Critical Reviews in Analytical Chemistry

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Supercritical Fluid Extraction of Pesticides

and Insecticides from Food Samples and Plant
Materials

Mohammad Yousefi, Mehdi Rahimi-Nasrabadi, Somayeh Mirsadeghi & Seied

Mahdi Pourmortazavi

To cite this article: Mohammad Yousefi, Mehdi Rahimi-Nasrabadi, Somayeh Mirsadeghi &
Seied Mahdi Pourmortazavi (2020): Supercritical Fluid Extraction of Pesticides and Insecticides
from Food Samples and Plant Materials, Critical Reviews in Analytical Chemistry, DOI:
10.1080/10408347.2020.1743965

To link to this article: https://doi.org/10.1080/10408347.2020.1743965

Published online: 15 Apr 2020.

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CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY
https://doi.org/10.1080/10408347.2020.1743965

Supercritical Fluid Extraction of Pesticides and Insecticides from

Food Samples and Plant Materials
Mohammad Yousefia , Mehdi Rahimi-Nasrabadib , Somayeh Mirsadeghic , and Seied Mahdi
Pourmortazavid
a
Department of Food Science and Technology, Faculty of Nutrition and Food Science, Tabriz University of Medical Sciences, Tabriz, Iran;
b
Faculty of Pharmacy, Baqiyatallah University of Medical Sciences, Tehran, Iran; cEndocrinology and Metabolism Research Center,
Endocrinology and Metabolism Clinical Sciences Institute, Tehran University of Medical Sciences, Tehran, Iran; dFaculty of Chemistry and
Chemical Engineering, Malek Ashtar University of Technology, Tehran, Iran

ABSTRACT KEYWORDS
The principal intention of this study is presenting the attempts carried out for extracting, separat- Food; insecticide; pesticide;
ing, and determining of the pesticide and insecticide residues existing in food and plant samples. plants; SFC; SFE;
In this regard, a set of content, including the explanations about the supercritical fluid extraction supercritical fluid
chromatography; supercrit-
(SFE), supercritical fluid chromatography, and various types of pesticides are indicated. Besides, ical fluid extraction
the parameters affecting the pesticides extraction composed of temperature, pressure, modifier,
drying agent, and so on are discussed. Also, examples of insecticides extraction by SFE technique
as an important subset of pesticides are indicated. Along with these items, some interesting
works, concerning the innovations implemented in the field of SFE of pesticide and insecticide res-
idues from foodstuff and plants are depicted.

Introduction exposure of humans to pesticides can cause chronic diseases

Today, the use of pesticides is considered as an intrinsic
approach to deal with plant pests, loss of products and capi-
tals, and increase of the food safety. After World War II, in
response to the increased needs for food products, the use
of pesticides was faced with a significant growth. Over 500
compounds are registered as pesticides, or metabolites of
pesticides.[1] US Environmental Protection Agency (EPA)
has defined pesticide as “any substance or mixture of
substances used to destroy, suppress or alter the life cycle of
any pest.” They include baits, bactericides, fungicides,
insecticides, herbicides, lures, repellents, and rodenticides.
Pesticides are also classified by chemical structure (for
example, organic, inorganic, and bio-pesticide), physical
state (for example, gaseous fumigant), and target organism
(bactericides, fungicides, insecticides, and etc.).[2]
Insecticides as defined by National Pesticide Information
Center (NPIC) are “pesticides that are formulated to kill,
harm, repel or mitigate one or more species of insect.” The
most well-known insecticides include N-methylcarbamate,
organophosphorus (OPP), organochlorine (OCP), pyreth-
roid, neonicotinoid, and ryanoid.[3,4] In a classification based
on plant-derived compounds, insecticides have been divided
into three groups of alkaloid-, flavonoid-, and terpenoid-
based insecticides.[5] In addition to advantages of pesticides,
the overuse and misuse of pesticides have resulted in
the occurrence of residues of them in foods, plants, soil,
and water. There are countless evidences indicating that
such as cancers, diabetes, Parkinson, Alzheimer, atheroscler-
osis, chronic nephropathies, coronary artery disease, and
etc.[6–8] Some of the characteristics and symptoms of preva-
lent pesticides in foods and plants are given in Table 1.
World Health Organization (WHO) in a report in 2002
has confirmed the death of 186,000 people and Disability
Adjusted Life Years (DALYs) of 4,420,000 people affected by
ingestion of preventable pesticides.[9] However, official evi-
dences show an increase in annual sales and use of pesti-
cides in the world. According to the new technical market
research, total market value is estimated reaching $65.3 bil-
lion in 2017, which was $37.5 billion in 2011.[10] Also,
European Crop Protection Association has reported the use
of 0.2 billion kg pesticides in 2010, where the share of con-
sumption of fungicides and insecticides were approximately
0.085 and 0.025 billion kg, respectively.[11] Hence, the
separation and determination of pesticide residues in foods
and plants is of double importance. In this regard, various
methods of liquid–liquid extraction (LLE),[12] pressurized-
liquid extraction (PLE),[13] microwave-assisted extraction
(MAE),[14] ultrasound-assisted extraction (UAE),[15] solid-
phase extraction (SPE),[16] quick, easy, cheap, effective, rug-
ged and safe (QuEChERS) method, and supercritical fluid
extraction (SFE) have been applied to extract pesticides and
insecticides.[17,18] Also, liquid chromatography (LC) and gas
chromatography (GC) in coupling with electron capture
detector (ECD), nitrogen–phosphorus detector (NPD), flame

