenamine with the use of microliter-level
receiving drop, doubled preconcentration fac-
tors were obtained with the use of a 0.50 μL
receiving drop [110].
Head space single-drop microextraction (HS-
SDME): The acceptor phase is suspended
above the sample solution, and extraction of
analytes from the sample solution into the
acceptor phase is carried out by stirring the
sample solution. Head space solvent microex-
traction (HSME), or more commonly head
space single-drop microextraction (HS-
SDME), was introduced for the first time by
Theis et al. in 2001 [111]. They used a 1-octanol
drop at the microliter level as the extraction
phase (acceptor phase) for the separation and
preconcentration of volatile compounds
including toluene, o-xylene benzene and ethyl-
benzene following GC or GC/MS detections. 1-
octanol was selected as the extraction phase
 1.2 Historical development of separation and preconcentration methods
due to its low vapor pressure, which led to
minimum evaporation during the extraction
process. The HS-SDME method provided an
inexpensive and convenient separation and
preconcentration for the trace amounts of vola-
tile organic compounds [111].
Continuous-flow microextraction/single-drop
microextraction (CF-SD-LPME): In 2000 Liu and
Lee introduced continuous-flow microextrac-
tion (CFME) as an LPME method. The method
is similar to the DI-SDME method [112]. But in
this mode of SDME, the sample solution flow-
ing at a certain speed interacts with the organic
drop. In this method, polyetheretherketone
(PEEK) connecting tube in a 0.5 mL glass
chamber is used to hold an organic drop at the
outlet tip of PEEK and used as a fluid delivery
duct. The connecting tube is immersed in a
continuously flowing sample solution up to
completion of the extraction process. They
used this CFME method for the separation and
preconcentration of trace chlorobenzenes and
nitroaromatic compounds in environmental
samples. After the microextraction process,
analysis of analytes was carried out by gas
chromatography electron capture detection.
They obtained enrichment factors between 260-
to 1600-fold by applying 10 min of extraction.
The CFME method provided a very low detec-
tion limit at femtogram-per-milliliter levels
[112].
Membrane-based LPME: In 1999 membrane-
based LPME as a different mode of LPME was
introduced by Pedersen-Bjergaard and
Rasmussen [113]. In these applications, dispos-
able and cheap hollow fibers, typically made of
polypropylene, are used. In these methods, the
analytes are transferred from the sample solu-
tion into the acceptor phase in the porous hol-
low lumen filled with a extraction solvent
through the pores. If the solution in the hollow
fiber is the same as the extraction solvent
imprinted in the pores of the hollow fiber, this
method is classified as two-phase HF-LPME.
But if these solvents are different, this method
New Generation Green Solvents for Separation and Preconcentration
21
is classified as three-phase HF-LLLME.
Extraction is carried out by magnetic stirring
or ultrasonic irritation.
Pedersen-Bjergaard and Rasmussen
extracted methamphetamine traces from aque-
ous sample solution (pH 13, 2.5 mL) in the 1-
octanol impregnated pores of an 8 cm piece of
a porous polypropylene hollow fiber, followed
into a 25 μL acidic acceptor solution inside the
hollow fiber. Methamphetamine concentration
in the last phase was measured with capillary
zone electrophoresis (CE). The extraction pro-
cess was carried out in a 4 mL sample vial and
two needles for introduction and collection of
the extraction phase. The preconcentration
factor, detection limit, and relative standard
deviation for methamphetamine were 75,
5 ng mL21, and 5.2%, respectively. The method
developed was applied for analysis of metham-
phetamine in human urine and human plasma
samples [113].
DLLME: In the 2000s, analytical chemists
continued their search for new sample prepara-
tion techniques that were more environmen-
tally friendly, easier and faster. This research
was turned into products in a short time, and
new-generation extraction methods were
developed. In 2006 a new LPME method based
on a ternary component solvent system, called
dispersive liquid liquid microextraction
(DLLME), was introduced to the scientific
world by Assadi and colleagues [114]. In this
method, the dispersing phase solution contain-
ing the extraction solution is rapidly injected
into the sample solution containing the ana-
lytes. A cloudy extraction solvent phase is
obtained. Obtaining a finely dispersed cloudy
extraction phase allows the extraction phase
and the analyte to interact more with each
other. Thus the analytes in the sample solution
are extracted into the finely dispersed cloudy
extraction solvent phase. The most important
point is that the dispersion phase can be mixed
with both water and extraction phases [114].
22 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods
Solidified floating organic drop microextraction:
Efforts to develop greener extraction methods
have led to a reduction in extraction and other
organic solvents in microextraction methods.
Scientists continued to concentrate on the
extraction process with a single drop of micro-
volume. However, the tendency to break on
the surface where the extraction drop is
attached, the problems during the transfer of
the drop to the analysis step after the extrac-
tion, and loss of the extraction liquid contacted
with a surface can limit the usability of these
methods. To solve these problems, in 2007
Zanjani et al. introduced solidified floating
organic drop microextraction (SFODME) as a
new mode of LPME [115]. The microvolume
organic extraction solvent drop with a melting
point close to room temperature (10 C 30 C)
is left on the sample solution, and the sample
solution is stirred on the magnetic stirrer at a
certain rotational speed. At this stage, analytes
are extracted from the aqueous sample solution
phase into the extractor drop. Then the sample
is cooled via an ice bath. In this way, the
extraction solvent solidifies into a drop while
the sample solution, having a low freezing
point, remains liquid. The solidifying extrac-
tion phase is taken up in a vial with a spatula,
melted, and analyzed [115].
Zanjani et al. used the SFODME method for
the separation and preconcentration of some
polycyclic aromatic hydrocarbons (PAHs) at
trace levels. They used 8 μL of 1-undecanol as
extraction solvent drop. After completion of
the extraction step, 1-undecanol, solidified in
an ice bath, was transferred into a vial and
melted. In the last step, 2 μL of 1-undecanol
was placed into a GC system for analysis of
analytes. The values of detection limit, enrich-
ment factor, and relative standard deviation
for PAHs were 0.07 1.67 μg L21, 594 1940,
and ,7%, respectively [115].
The amounts of organic extraction solvents
used are considerably reduced in the microex-
traction methods described herein. According
New Generation Green Solvents for Separation and Preconcentration
to the commonly used liquid liquid extraction
method, microextraction methods are classified
as faster, easier and more environmentally
friendly. However, in these methods, the use
of organic solvents, even in microvolumes, dis-
turbed scientists. Analytical chemists aimed to
use new-generation environmentally friendly
solvents. As a result, they began to use more
environmentally friendly solvents such as ionic
liquids, deep eutectic solvents, supramolecular
solvents and switchable solvents in microex-
traction methods.
1.2.3 Historical development of cloud-
point extraction
A different liquid liquid extraction method
called CPE was first introduced by Watanabe
et al. in 1978 [116]. Their method was based on
the extraction of Zn(II) ions as 1-(2-pyridyla-
zo)-2-naphthol (PAN) complex from aqueous
phase into Triton X-100 micellar phase. Cloud-
point extraction is the newest separation and
preconcentration method among the traditional
methods. CPE is also called surfactant-based
extraction [116 119].
CPE is based on the extraction of analytes in
aqueous solutions into the micelle phase
formed by nonionic, zwitterionic, cationic and
anionic nonionic surfactants containing a non-
polar tail and a polar head group. These two
sides are hydrophobic and hydrophilic in an
aqueous sample solution, respectively. The
hydrophobic tails gravitate to create aggregates
called micelles. When the solution including
aqueous sample and surfactants is heated to a
particular temperature, referred to as cloud-
point temperature (CPT), micelle formation is
started and a turbid solution is obtained.
Above the CPT, the micellar solution separates
into a surfactant-rich phase of a small volume
and an aqueous sample phase. Concentrations
of analytes in the surfactant-rich phase are
measured by a suitable detection system.
 1.2 Historical development of separation and preconcentration methods
CPE needs only a diminutive amount of rel-
atively nonflammable, nonvolatile and eco-
friendly surfactant; since the use of solvent is
at a minimum level, the level of secondary
wastes after extraction is significantly lower,
and this method has the ability to be safely and
easily applied in a short period of time
[119 124]. Moreover, the toxic, volatile, and
flammable organic solvents in large quantities
used in conventional methods such as
liquid liquid extraction, solid phase extraction
and coprecipitation methods are eliminated by
CPE. Hence CPE can be considered environ-
mentally friendly.
CPE has been used frequently for the sepa-
ration and preconcentration of trace amounts
of metal ions, bioactive compounds, organic
compounds, persistent organic pollutants and
drugs. Important parameters affecting CPE
efficiency are the type and concentration of
surfactants, pH and ionic strength of aqueous
phase, incubation time and equilibrium tem-
perature, and volume of the aqueous phase.
The most commonly used surfactants in the
CPE method are Triton X (polyoxyethylene-(n)-
octylphenyl ether), PONPE (polyoxyethylene-
(n)-nonylphenyl ether), Genapol X (oligoethy-
lene glycol monoalkyl ether), polyethylene gly-
col 600 monooleate (PEG600MO), and Brij
(polyoxyethylene-10-akyl ether) [117 128].
In 1991 Saitoh and Hinze synthesized 3-
[nonyl- (or decyl-) dlmethyl-ammonlojpropyl
sulfate (C-APS04 or C10-APSO4 zwitterionic
surfactants) for separation and preconcentra-
tion of hydrophobic species, some steroidal
hormones and vitamin E prior to HPLC deter-
mination. They obtained high recovery results
of more than 88% for analytes. When com-
pared with other commercial surfactants such
as polyoxyethylene (7.5) nonyl phenyl ether
(PONPE-7.5), the new surfactant provided
important superiority such as formation of
two-phase system in lower temperatures, high-
er extraction efficiency, homogeneous and
purer surfactant formation and minimum
New Generation Green Solvents for Separation and Preconcentration
23
background absorbance at UV detection wave-
lengths [117].
Okada used poly(oxyethylene) (7.5) nonyl-
phenyl ether as a surfactant for the cloud-point
ion-pair extraction of SCN2 complexes of tran-
sition metal ions. The concentration of SCN2
has an effect on the cloud point of this surfac-
tant. This mechanism can be explained by the
repulsive interaction between the surfactant
chains because of the partition of SCN2 into
the micelle, which is experimentally proved
with the analysis of SCN2 in the surfactant-
rich phase by ion chromatography [118].
Horvath and Huie investigated the salting-
out effect on the separation of Triton X-100 as a
nonionic surfactant from aqueous solutions
and the extraction efficiency of the trace
amounts of organic analytes. Improved extrac-
tion capabilities and enrichment factors were
obtained for the separation and preconcentration
of many hydrophobic and hydrophilic metal-
free porphyrins (protoporphyrin, coproporphyr-
in, hematoporphyrin, and uroporphyrin,) and
one metalloporphyrin (iron-protoporphyrin)
at room temperature [119].
Laespada et al. developed a CPE method for
the separation and preconcentration of ura-
nium as 1-(2-pyridylazo)-2-naphthol hydro-
phobic chelate form. They used Triton X-114 as
the nonionic extraction phase. The CPE method
was used for analysis of trace amounts of ura-
nium in tap and river waters [120].
Warner-Schmid et al. synthesized per-
methyl-hydroxypropyl-β-cyclodextrin (PMHP-
β-CD) as a new surfactant and used it for the
cloud-point extraction of many aromatic com-
pounds (i.e., aniline, acetanilide, N-methylaniline,
2,2ʹ-dihydroxybiphenyl, 2-naphthol, o-nitroani-
line, m-ni-troaniline, p-nitroaniline, o-nitrophenol,
m-nitrophenol, p-nitro-phenol, nitrobenzene,
2-phenylbenzimidazole, 3-phenylphenol, and
4-phenazophenol) from aqueous solution [121].
In a different CPE application, napropamide
and thiabendazole at trace levels in aqueous
phase was extracted into Genapol X-80
24 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods
surfactant phase with recovery rates of up to
95%. Concentrations of analytes in the
surfactant-rich phase were measured by fluo-
rescence. The method developed applied for
determination of analytes in soil samples with
detection limits below 0.2 μg L21 [122]. Akita
and Takeuchi used PONPE10 surfactant for
cloud-point extraction of trace amounts of
phenol and three pyridines [123]. The same
authors also searched the equilibrium distri-
bution of aromatic compounds between an
aqueous solution and a coacervate of poly-
oxyethylene nonyl phenyl ether nonionic
surfactant. The results showed that aromatic
compounds that lower the cloud point to
greater extent can lead to higher extraction
efficiency [124].
Ferrer et al. developed a CPE method to sep-
arate and preconcentrate polycyclic aromatic
hydrocarbons in water samples. They used
Triton X-114 as the extraction solvent phase.
After CPE, HPLC with fluorimetric detection
and wavelength programming was used for
determination of analytes in the surfactant-rich
phase. The detection changes from nanograms
per liter to even subnanograms per liter were
accomplished by this procedure [125].
Silva et al. used a CPE method for the sep-
aration and preconcentration of Er(III) traces
in Er(III)-2-(3,5-dichloro-2-pyridylazo)-5-
dimethylaminophenol complex form prior to
its spectrophotometric determination at
584 nm. Polyethyleneglycolmono-p-nonyl-
phenylether (PONPE-7.5) was used as extrac-
tion agent. The molar absorptivity, linear
range, and detection limit values were
27 3 105 L mol21 cm21, 0.02 2 mg L21, and
1.48 3 1027 mol L21, respectively [126].
Pourreza et al. used Triton X-100 surfactant
as extraction solvent for the separation and
preconcentration of malachite green at trace
levels in river water and fish farming samples
prior to UV visible spectrophotometer deter-
mination with recoveries in range of 95%
102% [127].
New Generation Green Solvents for Separation and Preconcentration
Tang et al. developed an easy CPE method
for the separation and preconcentration of trace
amounts of tricyclazole, diniconazole triadime-
fon, and tebuconazole triazole fungicides in
environmental waters by using polyethylene
glycol 600 monooleate (PEG600MO) nonionic
surfactant. Analysis was carried out by HPLC/
UV [128]. Average recovery results for river
water and tap water samples were between
82% and 92%, and RSDs were between 2.8%
and 7.8% [128].
Wang et al. applied CPE for the separation
and preconcentration of di-ethyl-phthalate
(DEP), 2-ethylhexyl-phthalate (DEHP) and di-
cyclohexyl-phthalate (DCP) in spiked water
samples following HPLC/UV analysis. The
CPE method provided the preconcentration
factors between 35 and 111 and recoveries
between 85% and 103% [129].
1.2.4 Historical development of solid
phase extraction/microextraction methods
Solid phase extraction started with a process
in which users were not aware of scientific
facts and therefore used different names such
as “adsorption,” “sorption,” “retained on solid
materials” for thousands of years. Some scien-
tists claim the first literature reference is to be
found in the Bible, Ex. 15: 24 25 to be exact
[130]. In the medieval period, in the city of
Grasse in France, rose petals were placed in
paraffin wax, and the extraction of the volatile
fragrances of the rose petals is considered a
solid phase extraction application [130]. The
use of charcoal, diatomaceous earth, and zeo-
lite to remove pigments from chemical reaction
mixtures can be considered the first modern
application of solid phase extraction. In such
applications, the charcoal, diatomaceous earth,
or zeolite was passed through the filter and
discarded together with the compounds it
absorbed. It should be noted that this is a bulk
extraction rather than a solid phase extraction
 1.2 Historical development of separation and preconcentration methods
method. The main goal is to collect but not to
discard the compounds of interest, preferably
by preconcentrating them from a sample in
order to analyze and remove the unwanted
compounds, that is, those we do not wish to
analyze [130,131].
Solid phase extraction can be considered
low-performance liquid chromatography, used
in two extreme conditions: minimum and max-
imum retention during extraction (adsorption)
and elution (desorption), respectively. In these
systems, organic, inorganic or biological ana-
lytes are adsorbed on the sorbent in column,
and the sorbent is washed with pure water to
remove the matrix components. In this way,
while analytes are adsorbed on the sorbent,
unwanted matrix components are removed.
Then analytes retained on the sorbent are
eluted with a proper liquid phase. Elution
reverses the adsorption process, leading to the
analytes passing from the adsorbed layer into
solution again. Concentrations of the analytes
in the last phase are measured by a detection
system. The mechanism of adsorption of ana-
lytes on active sites of the surface sorbent
can be explained the dipole-induced dipole,
dipole dipole, hydrogen bonding, ionic bond-
ing, covalent bonding and dispersive interactions
[130 144].
The US Public Health Service group
(Cincinnati, Ohio, United States) published a
pioneering study based on the column system
for the enrichment of organic compounds
[132]. They filled 1200 1500 g of granular acti-
vated carbon in an iron cylinder for the precon-
centration of organic compounds in raw and
filtered surface waters. Using these carbon fil-
ters, they sampled at six water plants along the
Ohio River from Midland, Pennsylvania,
United States, to Louisville, Kentucky, United
States, during the spring of 1949. The carbon
filters through which the known volume of
water samples passed were removed and dried
with air. The organic compounds on the sur-
face of carbon filters were extracted with
New Generation Green Solvents for Separation and Preconcentration
25
diethyl ether in the Soxhlet extractor. Five
groups of organic residues were formed, and
specific chemicals were identified within these
groups [132].
Then the carbon filter method was used by
Rosen and Middleton for the determination of
the petroleum refinery wastes in surface
waters. For this purpose, thousands of gallons
of surface water are pumped into the solid
phase sorbent system consisting of a carbon fil-
ter to enrich the petroleum components on the
carbon filters. The compounds resting on the
sorbent were then desorbed with chloroform