CONTACT Somayeh Mirsadeghi sshmirsadeghi@sina.tums.ac.ir Endocrinology and Metabolism Research Center, Endocrinology and Metabolism Clinical
Sciences Institute, Tehran University of Medical Sciences P.O. Box 1411713137, Tehran, Iran.
ß 2020 Taylor & Francis Group, LLC
2 M. YOUSEFI ET AL.

Table 1. Specifications of some common pesticides in plant materials and edible samples.
Compound Characteristic Pests affected Sources Some symptoms Structure Reference
[127]
Diazinon Organophosphate Cockroaches, ants, Soil, ornamental plants, Headache, feelings of
insecticide silverfish and fleas fruit and vegetable anxiety, pinpoint
field crops pupils and cancer
[128]
Chlorpyrifos Organophosphate Mosquitoes, Numerous crops Headache, cancer
insecticide cockroaches, flea,
grubs, beetles and
fire ants
[129]
Permethrin Pyrethroid pesticide Multitude of pests, Wheat, corn and alfalfa Redness and Pain in
particularly skin and eyes,
mosquitos diarrhea, Vomiting
[130]
Dieldrin Organochlorine Termite Watershed, soil and Headache, dizziness,
insecticide animal fat uncontrolled muscle
movements, death
[131]
Atrazine Triazine herbicide Herbs Drinking water, Endocrine disruption,
watermelon, low birth weight
cucumber, green and cancer
onion and etc.
[132]
Propiconazole Triazole fungicide Fungi, bacteria, Food crops and Corneal opacity
and viruses ornamental plants