and separated by column adsorption chroma-
tography. Concentrations of these components
were analyzed by infrared spectroscopy at the
parts per million level [133]. The same working
group combined the carbon filter system with
adsorption chromatography and infrared spec-
trometry. This combined method was used to
isolate, enrich, and detect insecticides com-
monly found in surface waters. As with the
previous method, they pumped thousands of
gallons of surface water into the solid phase
sorbent system 1833 in ID (1 in 52.54 cm)
inches consisting of a carbon filter to precon-
centrate the insecticides on the carbon filters.
These applications increased the popularity of
activated carbon use for analytical applications
[134].
The problems encountered due to the non-
homogeneous structure of activated carbon
have seriously prevented the use of the carbon
filter method in solid phase extraction applica-
tions. Problems in the use of activated carbon
such as irreversible adsorption, chemical reac-
tions during extraction and low recovery
values have led scientists to investigate other
sorbents.
But it should be noted that activated carbon
has an important role in the development of
the solid phase extraction method. Moreover,
the use of activated carbon in the enrichment
of trace organic analytes has led to the interest
of scientists. It should be noted that, even
26 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods
though classic activated carbon is losing its
popularity in the separation and enrichment of
organic and inorganic analytes, it is still very
popular in water treatment technologies
[135 160].
In this sense, solid phase extraction only
became a scientific technique in the 1970s. The
process of development as an analytical prac-
tice progressed from initial latency (before
1968) through the next three stages.
1. 1960 77: The period of searching for the
most suitable materials for SPE
2. 1977 89: The period of technical
developments in SPE
3. 1989 present: The modern period of SPE
In solid phase extraction methods, advance-
ment has been stepped up in order to meet the
needs of the time. This progress is closely
linked to the development of new-generation
technologies, the production of new solid
phase materials, and the development of prod-
uct diversity.
Solid phase extraction methods can be
divided into three basic groups based on the
adsorbent used: (1) inorganic materials,
(2) organic materials, and (3) organic/
inorganic hybrid materials. Up to now, many
adsorbents have been used in SPE such as gel-
type, macroporous and hypercross-linked,
and ion-exchange polymer resins, silica-based
nano/microsized materials, carbon-based
nano/microsized materials including acti-
vated carbon, graphitized carbon black (GCB),
porous graphitic carbon (PGC), graphene, gra-
phene oxide (GO), carbon nanotubes (CNTs),
fullerenes (C60 or C70), metal oxide micro/
nanoparticles including TiO2, SiO2, Fe3O4,
Fe2O3, Al2O3, restricted-access materials
(RAM), monolithic materials, magnetic mate-
rials, metal organic frameworks (MOFs),
among others [135 197].
For a sorbent to be used in SPE extraction
methods, one or more of the following features
must be present (Fig. 1.3).
New Generation Green Solvents for Separation and Preconcentration
But in the first applications of solid phase
extraction methods, the following adsorbents
were used: (1) porous polymeric sorbents cate-
gorized as gel-type, macroporous, and
hypercross-linked sorbents, (2) ion-exchange
resins, (3) silica-based sorbents, modified with
C18, C8, phenyl, CH, CN, or NH2 groups, (4)
carbon-based sorbents, including GCB and
PGC [132 134].
Solid phase extraction was used from the
1940s to the 1970s, when synthetic polymers
such as porous polymeric sorbents (primarily
the macroporous polystyrene-divinylbenzene
[PS-DVB]) were first reported in the literature
[130,138]. As polymeric supports, the commer-
cially available porous polymeric sorbents cate-
gorized as gel-type, macroporous, and
hypercross-linked sorbents polymer-based
resins are very promising solid phase extrac-
tion materials because of the their effective
chemical and physical features such as high
surface area, purity, strength, no solubility in
aqueous and organic solvents, and improved
pore structures and adsorption capacity, which
is comparable with activated carbon around
1000 m2 g21. Moreover, they can be designed
in many different forms to control their resin
structure, pore size distribution, internal sur-
face area, polarity and so on. For example, the
hydrophobic character (apolar) of polystyrene-
divinylbenzene resins is dominant; hence it can
be used for solid phase extraction of hydropho-
bic analyte or analytes, while hydrophilic
(polar) character of polyacrylate-divinyle ben-
zene resins is dominant so it is suitable for
solid phase extraction of hydrophilic analyte or
analytes. They have been used frequently since
the mid-1960s in the separation and preconcen-
tration of trace organic, inorganic and bioactive
species.
Important improvements on separation and
preconcentration methods were lived in the
1960s by production of the macroporous resins
as adsorption material [136 139]. They are
capable of effectively adsorbing organic,
 1.2 Historical development of separation and preconcentration methods
inorganic and biological compounds because
of their porous polymeric matrix. These proce-
dures are generally called solid phase extrac-
tion (SPE), liquid solid extraction (LSE),
liquid solid adsorption (LSA), or sorbent
extraction. In this book, the most common
name, solid phase extraction (SPE) will be
used. Developments in the usage of resins has
played an important role not only in solid
phase extraction studies but also in the devel-
opment of wastewater treatment methods and
recovery of valuable metals (Au, Pt, Pd, etc.),
minerals (Ca, Mg etc.), radioactive species (U,
Th, Ac, etc.), organic compounds (antioxidant,
azo dyes, pharmaceutical compounds) and bio-
logical materials (proteins, amino acids, DNA,
RNA, etc.).
In the 1960s, Amberlite XAD-1, a cross-linked
polystyrene resin, was fabricated by Rohm and
Haas [137]. By the end of the 1960s, polymer
New Generation Green Solvents for Separation and Preconcentration
27
FIGURE 1.3 Features of sor-
bents used in solid phase extrac-
tion/microextraction procedures.
materials were used first a first time by Riley
and Taylor for the separation and preconcentra-
tion of organic compounds in water samples.
They used a column system designed with a
1 cm diameter, Amberlite XAD-1 resin fastened
to a column depth of 7 cm. After the SPE proce-
dure, concentrations of organic analytes in sea-
water samples were measured by fluorimetry,
photometry, 14C counting, and GLC detection
systems. Moreover carbohydrates, amino acids,
and humic acids were studied [137].
Many types of polymeric resins were pro-
duced in the 1970s, and they became a focus of
intense interest for separation and preconcen-
tration applications.
In 1972 Burnham et al. used styre-
ne divinylbenzene Amberlite XAD-2 and
ethylene dimethacrylate-XAD-7 resins for
solid phase extraction to extract trace organic
contaminants in potable water. Particularly,
28 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods
the resins have been used to preconcentrate
neutral organic compounds, metal-ligand com-
plex, weak organic acids, and bases from aque-
ous solutions at parts per billion levels [138]. In
1973 Harvey et al. used an SPE liquid liquid
extraction (LLE) approach with XAD-2 in order
to determine polychlorinated biphenyls (PCBs)
in North Atlantic Ocean water [140].
In the same years, apart from Amberlite
resins, other polymeric materials for precon-
centration studies were employed for the first
time. Gesser et al. used porous polyurethane
foam for the solid phase extraction of poly-
chlorinated biphenyls (PCB) in water samples
prior to GC analysis [141].
Mieure and Dietrich used Chromosorb 102
filled a column in order to extract and precon-
centrate organic compounds from water sam-
ples. After the SPE step, the Chromosorb 102
column was then coupled to the head of ana-
lytical column of a GC system, and organic
compounds were thermally desorbed by the
flow of the carrier gas [142].
In 1974 Junk et al. reported a comprehensive
preconcentration strategy by using XAD-2 resin
[143]. In this study, they used a small column
of a macroreticular resin to preconcentrate and
isolate the organic impurities from water with
solid phase extraction. In this study, many
model organic compounds between parts per
billion and parts per trillion levels were added
into water samples, and the organic com-
pounds adsorbed was eluted with diethyl ether
and analyzed by gas chromatography.
Recovery studies for organic compounds
proved the applicability of polymer-based
adsorbents such as styrene divinylbenzene
materials for trace analysis applications. After
these important steps, hundreds of articles
based on the use of polymers such as styre-
ne divinylbenzene, ethylene dimethacrylate
copolymers (Amberlite XAD-7 and Ambelite
XAD-8), separon and spheron acrylate copoly-
mers, porapaks, chromosorbs, polypropylene,
New Generation Green Solvents for Separation and Preconcentration
polytetrafluoroethylene, polyurethanes, poly-
urethane foam, tenax, ion-exchange resins,
among others, have been published in the ensu-
ing decade for the separation and preconcentra-
tion of organic, inorganic, and bioactive species
[144 153].
A few examples of the first application of
polymer-based solid phase extraction applica-
tions are described next.
In 1978 Tateda and Fritz prepared a mini
solid phase extraction column system
(1.2 1.8 mm 3 25 mm) containing Amberlite