photometric detector (FPD), mass spectrometry (MS),
diode-array detector (DAD), and fluorescence detector are
the most widely used techniques to detect the pesticide resi-
dues in foods and plant materials.[19] A number of selected
and recovered pesticides and insecticides are briefly sum-
marized in Table 2 from 2010 onwards.
The main purpose of this review is the investigation of
SFE and supercritical fluid chromatography (SFC) systems
and their functions in the extraction and separation of the
pesticide and insecticide residues existing in foodstuff and
plant materials.
An overview of SFE
In today’s world, the subject of extraction from foodstuff has
become a worldwide issue among scientific papers and food
industries. Many methods have been developed and applied
to extract substantial compounds from foods. Some of the
most important of them include pressurized liquid extraction,
microwave-assisted extraction, pressurized hot water extrac-
tion, solid-phase micro extraction, membrane-assisted solvent
extraction, stir-bar sorptive extraction and SFE.[20]
The term “supercritical fluid” refers to a matter in a sin-
gle-phase and non-condensing state when placed above its
critical pressure (Pc) and critical temperature (Tc).[21]
Beyond this point, the surface of demarcation between
liquid and gas disappears and emerges a homogeneous
fluid.[22] In this conditions, the properties of substances
changes and the new abilities appears. The ability to
manipulate the temperature and pressure for obtaining a
desired selectivity are the main characteristics of a supercrit-
ical fluid (SF). Investigations have revealed that the density
and the solvent power of a SF to extract a particular mater-
ial are proportional to its pressure and temperature.[23] So
that the slightest modification in the pressure and tempera-
ture could lead to differences in the amount of materials
separated.[24,25] The most important compounds used to
form a SF have been presented in Table 3. Carbon dioxide
is the most commonly used SF among other fluids.[26]
Many papers have introduced SFE as a method containing
salient features such as selectivity, short time requiring, low
solvent consuming, and environmentally friendly nature.[27–29]
The basic parts of a SFE system (Figure 1) are composed
of a CO2 or other fluids source, an oven containing the
extraction vessel, a pump to pressurize the gas, a trapping
or collecting vessel, and a restrictor to retain the high pres-
sure into the extraction section.[30] The CO2 gas becomes a
supercritical fluid at the pressure and temperature above
31.1
C and 7.29 MPa.[31] This SF is sent to collection vessel
after the extraction step. The collection stage is considered
very important due to its decisive role in purification and
separation of the intended compound. This step divides the
SFE system into two forms of off-line and on-line.
Off-line and on-line systems of SFE
The off-line collection includes solid-phase trapping and
solvent collection. In the solvent collection method, effluent
(CO2–analyte mixture) is connected to the solvent by the
restrictor or depressurized directly into the solvent.[32]
Trapping with solvents is generally nonselective, and offers
high trapping efficiencies except for a number of volatile
components, also it is rather simple and inexpensive to carry
out and the extracts are instantly ready for chromatographic
analysis. The select of a proper solvent or a mixture of sol-
vents to optimize the collection efficacy is likewise import-
ant. For instance, Liu et al. extracted and collected several
pesticides, including chloramphenicol, thiamphenicol, and
florfenicol obtained by SFE and in situ derivatization
method from shrimp.[33] They employed solvents of aceto-
nitrile, acetone, hexane, and ethyl acetate containing Sylon
BFT (99:1 mixture of N,O-bis (trimethylsilyl) trifluoroaceta-
mide (BSTFA)-trimethylchlorosilane (TMCS)) as derivatiza-
tion reagent to collect the pesticides. As a result of their
work, the highest collection efficiency was observed with ethyl
Table 2. Pesticides and insecticides residues detected in some foods and plant materials reported after 2010.
Relative standard Limit of Limit of
Origin Most detected pesticides Separation/Detection method deviation (RSD) detection (LOD) quantification (LOQ) References
[133]
Bean sprouts 6-Benzylaminopurine, carbendazim and thiabendazole Liquid chromatography tandem mass spectrometry (LC/ Less than 3.3% 2.1–3.7 ng/g 6.3–11.1 ng/g
MS/MS)
[134]
Brazilian grape Juices Organochlorides, organophosphorides and fungicides Gas chromatography coupled to mass spectrometer Less than 4.9% 1.2–6.6 mg/L 3.7–9.4 mg/L
(GC-MS)
[135]
Some fruits and vegetables Chlorpyrifos, primiphos methyl, procymidone, GC-MS – 3.3–13.3 ng/g 10.0–40.0 ng/g
dimethoate and dieldrin.
[136]
Cereals, fruit and vegetables from Dieldrine, aldrin, hexachlorocyclohexane isomers and Gas chromatography-electron capture (GC-EC) Less than 14% 1.0–21.4 ng/g –
East Europe and Central Asia dichlorodiphenyltrichloroethane (DDT)
[137]
Fruits and vegetables from the Boscalid, dithiocarbamates and cyprodinil (LC/MS/MS) Less than 20% – 5.0–50.0 ng/g
Retail Market in Poland
[138]
Fruits and vegetables from Imidacloprid, cypermethrin, carbendazim, benomyl and GC-MS and gas chromatography using tandem mass – – 4.0–100.0 ng/g
Southeast Asia chlorpyrifos spectrometry (GC-MS/MS) and LC-MS
[139]
Khat (Catha edulis) plant Dichlorodiphenyltrichloroethane (DDT) and GC-EC 3.68%–8.87% 0.017–0.046 mg/L
dichlorodiphenyldichloroethylene (DDE)
[140]
Sunflower and oilseed rape Metazachlor, quinmerac, oxyfluorfen GC-MS and high-pressure liquid chromatography mass Less than 20% 0.1–2.0 ng/g 0.3–60.2 ng/g
plant matrices spectrometry (HPLC-MS)
[141]
Dill Azoxystrobin, bromopropylate, fluazifop-P-butyl, GC-EC with phosphorus detection (GC-EC/NPD) Less than 12% – 10.0 ng/g
flusilazole, lambda-cyhalothrin, pyrimethanil,
pirimicarb, quinalphos, and trifloxystrobin
[142]
Medicinal plants Chlorfenvinphos, parathion, fenitrothion, quinalphos, Sweeping micellar electrokinetic chromatography Less than 6.5% 2.0–8.0 ng/g –
azinphos-ethyl, parathion-methyl, methidathion,
fensulfothion, and paraoxon
[143]
Cannabis plants Propamocarb, propiconazole, tebuconazole, tolylfluanid Ultra performance liquid chromatography-tandem mass – 1.0–30.0 ng/g 50.0–150.0 ng/g
imidacloprid, hexythiazox, and bifenthrin spectrometer (UPLC-MS/MS)
[144]
Pork ham DDT, hexachlorocyclohexane, heptachlor epoxide, and GC-MS Less than 15% 0.5–0.2.4 ng/g 0.0–7.0 ng/g
alpha-chlordane
[145]
Fruit juices Omethoate, dichlorvos, methamidophos, chlorpyrifos, Sensitive visual screening card based on inhibition of 2.45%–3.74% 0.1–2.0 mg/L –
carbaryl, and pirimicarb acetylcholinesterase (AChE)
[146]
Some food samples Diazinon, permethrin, cypermethrin GC-EC and GC-MS – 1.0 ng/g –
[147]
Cabbage, cucumber, and apple Acetamiprid, clothianidin, nicotine, and nitenpyram Polyclonal antibody-based enzyme-linked immunosorbent Less than 10% 0.00003–0.0016 mg/L –
assay (pAb-ELISA)
CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY
3
4 M. YOUSEFI ET AL.