XAD-4 resin or Spherocarb to preconcentrate a
wide range of organic contaminants from
water samples. After the SPE method, the
adsorbed analytes were treated with a microli-
ter volume of organic solvent and analyzed by
gas chromatography. They obtained excellent
recovery results for the studied organic com-
pounds. The adsorption and desorption perfor-
mances of Amberlite XAD-4 and Spherocarb
adsorbents were compared. It was found that
Amberlite XAD-4 and Spherocarb adsorbents
can be used for solid phase extraction of
organic compounds in wastewater samples
[144].
In 1983 Zygmunt et al. used LC-grade styre-
ne divinylbenzene polymer for the separation
and preconcentration of 20 pollutants in indus-
trial wastewater prior to LC determinations.
With this developed procedure, it was possible
to analyze 20 different organic pollutants at
parts per billion levels [145].
In 1985 Tabor and Loper used a special col-
umn system containing Amberlite XAD-2 and
Amberlite XAD-7 resins for the separation
and preconcentration of mutagenic residue
organics in drinking water samples. The
organic residues adsorbed were eluted with
organic solvents prior to bioassay for mutage-
nicity [146].
Richard and Junk reported a combination
use of Amberlite XAD-4 resin based solid
phase extraction and a GC-electron capture
 1.2 Historical development of separation and preconcentration methods
detection system to determine parts per billion
levels of munitions in water samples. They
tested some of nitrobenzene, nitrotoluene and
triazine derivatives as model analytes. They
used solid phase extraction in the field instead
of the laboratory. Hence, the transportation
cost of water samples to the laboratory was
eliminated [147].
Pankow et al. developed an electronically
controlled rain sampler and solid phase extrac-
tion system for the collection and preconcen-
tration of organic compounds in rain water,
such as naphthalene, hexachlorocyclohexane
( HCH), acenaphthylene, phenanthrene, and
fluorene in 1984. They used this system for the
in situ filtration of the collected sample and
preconcentration of apolar organic species
with cartridges of the sorbent Tenax GC.
Moreover a ion-exchanging resin cartridge
was used to preconcentrate organic acids in
rain water. After the SPE procedure, gas chro-
matography mass spectrometry (GC MS)
was used to analyze 27 compounds in the rain
water [148].
In 1987 Bitteur and Rosset compared the
trace enrichment performances of octadecyl-
bonded silica and styrene divinylbenzene
copolymer sorbents [149]. In 1988 Pankow
et al. suggested a solid phase extraction and
gas chromatography procedure for analysis of
various semivolatile compounds in water sam-
ples. Semivolatile compounds adsorbed on the
Tenax cartridges (0.68 cm3 of bed volume)
were desorbed thermally into a fused-silica
capillary gas chromatography column [150].
The first applications of the solid phase
extraction method were carried out on the cap-
illary columns, which were packed with gram
levels of sorbent. Columns were fabricated
from quartz, polyethylene, or poly-
tetrafluoroethylene (PTFE) in 1977 and this
step can be considered an important revolution
in preparing a more suitable, simpler and
more effective solid phase extraction system.
New Generation Green Solvents for Separation and Preconcentration
29
This technique was introduced in 1978 on the
cover of a catalog of laboratory equipment. In
the same year, the first article in this area was
published. The published article described the
use of a C18 silica based solid phase extrac-
tion system as a commercial product (Sep Pak
C18 “cell”) to remove histamine from wine
samples. The commercial chromatographic sor-
bents and reverse phases capable of extracting
the desired analytes from aqueous phases
marked the start of solid phase extraction
applications in the environmental, analytical,
pharmaceutical, and clinical markets. These
important developments led to the transforma-
tion of the solid phase extraction method from
a laboratory innovation into a accepted and
widely used form of chromatographic applica-
tion [150,152,153].
At the end of the 1980s, the production of
support materials called membrane and solid
phase extraction discs led to an innovative
period in solid phase extraction methods. Such
apparatus consists typically of discs containing
glass fiber pads, glass fibers, or a Teflon matrix
with a sorbent stuck between them. As a result
of these developments, a very short and very
thick solid phase extraction cartridge was
obtained [154 156].
Packaged cartridges, columns or discs are
now used in virtually all laboratories in the
world where sample preparation is needed.
Designs for housing SPE sorbents, from
“pipette tip” models to glass minicolumns or
plastic with steel or Teflon or polymer frits
have all been well established. Some solid
phase extraction apparatuses are fabricated for
vacuum use, facilitating the sample to be
“pulled” through, while others are used for the
sample to be “pushed” through the sorbent.
However, for nearly 40 years, megacolumns
containing several grams of sorbent, extraction
membranes, or discs have become popular in
solid phase extraction applications because of
the increased market for SPE [150 156].
30 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods
Many publications on the use of silica since
1978 do not express the widely accepted term
“solid phase extraction.” Since this term has
not been used in the main title of many studies
based on sorption for so long, solid phase
extraction has been given different names dur-
ing its historical development (Fig. 1.4). Hence
it is necessary to look at the details of literature
FIGURE 1.4 Tracking solid phase extraction synonyms:
a list of terms used [130].
New Generation Green Solvents for Separation and Preconcentration
studies in order to understand the historical
developments of SPE.
Growth in the number of citations on solid
phase extraction started with the first use of
the SPE term by the employees of the J.T.
Baker Chemical Company [130]. When the last
half of the 1980s is examined, it is seen that
SPE studies were used in clinical, pharmaceuti-
cal and analytical applications. In the 1990s,
there is a rapid increase in the number of pub-
lications on the environmental applications of
SPE. It has been seen that solid phase extrac-
tion has been used frequently in all applicable
areas. Significant developments, important
applications, and milestones in solid phase
extraction methods for the preconcentration
and separation of trace analytes from past
years to the present will now be explained in
detail in the literature studies [157 161].
In 1977 Tjaden et al. used methyl silica as
the solid phase in the high-pressure liquid
chromatography (HPLC) system for the sepa-
ration of barbiturates. They obtained good
results for the determination of barbiturates at
trace levels in blood samples [157]. In 1985
Kubo et al. provided an accurate and simple
solid phase extraction method for the separa-
tion of trace levels of procainamide (PA) and
N-acetylprocainamide (NAPA) in breast milk
and serum samples prior to their high-
performance liquid chromatography determi-
nations [158]. In 1986 Bardalaye and Wheeler
developed a solid phase extraction method for
preconcentration of trace amounts of triazine
herbicides, prometryn, arnetryn and terbutryn
in water. They used chromatographic-grade
silica gel particles, chemically modified with a
nonofunctional C8H17 group. In the modifica-
tion procedure, the C8H17 group covalently
bonded on the surface of silica gel particles.
The triazine herbicides adsorbed on the silica
gel particles were eluted by using 2-propanol.
Concentrations of prometryn, arnetryn, and
terbutryn in the last phase were analyzed
by capillary gas chromatography with a
 1.2 Historical development of separation and preconcentration methods
nitrogen-phosphorus detector. The limits of
detection values for analytes were found in the
range of 0.1 10 μg L21 [159].
At this time, as a result of the developments
in instrumental devices, the transition from off-
line to online solid phase extraction systems
has found a lot of application areas and has
gained momentum. These developments have
led to new horizons in the minds of scientists:
automatic sampling and detection, minimum
sample manipulation, improved sensitivity
and selectivity, completion of the preconcentra-
tion and analysis steps. The combined usability
of online SPE methods with spectroscopic and
chromatographic methods such as AAS, AFS,
AES, UV VIS spectroscopy, GC, GC MS, LC,
LC MS, HPLC, and the like, is one of the most
important steps in the development of this
method [160 168].
In the online solid phase extraction and
detection systems, first, polymer-based and
carbon-based sorbents were used. A few
examples of the first online solid phase
extraction and detections applications are
described here. Liska et al. suggested an
online solid phase extraction and column liq-
uid chromatography procedure for 50 pesti-
cides in surface water at trace levels. They
accomplished online preconcentration of pes-
ticides on a styrene divinylbenzene copoly-
mer (PLRP-S) precolumn prior to liquid
chromatography detection [160]. In an
another study provided by Hennion and
Coquart, solid phase extraction performers
such as porous graphitic carbons, nonpolar
styrene divinylbenzene copolymers, and
alkyl-bonded silicas as reversed phase extrac-
tion sorbents were compared by the online
mini column preconcentration and liquid
chromatographic separation system for polar
organic compounds in environmental water
samples. The results showed that porous gra-
phitic carbon was the most suitable sorbent
for the preconcentration of trace levels of
polar organic compounds [161].
New Generation Green Solvents for Separation and Preconcentration
31
Liska et al. carried out a comprehensive
study to compare the sorption features of 10
different sorbents used in preliminary precon-
centration studies. They used online a solid
phase extraction system to compare the
adsorption features of sorbents, including three
C18 bonded polymers with neutral, weak
anion- and cation-exchange properties and two
C18, a phenyl- and a diol-bonded silica,
together with a styrene divinylbenzene copol-
ymer and two carbon phases obtained from the
controlled pyrolysis of saccharose (CF) and cel-
lulose (CPP-50). The adsorption features of the
selected sorbents were checked on the model
solutions, including atrazine, aniline, 2-
nitrophenol, diuron, and 2-chloroaniline. The
obtained results showed that a styrene-
divinylbenzene copolymer with a C18 silica-
bonded analytical column was the optimum
and most effective solid phase extraction sys-
tem for preconcentration applications. This
study also shed light on the solid phase extrac-
tion studies to be done later [162].
In 1994 a flow injection online SPE-AAS
method was provided by Lancaster et al. in
order to preconcentrate and analyze metal ions.
They prepared ligand-adsorbed hydrophobic
solid phase extraction material by using 4-(2-
pyridylazo)resorcinol, diethyldithiocarbamate
(DDC), 1-(2-pyridylazo)-2-naphthol, quinolin-8-
ol, and dithizone and checked the adsorption
efficiency of these new ligand-adsorbed SPE
materials. The diethyldithiocarbamate- (DDC)
and quinolin-8-ol-adsorbed SPE were selected
to preconcentrate lead and copper ions. They
obtained preconcentration factors in range of 50
and 100 with parts per billion levels of detec-
tion limits [151].
A comprehensive online solid phase extrac-
tion study, which compared SPE performance
of different sorbents, was reported in 1995 by
Naghmush et al. [163]. In this study, they
checked the online SPE performances of com-
mercial chelating sorbents (Spheron Oxin 1000
and Chelex 100), nonpolar sorbent Amberlite
32 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods
XAD-2 modified with Pyrocatechol Violet and
several cation-exchange resins, C18 sorbent
nonmodified and modified with 8-quinolinol
or Pyrocatechol Violet, cellulose sorbents with
carboxymethyl groups, and phosphonic acid.
Pb(II) was selected as a model analyte, and
online analysis was carried out with FAAS.
Functionalized cellulose sorbents were found
as the best sorbent material in this study. The
detection limit for Pb(II) was found as
0.17 μg L21 at a flow rate of 7 mL min21 [163].
A different online solid phase extraction
thermospray tandem mass spectrometry (TSP-
MS-MS) combination was applied for the pre-
concentration and determination of β-agonists
in urine of cattle. In this method, a sorbent hav-
ing both hydrophobic and ionic properties
were used [164]. Hollenbach et al. provided a
flow injection (FI) analysis procedure consist-
ing of SPE and ICP-MS steps in order to ana-
lyze 230Th, 240Pu, 239Pu, and 234U in soils. The
elution solution was injected into the nebulizer
of the ICP-MS. A 20 preconcentration factor
was obtained in this method. The detection
limits for 230Th, 240Pu, 239Pu, and 234U were
found as 4, 0.3, 0.2, and 3 ng kg21, respectively
[165].
In 1997 Daghbouche et al. combined a fully
designed online solid phase extraction FT-IR
methods to analyze caffeine in soft drinks. The
samples, degasified, were directly passed
through a C18 SPE cartridge by using a flow
manifold. Caffeine adsorbed on the C18 was
eluted with chloroform and analyzed at 1658
cm21 by using a flow injection FT-IR system.
Limit of detection, relative standard deviation,
and sampling frequency values were
10 μg mL21, 3.5%, and 30 h21, respectively
[166].
The 1990s are an important turning point for
solid phase extraction methods, since new
extraction devices, new-generation sorbents,
and microvolume systems were introduced for
the first time in these years. One of the most
important of these developments is the use of
New Generation Green Solvents for Separation and Preconcentration
membrane extraction discs. This system was
first used by Hagen et al. in 1990 [167]. The
researchers prepared membrane discs by mod-
ifying a network of PTFE fibrils with hydro-
phobic octyl and octadecyl-bound silica (47 or
25 mm diameters) and used these discs in the
reverse phase solid extraction of environmental
pollutants from aqueous media. Water samples
were passed through the disc under optimum
test conditions, and thus organic species were
adsorbed on the disc. After the adsorption pro-
cess, the organic species retained were eluted
with a small volume of eluent and given to the
chromatographic separation system. In last
step, the new method was used for analysis of
parts per billion levels of phthalates, pesticides
and polychlorinated biphenyls in tap ground-
and surface water samples [167]. Membrane
discs composed of the fibrilized PTFE matrix
were modified with different nanoparticles,
silicas, polymers, or ion exchangers. High
recovery values can be obtained at a high sam-
ple flow rates because of the internal structure
of the membrane discs. The SPE method based
on membrane extraction discs can be applied
in online and offline modes for sample
solutions and can be combined with chro-
matographic and spectroscopic detection sys-
tems. Membrane discs are widely used for the
separation and preconcentration of organic and
inorganic analytes in different matrix media
[168 174].
Antibodies have been used frequently in
biosensors, affinity chromatography and very
popular immunoanalysis studies for 50 years.
By the end of the 1980s, researchers realized
that the analyte antibody interaction can be
used in the solid phase extraction method and
thus a new SPE application, which is classified
as immunoaffinity, has emerged. In these sys-
tems, immunosorbents are obtained by fixing
the antibodies in monoploid or polyploid form
produced against the target compounds onto a
support material. Immunosorbents were first
used by Farjam et al. in 1988 for the isolation
 1.2 Historical development of separation and preconcentration methods
and enrichment of 19-nortestosterone from bio-
logical samples [175]. In this study, scientists
suggested an automated extraction and analy-
sis procedure for the anabolic hormone β-19-
nortestosterone (β-19-NT) and its metabolite
α-19-nortestosterone (19-norepitestosterone) in
calf urine samples. In this method, the liquid
chromatographic column-switching system
was used. For this purpose, they prepared an
immunoaffinity precolumn by modifying the
sepharose with polyclonal antibodies against
α-19-NT and used a C18-bonded silica-loaded
precolumn as a second column and an analyti-
cal C18 column [175].
Twenty-five milliliters of urine sample were
passed through the antibody-immobilized pre-
column to allow the analytes to adsorb on the
column. The analytes were then selectively
desorbed with a solution containing an amount
of the steroid hormone norgestrel that was
cross-reacted with analytes and transferred to
the analytical column via a second precolumn.
The recovery of β-19-NT in spiked urine sam-
ples was over 95%. The detection limit was
50 ng L21 for a 25 mL urine injection. The sys-
tem showed no loss of analytical performance
over a 6-month period, during which about
100 samples were analyzed with the same
immuno precolumn. Recovery values of more
than 95% with 50 ng L21 of detection limit for
analytes were obtained. The immunosorbent
column was used over a 6-month period for
about 100 samplings [175]. Until now, the
immunosorbents obtained from different anti-
bodies have been widely used as an effective
solid phase extraction material for trace ana-
lytes such as pesticides, herbicides, active
ingredient, PAHs, and the like in environmen-
tal, biological, and pharmaceutical samples
[154,175 178].
The need for the development of analytical
methods that provide improved selectivity
and sensitivity has accelerated the studies on
the development of molecularly imprinted
polymers (MIPs) for solid phase extraction
New Generation Green Solvents for Separation and Preconcentration
33
applications. In the molecular imprinting
technique, a target molecule as a template is
used to fabricate highly selective binding
matrices by applying a casting methodology.
MIPs are obtained by producing highly cross-
linked polymers in the presence of a template
molecule, leading to the formation of func-
tional groups in a specific arrangement
within the polymer. High selectivity is
achieved for analyte or analytes since the
MIPs show antibody-like affinities to specific
analytes. Hence molecularly imprinted solid
phase extraction (MISPE) applications elimi-
nate the needs of a chromatographic separa-
tion of analytes, which lead to faster and
simpler access to analytical results. Sellergren
introduced a different MISPE method for the
first time in 1994 [179]. Pentamidine (PAM) is
used as a drug molecule for the treatment of
AIDS-related pneumonia. In this study, scien-
tists compared the solid phase extraction
performances of PAM-selective polymer
and benzamidine-(BAM-)imprinted reference
polymer for the separation and preconcentra-
tion of PAM at trace levels. The enrichments
factors for PAM-selective polymer and ben-
zamidine-(BAM-)imprinted reference poly-
mer were found as 54 and 14, respectively.
The PAM concentration in eluent was
directly analyzed in urine samples since the
use of the high selectivity of polymer elimi-
nated the second chromatographic separation