Figure 1. A simple schematic of supercritical fluid extraction system.

Table 3. Some of the most used fluids as supercritical fluid and their critical properties.[148]
Critical property
Solvent

Temperature ( C) Pressure (atm) Density (g/mL) Solubility (cal–1/2 cm–3/2)
Carbon dioxide 31.2 72.9 0.470 7.5
Ethane 32.4 48.2 0.200 5.8
Ethene 10.1 50.5 0.200 5.8
Methanol 34.4 79.9 0.272 8.9
Nitrous oxide 36.7 71.1 0.460 7.2
n-Butene 139.9 36.0 0.221 5.2
n-Pentane 76.5 33.3 0.237 5.1
Sulfur hexafluoride 45.8 37.3 0.730 5.5
Water 101.1 217.6 0.322 13.5

acetate. This method is widely used for extracting from envir-
onmental materials.
The solid-phase trapping is designed in three models,
including cryogenic trapping, adsorption on trapping solids,
and empty vial collection. Empty vial has the poor collection
efficiency in purification of components and it is only consid-
ered as a gathering vessel without purification. This system
is done with one or numerous empty vials. The cryogenically
trapping columns have the ability to concentrate the analyte
of interest. The cooled surfaces are usually employed to col-
lect the volatile compounds such as fragrances efficiently.[34]
Today, the application of these two types of collection sys-
tems alone has been severely reduced due to the lack of
selectivity in purification of the targeted compound.
The adsorption on trapping solids (solid-phase trapping)
is the third method which employs the sorbents substances
such as silica gel, cellulose, aluminum oxide, bentonite, and
magnesium silicate to concentrate and purify the intended
components.[35] A prominent advantage for this collection
system is that the selectivity can be more improved by a
selective trapping solid coupled with selective eluting sol-
vents. For instance, polar compounds can be easily trapped
on a silica gel column and then be eluted with proper sol-
vents.[36,37] However, desorption to the chromatographic
column in this system is difficult, depending on how
strongly the compounds are retained to the trap. Analyte
desorption is generally achieved by adding a large amount
of modifier to the mobile phase or by increasing the trap
temperature. Besides, an improperly selected modifier solv-
ent may result in substantial losses of the targeted
compounds because they could be eluted through the trap.
In general, for pesticides, both solvent collection and solid-
phase trapping are common methods in analytical-scale SFE.
The on-line system couples the SFE, directly, with an
analytical technique such as high-pressure liquid chromatog-
raphy (HPLC), GC, or Fourier transform infrared spectroscopy
(FTIR). In comparison between the off-line and on-line
systems, on-line method needs minimal sample handling, has
1000-fold or higher analyte sensitivity enhancement, requires
small load of sample. The off-line method uses the larger sam-
ple size (>5–10 g), could be done at faster flow rate, easy to
clean-up, possibility of applying different collection methods,
and the simplicity of the operation.[38] Also, in comparison
with solid-phase trapping and solvent collection in off-line sys-
tem, the on-line SFE technique offers higher sensitivity owing
to the direct transfer of the whole portion of extracted compo-
nents to the analytical instrument. On the other hand, many
of the practical activities such as separation, recovery, and the
quantification need an on-line system.
SFE limitations
Other than the advantages of SFE technique, there are
still some limitations. The main disadvantage of CO2 is its