step [179].
Nanotechnology has been a multidisciplin-
ary discipline that has, in the last 35 years,
brought innovation to all fields, from environ-
mental science, medical science, engineering,
pharmacy, science, and chemistry to veteri-
nary science. Nanotechnology is a science that
examines the production, characterization,
and properties of new and revolutionary
materials of 100 nm or less in size and paves
the way for these materials to be used in dif-
ferent areas. One of the branches of science
affected by developments in nanotechnology
34 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods
is sample preparation methods in analytical
chemistry [177,180 182].
The most important developments in the
solid phase extraction method were experi-
enced with nanotechnology. Nanotechnology
began to affect solid phase extraction with the
discovery of fullerene (C60) as a carbon allo-
trope (zero-dimensional) in 1985 [183].
Scientists noticed that, as the size of the mate-
rial becomes smaller, most features of the
material may change. The discovery of this
new stable form of carbon, which differs from
graphite and diamond, has led scientists to
research other types of carbon. In 1990 when
the C60 was found to be able to be produced
in a simple arc-evaporation apparatus (avail-
able in many laboratories), research on this
topic accelerated. This development was fol-
lowed by the discovery of carbon nanotubes
as one-dimensional material (single-walled,
double-walled, and multiwalled CNTs) as
another carbon allotrope in 1991. Iijima used
arc-evaporation apparatus to fabricate CNTs
[184]. CNTs are graphene sheet structures
rounded into the shape of a cylinder. The dis-
covery of the fullerene and carbon nanotubes
has led to the idea that nanomaterials offering
high surface area ( . 1000 m2 g21) can be
effectively used in solid phase extraction.
Transition from micro size to nano size has
caused excitement over scientists working in
solid phase extraction, as in all branches of
science.
Fullerenes and carbon nanotubes became
very attractive materials after the discovery of
their wonderful physical, chemical, and ther-
mal stability, high surface area, and improved
π π interactions. The fact that all adsorbents
used up to 1990s could not be used in the
extraction of polar and apolar analytes at the
same time, which was the most important dis-
advantage limiting the applicability of the solid
phase extraction method. But the usability of
these carbon nanomaterials for either nonpolar
analytes or polar analytes with the
New Generation Green Solvents for Separation and Preconcentration
functionalization of these nanomaterials led to
a significant increase in the use of solid phase
extractions in a wide range [185 187].
In these years, a race has started for the pro-
duction of new nanomaterials and important
nanomaterial production methods such as arc-
evaporation, vapor deposition, solvothermal,
sol gel, in situ growth/polymerization, copre-
cipitation, electrospinning, and direct coating
were introduced. These nanomaterial produc-
tion methods have led to the discovery of
nanosized materials based on carbon (CNT,
fullerene, nanodiamond, carbon dot, etc.),
nanofibers, metals (Cu, Au, Pd, Pt, etc.), metal
oxides (SiO2, TiO2, Al2O3, etc.), magnetic nano-
particles (Fe3O4, γ-Fe2O3, ZnFe2O4, and
ZnFe2O4), and polymers, which are commonly
used in solid phase extraction [185 191].
Analytical chemists paid more interest to
these nanomaterials than to other classic mate-
rials used in solid phase extraction because of
the their high surface area, high adsorption
capacity, ability to be modified with different
organic and inorganic matrices, corrosion resis-
tance, mechanical, and chemical and thermal
stability. For 25 years, nanomaterials have been
used in the solid phase extraction of almost all
of the organic, inorganic and bioactive traces in
environmental, food, drug and biological
samples.
In 2004 graphene (G) was introduced as one
of the most important carbon materials with
a hexagonal structure consisting of sp2 hybrid-
ized carbon atoms arranged in a honeycomb
pattern. Graphene is characterized as the
mother of all carbonaceous materials because it
can be used not only in the production of car-
bon nanotubes by “rolling” but also as a build-
ing block of graphite by stacking together with
strong Van der Waal forces [192]. Graphene
provides some very good and unique features
to users, such as high electrical conductivity,
effective thermal stability, high Young’s modu-
lus, high surface area (2630 m2 g21), zero band
gap, and transparency for monolayer G sheets.
 1.2 Historical development of separation and preconcentration methods
Due to these unique features, graphene is one
of the most commonly used materials in many
fields such as electronics, medicine, pharmacy,
engineering, physics, chemistry, biology and
others. Perhaps there is no area left in which to
use graphene [192].
After the discovery, graphene and graphene
oxide are among the most frequently used
new-generation materials used in the enrich-
ment of almost all organic and inorganic spe-
cies found in environmental samples.
Graphene, mainly because it is a material with
a theoretically large surface area (2630 m2 g21),
is one of the most commonly used materials in
adsorption-based methods, and it provides
high selectivity and adsorption capacity for
analytes by providing the analytes noncovalent
interactions such as π π stacking, Van der
Waals, hydrogen bonds, hydrophobic effect,
dispersing forces, and electrostatic and dative
bonds [193 195].
In 1990 an important revolution occurred
with the introduction of the SPME, as one of
the most popular green techniques, by
Pawliszyn and Arthur [196,197]. Since then, the
solid phase microextraction method has
become one of the most widely used methods
in the separation and enrichment of organic,
inorganic and bioactive species found in vari-
ous matrix environments. Conventional solid
phase extraction procedures have some disad-
vantages such as slow extraction process; use
of excessive amounts of sorbent, reagents, and
solvents; formation of excess waste after the
process; necessity of high volume or amount of
samples; the need for complicated and expen-
sive extraction apparatus; and the inability to
obtain the desired sensitivity. SPME has
proven itself as a successful method for elimi-
nating most of these drawbacks. The fact that
the solid phase microextraction method can be
applied to all samples in different physical
states—liquid, gas and solid—has made a sig-
nificant contribution to its being one of the
most important techniques available all over
New Generation Green Solvents for Separation and Preconcentration
35
the world. Hence SPME is a hot topic and
taken its place as a separation and preconcen-
tration method in sample preparation laborato-
ries all over the world [196 201].
SPME consists of two main steps [11]:
1. Adsorption of analytes on the sorbent
surface at the optimum conditions and
2. Desorption of analytes by applying high
temperature or elution.
In SPME, fine fibers made of molten silica
coated with a suitable sorption material for the
adsorption of the target analytes onto the solid
phase are used. The analytes in the sample are
dispersed between the coated fiber and the
matrix. In this way, both the separation and
the enrichment processes are performed. Then
the desorption of analytes on the fiber are per-
formed by applying high temperature, leading
to the release of analytes in gaseous form or
eluting with organic or inorganic solvents.
Analytes in gas form are transported to the
detection system, generally a GC column, or
elution solutions are injected into the detection
systems. According to the interaction of the
fiber on the solid phase with the sample, the
solid phase microextraction method can be
applied in nine different ways:
1. direct (direct immersion, DI);
2. adsorption from the headspace (HS);
3. in-tube SPM;
4. solid phase dynamic extraction (SPDE);
5. micro-SPE (μ-SPE);
6. adsorptive microextraction (AμE);
7. stir-cake sorptive extraction (SCSE);
8. rotating-disc sorbent extraction (RDSE); and
9. stir-rod sorptive extraction (SRSE).
As detailed explanations about these meth-
ods are made in Chapter 3, Historical back-
ground: milestones in the field of development
of analytical instrumentation, the methods in
this section have been mentioned only in
headings.
36 1. Historical backgrounds, milestones in the field of development of separation and preconcentration methods
1.3 Conclusions
In a world where technology, industrializa-
tion and consumption are increasing day by
day, there will be significant increases in the
amount of organic, inorganic, and biological spe-
cies in living areas, in living organisms and in
the ecological environment. Accurate and sensi-
tive analysis of these toxic species in all environ-
mental samples, as well as in food, water,
pharmaceutical, and similar consumer products
directly related with living cells, is becoming an
ever more important issue. Therefore as life goes
on, separation and preconcentration-based sam-
ple preparation methods for trace organic and
inorganic species will remain popular. Despite
the rapid development in separation and
preconcentration-based sample preparation
methods the past 100 years and more, the ever
increasing production and consumption of
human beings are signs that this trend will con-
tinue rapidly with the contributions of other dis-
ciplines such as nanotechnology, material
science, engineering, and others.
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*** START OF THE PROJECT GUTENBERG EBOOK SÄUGETHIERE VOM

CELEBES- UND PHILIPPINEN-ARCHIPEL ***
[Inhalt]

[I]

[Inhalt]
 Abhandlungen und Berichte des
Königlichen Zoologischen und
Anthropologisch-Ethnographischen
Museums zu Dresden 1896/97

Nr. 6

Säugethiere
vom
Celebes- und Philippinen-
Archipel

I
 von
A. B. Meyer

Mit 9 colorirten und 6 Lichtdruck-Tafeln

Verlag von R. Friedländer & Sohn in Berlin

1896
[III]

[Inhalt]

Dem Andenken
Alexander Schadenberg’s
gewidmet [V]

[Inhalt]
 Inhaltsverzeichniss
Seite

Widmung III
Tafelerklärung VII
1. M a c a c u s m a u r u s F. Cuv. mit Taf. I, II Fig. 1–2 und III Fig. 1–2 1
2. und 3. M a c a c u s c y n o m o l g u s L. und p h i l i p p i n e n s i s Js.
Geoffr. 4
4. und 5. C y n o p i t h e c u s n i g e r (Desm.) und n i g r e s c e n s
(Temm.) mit Taf. II Fig. 3–4 und III Fig. 3–4 5
6. Ta r s i u s f u s c u s Fisch.-Waldh. 8
7. Ta r s i u s s a n g i r e n s i s n. sp. 9
8. Ta r s i u s p h i l i p p e n s i s A. B. Meyer mit Taf. IV 9
9. Ta r s i u s s p e c t r u m (Pall.) 9
10. P a r a d o x u r u s m u s s c h e n b r o e k i Schl. mit Taf. V und VI 10
11. B u b a l u s m i n d o r e n s i s Heude mit Taf. VII und VIII 12
12. B a b i r u s a a l f u r u s Less. mit Taf. IX 15
Vorkommen und damit in Verbindung stehende Fragen 15
Zahnformel 22
Bewehrung der Sau 23
13. S c i u r u s t o n k e a n u s n. sp. mit Taf. X Fig. 1 25
14. S c i u r u s l e u c o m u s M. Schl. mit Taf. X Fig. 2 25
15. S c i u r u s r o s e n b e r g i Jent. mit Taf. X Fig. 3 26
16. S c i u r u s t i n g a h i n. sp. mit Taf. X Fig. 4 27
17. S c i u r u s s t e e r i Gthr. 27
18. S c i u r u s m i n d a n e n s i s Steere mit Taf. XI Fig. 1 28
19. S c i u r u s s a m a r e n s i s Steere mit Taf. XI Fig. 2 29
20. P h l œ o m y s c u m i n g i Wtrh. mit Taf. XII und XIII Fig. 1–2 29
21. C r a t e r o m y s s c h a d e n b e r g i (A. B. Meyer) mit Taf. XIII Fig.
3–6 und XIV 32
22. P h a l a n g e r c e l e b e n s i s Gr. mit Taf. XV Fig. 1 33
23. P h a l a n g e r s a n g i r e n s i s n. sp. mit Taf. XV Fig. 2–3 34
24. P h a l a n g e r u r s i n u s (Temm.) 34
 Index 35

[VII]

[Inhalt]
 Tafelerklärung

Tafel I M a c a c u s m a u r u s F. Cuv. von Celebes. 1 fem. Seite 2 und 3

juv., 2 mas juv., 3 und 4 fem. juv., 5 mas ad. Circa ⅙
nat. Grösse.
Tafel II 1–2 S c h ä d e l von M a c a c u s m a u r u s F. Cuv. Seite 3
von Celebes, mas ad., norma facialis und lateralis.
¾ nat. Grösse.
3–4 S c h ä d e l von C y n o p i t h e c u s n i g e r Seite 5
(Desm.) von Nord Celebes, mas ad., norma facialis
und lateralis. ¾ nat. Grösse.
Tafel III 1–2 S c h ä d e l von M a c a c u s m a u r u s F. Cuv. Seite 3
von Celebes, mas ad., norma verticalis und basalis.
¾ nat. Grösse.
3–4 S c h ä d e l von C y n o p i t h e c u s n i g e r Seite 5
(Desm.) von Nord Celebes, mas ad., norma
verticalis und basalis. ¾ nat. Grösse.
Tafel IV Ta r s i u s p h i l i p p e n s i s A. B. Meyer von den Seite 9
Philippinen. Nat. Grösse.
Tafel V P a r a d o x u r u s m u s s c h e n b r o e k i Schl. von Seite 10
Nord Celebes, mas ad., fem. juv. ⅕–⅙ nat. Grösse.
Tafel VI 1 S k e l e t von P a r a d o x u r u s Seite 11
m u s s c h e n b r o e k i Schl. von Nord Celebes, mas
ad. ⅓ nat. Grösse.
2 Linke V o l a desselben Exemplares. Nat. Grösse. Seite 11

Nagel-
a–e oder Endballen
Metacarpophalangealballen
α–δ
Radialballen
r
Ulnarballen
u
Pisiformballen
P
1.–5.
I–VFinger
 3 Linke P l a n t a desselben Exemplares. Nat. Seite 11
Grösse.

Nagel-
a–e oder Endballen
Metatarsophalangealballen
α–δ
Tibialballen
t
Fibularballen
f
1.–5.
I–VZehe

Tafel VII B u b a l u s m i n d o r e n s i s Heude von Mindoro, Seite 14

mas ad. (stehend), fem. ad. (liegend) und fem. juv.
Circa 1⁄12 nat. Grösse.
Tafel VIII 1 S k e l e t von B u b a l u s m i n d o r e n s i s Heude Seite 14
von Mindoro, fem. ad. Circa ⅛ nat. Grösse.
2 S c h ä d e l derselben Art, fem. juv. ⅓ nat. Grösse. Seite 14
Tafel IX 1 Zwei aneinander gebundene, abnorm kreisförmig Seite 18[VIII]
gewachsene untere S c h w e i n e h a u e r von
Nordost Neu Guinea, Brustschmuck der
Eingebornen. Der obere Zahn ist ein linker, der
untere ein rechter. Nat. Grösse.
2 Abnorm. kreisförmig gewachsener Hauer im Seite 20
Unterkiefer von B a b i r u s a a l f u r u s Less., mas
ad. Nat. Grösse.
3 Vorderer Schädeltheil von B a b i r u s a a l f u r u s Seite 24
Less. von Nord Celebes, fem. ad. Nat. Grösse.
Tafel X 1 S c i u r u s t o n k e a n u s n. sp. von Nordost Seite 25
Celebes. Circa ¾ nat. Grösse.
2 S c i u r u s l e u c o m u s M. Schl. von Nord Seite 25
Celebes. Unter ⅓ nat. Grösse.
3 S c i u r u s r o s e n b e r g i Jent. von den Sangi Seite 26
Inseln. Circa ⅓ nat. Grösse.
4 S c i u r u s t i n g a h i n. sp. von Tagulandang. Seite 27
Circa ⅗ nat. Grösse.
Tafel XI 1 S c i u r u s m i n d a n e n s i s Steere von Seite 28
Mindanao. Circa ⅔ nat. Grösse.
 2 S c i u r u s s a m a r e n s i s Steere von Samar. Seite 29
Circa ⅔ nat. Grösse.
Tafel XII P h l œ o m y s c u m i n g i Wtrh. Circa ¼ nat. Seite 29
Grösse.

mas ad.
1 von Nord Luzon
2
fem. ad.
,, ,, ,,
3
mas ad.
,, ,, ,,
mas ad.
4 von Marinduque
5
fem. ad.
,, ,,
6
mas ad.
,, ,,
7
mas juv.
,, ,,

Tafel XIII 1 S k e l e t von P h l œ o m y s c u m i n g i Wtrh. Seite 32

fem. ad. von Nord Luzon. ⅔ nat. Grösse.
2 P e n i s k n o c h e n derselben Art. Nat. Grösse. Seite 32
3 S c h ä d e l von C r a t e r o m y s Seite 33
s c h a d e n b e r g i (A. B. Meyer) von Nord Luzon,
mas ad., norma lateralis. Nat. Grösse.
4 Derselbe, norma verticalis. Nat. Grösse. Seite 33
5 Derselbe, norma basalis. Nat. Grösse. Seite 33
6 U n t e r k i e f e r von demselben, von oben. Nat. Seite 33
Grösse.
Tafel XIV C r a t e r o m y s s c h a d e n b e r g i (A. B. Meyer) Seite 32
von Nord Luzon. ⅓–¼ nat. Grösse. Fig. 2 und 3 mar.
ad.
Tafel XV 1 P h a l a n g e r c e l e b e n s i s G r . von Nord Seite 33
Celebes. Circa ⅓ nat. Grösse.
2–3 P h a l a n g e r s a n g i r e n s i s n. sp. von den Seite 34.
Sangi Inseln. Circa ⅓ nat. Grösse.
[1]
[Inhalt]
 1. Macacus maurus F. Cuv.