non-polarity nature, which makes the supercritical carbon
dioxide (SC-CO2) to extract mainly non-polar or low-polar
compounds.[39,40] Although the use of polar modifiers
increases the range of substances that can be extracted, how-
ever modifiers may interfere with collection step by deacti-
vating the sorbent. Also, modifiers need to be removed later
at cleanup step.
Besides the requirement for a high purity of CO2 or other
supercritical solvent, requirement for high-input investments
are of the most important factors limiting the usage of SFE.
Despite that the implementation of SFE is fast, effective, and
relatively inexpensive, but the necessity of having expensive
equipment and materials is undeniable.[41]
The other problem of SFE is its difficulty in dealing with
natural and spiked materials. Many studies, contrary to pro-
jections, have resulted in the lower recovery range of tar-
geted compounds from natural samples compared to spiked
samples by the SFE technique. The explanation of this man-
ner is that target compounds in natural tissues are incorpo-
rated in cell wall or bonded to other compounds which
hinder the extraction of these bioactive compounds, also,
the spiked analytes may not be located on the same sites as
natural analytes. Besides, analytes that have supposed to be
spiked usually require an organic solvent to deposit onto the
sample, and this solvent may compete with spiked analytes
for strong adsorption. Therefore, it causes the targeted ana-
lytes to be adsorbed on weak sites and gets higher recoveries
than a natural sample.[42]
The SFE technique also needs the clean-up steps fre-
quently. In some cases the resulting extracts are not pure
and they are with unwanted matrix components, thus clean-
up steps are necessary, particularly when the analytes are
fat-soluble. Generally, the extracts obtained by using SC-
CO2 are relatively much cleaner than those obtained by
other solvents, which make SC-CO2 possible to inject dir-
ectly into the gas chromatograph.
An overview of SFC
In addition to extraction by SFE technique, SC-CO2 can be
used as a mobile phase in analytical instruments such as GC
and HPLC. This method is known as SFC. Today, the SFC
technique has been famous as an efficient method in separ-
ation and isolation of extensive range of substances in food
and drug industries.[43] The fundamental planning and imple-
mentation of SFC dates back to 1962 when the Klesper et al.
identified the features of CO2 reached above the critical
point.[44] Although, there was difficulties with backpressure
regulation, flow rates, sample injection, and modifier addition
at the early, but most of them were solved via introduction
and development of the state-of-the-art SFC systems.
This method was initially carried out with pure CO2 as
the mobile phase, but the problem of CO2 to separate polar
components has forced the researchers to use CO2 in sub-
critical conditions owing to modification of CO2 with a
polar modifier; yet SC-CO2 is always the main part of the
mobile phase. The role of SFC in successful separation of
lipids and other compounds related to fats such as, fatty
CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY 5
acids, triacylglycerol, phospholipids, carotenoids, and fat-sol-
uble vitamins repeatedly has been reported in several stud-
ies.[45–48] Along with fat-based or fat-soluble components,
SFC also has been introduced as a prosperous method to
isolate and separate the polar compounds, particularly car-
bohydrates and proteins from foodstuff and plants.[49,50] In
these situations, the application of modifiers and an appro-
priate stationary phase has become more vital. Typically, the
amount of 5%–50% of modifiers is added to a mobile phase
to achieve an appropriate condition to separate targeted sub-
stances. Alcohols such as methanol, ethanol, and isopropa-
nol as well as acetonitrile are the most used modifiers. They
offer unique properties. For example, methanol has higher
eluotropic strength than isopropanol and ethanol.[51] Also,
ethanol has been regarded as a solvent with low side effects
based on selectivity and retention time.[52]
Today, SFC is more preferred than normal HPLC owing
to its several benefits, including (1) shorter run time and
more efficient separations due to lower viscosity and higher
diffusivity of SF relative to liquids, (2) longer, stacked col-
umns with total theoretical plates more than 100,000, (3) an
inert, environmentally “green,” carbon dioxide-based mobile