Tafel I, II Fig. 1–2 und III Fig. 1–2

M a x W e b e r hat vor Kurzem (Zool. Ergebn. I, 103 1890) den

interessanten Nachweis geführt, dass Macacus maurus F. Cuv. und
Macacus ocreatus Ogilb. ausschliesslich auf Celebes 1 zu Haus und
wahrscheinlich identisch sind. Er hat damit das Dunkel, in dem diese
beiden Formen bisher standen, erhellt, und wenn er das Resultat
seiner scharfsinnigen Darlegung auch nur eine „supposition“ nennt
(p. 108), so glaube ich doch, dass es sich so verhält, wie er
vermuthet. Wenn W e b e r M. maurus aber lediglich auf Süd Celebes
und die Insel Buton beschränkt sein lässt 2, so ergeben zwei
Exemplare, die das Museum kürzlich von Tonkean, auf der
nördlichen Halbinsel, gegenüber dem Banggai Archipel 3, erhielt,
dass die Art eine viel weitere Verbreitung hat. Bis dahin war sie
allerdings nur aus dem Süden und von Buton bekannt geworden,
und zwar nach W e b e r (p. 103) von Maros, Tanralili, Bantimurung,
Parepare, Bonthain 4 und Katjang auf der Südwest Halbinsel, von
Kandari auf der Südost Halbinsel, sowie von Buton, ferner nach
S c h l e g e l (Cat. VII, 118 1876) und J e n t i n k (XI, 32 1892) von
Makassar, womit jedenfalls die w e i t e r e Umgebung der Stadt
gemeint ist, und von wo mir auch die Herren S a r a s i n schrieben,
dass sie M. maurus reichlich bekämen. Ich selbst beobachtete
diesen Affen am 16. Sept. 1871 in Mandalli, ungefähr in der Mitte
zwischen Makassar und Parepare; die holländischen Beamten, mit
denen ich zusammen war, wollten jedoch durchaus nicht zugeben,
dass ich einen schösse. Im October erhielt ich welche in Makassar
und reflectirte über die Unterschiede von Cynopithecus niger (Desm.)
bezüglich Färbung und Physiognomie; am 29. Oct. erlegte ich am
Wasserfalle von Bantimurung, östlich von Maros, ein grosses
Weibchen, das Milch hatte, und dessen Unbehaartheit mir auffiel.
Das auch geschossene Junge war im Dickichte nicht auffindbar. Der
Affe kam hier in Schaaren vor. Ich notirte auch, dass die
Gesässchwielen dunkel seien, gegenüber den rothen von C. niger in
der Minahassa, was mit W e b e r s Angabe (p. 104) nicht
übereinstimmt, der sie als „rosy“ angiebt.

Wenn nun durch die Tonkean Exemplare das Vorkommen von M.

maurus im Nordosten, so weit vom Süden der Insel entfernt, sicher
gestellt ist, so wird damit ohne Weiteres w a h r s c h e i n l i c h , dass
er auch das ganze dazwischen liegende Gebiet bevölkert. Durch
zwei im Ethnographischen Museum befindliche Kopfbedeckungen
mit Affenfell, die eine von „Ost Celebes“, die andere vom Poso See 5,
kann ich jedoch e r w e i s e n , dass dem so ist; denn ein Vergleich
der Haare mit denen von C. niger und M. maurus ergiebt, dass sie
von M. maurus, und nicht von C. niger stammen. P. und F.
S a r a s i n sagen von den Wäldern von [2]Central Celebes (Z. Erdk.
Berlin XXX, 328 1895), dass Affen sich nicht blicken liessen, doch
fanden sie bei den Toradjas Mützen mit schwarzem langhaarigen
Affenfell überzogen (p. 339), jedenfalls solche, wie die eine der eben
aus dem Ethnographischen Museum vom Poso See erwähnten. In
Luhu hörte W e b e r (p. 103) Nichts von einem Affen, allein obige
Thatsachen lassen es mir nicht zweifelhaft erscheinen, dass M.
maurus ganz Celebes bis auf die langgestreckte nördliche Halbinsel
bevölkert. Hier kennt man (S c h l e g e l Cat. VII, 120 1870) von der
Nordspitze der Minahassa bis Tomini (in der Nordwestecke des
Golfes gleichen Namens) C. niger (resp. nigrescens), und wenn die
beiden Affen, wie es scheint, nicht in derselben Gegend zugleich
vorkommen, so bliebe nur die Strecke Tomini-Kajeli-Mandar unsicher
hinsichtlich der Art, die sie beherbergt, oder, da es nicht
unwahrscheinlich ist, dass sich Kajeli-Mandar in dieser Beziehung
Süd und Central Celebes anschliessen, nur die schmale Landzunge,
die den Körper von Celebes mit dem nördlichen Arme verbindet.
Dieses scheint aber für die Frage der geographischen Verbreitung
der zwei Arten im Grossen und Ganzen nicht wesentlich, so
erwünscht es auch ist, genaue Kenntniss davon zu haben. Von der
Tonkean nahen Insel Peling erhielt das Museum M. maurus nicht,
und da deren Fauna schon keinen echt celebischen Charakter mehr
hat (s. Abh. Mus. Dresden 1896/7 Nr. 2), so ist das Nichtvorkommen
daselbst auch nicht auffallend.

Auf Tafel I findet sich M. maurus in verschiedenen Haarkleidern (c. ⅙

n. Gr.) dargestellt, und zwar nach Exemplaren des Dresdner
Museums und nach W e b e r schen aus der Sammlung des
Amsterdamer Zoologischen Gartens, von denen mir zwei von Dr.
K e r b e r t gütigst geliehen wurden. Man dürfte, da bis jetzt nur
jüngere Menagerie-Exemplare abgebildet worden sind, die
Wiedergabe charakteristischer Individuen von sicheren Fundorten
nicht für überflüssig erachten, besonders auch in Anbetracht der
Verwirrung, die bis zur W e b e r schen Darstellung über M. maurus
und ocreatus herrschte; ein adultes, wie das Dresdner von Tonkean,
ist überhaupt noch nicht abgebildet worden.

F i g u r 1 . J u n g e s W e i b c h e n von Bantimurung (2076). 3.

Molar noch unentwickelt. So gut wie einfarbig, mit nur schwachen
Spuren einer helleren Zeichnung hinten. Es entspricht ungefähr der
C u v i e r schen Abbildung (Hist. nat. III 1823 Avril) eines M. maurus
„d’un pelage uniformément brun foncé“, nach der man diesen Affen
aber schwer identificiren kann 6, sowie der G r a y schen (P. Z. S.
1866 pl. XIX) von M. inornatus (= maurus) eines jüngeren
Individuums, „blackish brown, nearly uniform … the hinder part of the
thigh greyish white“ (p. 202), das wohl etwas mehr Zeichnung hinten
hatte. — Vom Vertex zum Anus 380 mm, Hinterhand 125,
Schädellänge 106.5, Jochbogenbreite 69.2.

F i g u r 2 . J u n g e s M ä n n c h e n von der Insel Buton, aus dem

genannten Amsterdamer Museum, von W e b e r (p. 103) lebend
heimgebracht. 3. Molar unentwickelt, Milchgebiss zum Theile noch
vorhanden. Etwas grösser als das Exemplar Figur 1.
Gesammtfärbung noch bräunlich, wenn auch grauer als bei Figur 1,
die helle Zeichnung hinten gut ausgeprägt, Unterarm und
Unterschenkel deutlich heller grau abgesetzt. — Vom Vertex zum
Anus 410 mm, Hinterhand 140, Schädellänge 115, Jochbogenbreite
68,1.

F i g u r 3 . J u n g e s W e i b c h e n von Kandari, aus dem

genannten Amsterdamer Museum, auch von W e b e r (p. 103)
lebend heimgebracht. 3. Molar noch unentwickelt. Ziemlich von
derselben Grösse, wie das junge Männchen Figur 2, aber bereits
schön glänzend schwarz mit weisslicher Zeichnung hinten (hier in
der Behaarung defect) und mit lebhafter grauem Unterarm und
Unterschenkel als das Männchen Figur 2. Es entspricht am Besten
der S c l a t e r schen Abbildung eines nicht adulten Exemplares von
M. ocreatus (P. Z. S. 1860 pl. LXXXII und S c l . & W o l f : Zool.
Sketches II 1867 pl. I), das die helle Zeichnung hinten noch nicht
ausgeprägt aufweist 7. — Vom Vertex zum Anus 420 mm, Hinterhand
140, Schädellänge 115, Jochbogenbreite 71.

F i g u r 4 . J u n g e s W e i b c h e n (nach einem Fell ohne Schädel

gezeichnet) von Tonkean (B 3167) in der ungefähren Grösse der
Exemplare Figur 2 und 3, mit ausgeprägter heller Zeichnung hinten
und von bräunlich schwarzer Färbung, nicht so tief glänzend schwarz
wie Figur 3, aber die E x t r e m i t ä t e n ebenfalls
b r ä u n l i c h s c h w a r z , nicht heller. [3]

F i g u r 5 . A d u l t e s M ä n n c h e n von Tonkean (2469), dessen

Schädel Tafel II Fig. 1–2 und III Fig. 1–2 in ¾ n. Gr. in der norma
facialis, lateralis, verticalis und basalis wiedergegeben ist. Stumpf
schwarz, leicht graubläulich angeflogen, mit sehr ausgeprägter heller
Zeichnung hinten, aber ebenfalls mit d u n k l e n E x t r e m i t ä t e n ,
und zwar: Unterarm und Unterschenkel aussen stumpf schwarz,