phase in large scale separations, and (4) selectivity for
choosing the desire pressure and temperature.[75]
Discussion about the SFC instruments
In brief, a SFC system is composed of two containers having
SC-CO2 fluid and a modifier solvent, which are transported
by two pumps, an injector, a column placed in an oven, a
restrictor to control the back pressure, and a detector. The
whole system is similar to GC with exception of the restric-
tor. The SFC columns have been designed in two forms of
packed and capillary columns. The capillary columns, such as
open tubular fused silica columns provide greater numbers of
theoretical plates owing to their longer length. Also, GC
detectors such as flame ionization, nitrogen phosphorus, and
electron capture were popular with open tubular SFC.
However, the main problem of such columns is their low
sample capacity. Historically, capillary columns tended to be
utilized at temperatures above the critical temperature of
CO2. Packed columns operated at SFC system, indicates usu-
ally faster analyzing, lower detection limits, and greater sam-
ple injection, but higher pressure drops through the packed
columns compared to open tubular columns which reduces
the efficiency and resolution.[53] Although, the problem of
pressure drop in packed columns has been already resolved
by using a pressure regulator. Nowadays, the packed columns
at SFC system have almost taken the capillary columns place.
Concerning the detectors utilized in a SFC system, exten-
sive developments have taken place. Some researchers have
considered the advances of detectors from the GC type to
the LC type as the renaissance of SFC.[54] Nowadays, several
kinds of detectors such as UV–vis detectors, the most
recently incorporated mass spectrometer detector (MSD),
the evaporative light scattering detector (ELSD), and the
quadrupole-time-of-flight MS[55] have been developed to
optimize the separation of various substances.
6 M. YOUSEFI ET AL.
Figure 2. System configuring of 2D online SFE-SFC-MS.
Preparative SFC
The potential application of SFC is likewise considerable for
preparative purposes, as well as the analytical functions.
Preparative SFC (prep-SFC) is frequently employed for the
fractionation and purification of extracts achieved by extrac-
tion methods, such as SFE. The columns used in prep-SFC
(with 25 cm length) are longer than those made for analyt-
ical (5 cm length) objects.[56] The separation by prep-SFC
could be performed by either a single column or multi-col-
umn chromatography (MCC). The single column chroma-
tography has several advantages, such as its straightforward
implementation and its suitability for the separation of
multi-component mixtures. However, its productivity is
rather limited due to the fixed-bed configuration. To purify
large batches, MCC offers significant advantages in terms of
solvent consumption and productivity.[57] One of the most
popular types of the MCC is the simulated moving bed
(SMB) chromatography.[58] This technique has been based
on the continuous counter-current movement of mobile and
stationary phases which makes the method highly product-
ive. A comprehensive information about SMB as a process
for separation and purification of chiral and achiral substan-
ces has been given by Schulte and Strube in 2001.[59]
Examples of SFC utilization for separating and
determining the pesticide residues in foodstuff
and plants
Some examples of SFC application for identifying pesticide
residues in foods and plants are given as follows. Ishibashi
et al. investigated the detection power of SFC coupled with
high-resolution MS to analyze the pesticides existing in spin-
ach extracts. First, they extracted the spinach extract by
QuEChERS procedure and the extracts were then mixed
with standard solutions containing targeted pesticides, next
the extracts were analyzed by SFC technique. SC-CO2 was
used as mobile phase with methanol as the modifier where
its concentration changed from 5% to 30% to dissolve all
kinds of pesticides as much as possible. The system was
coupled with a Q Exactive, a high-performance mass spec-
trometer. Their analyzing results of 444 pesticides identified
391 pesticides under 0.01 mg/L limit of detection (LOD).[60]
SFC also has been studied in enantiomeric separation of
pesticides. In this regard, Toribio et al. separated the six
enantiomeric triazole pesticides, including cyproconazole,
propiconazole, hexaconazole, diniconazole, tetraconazole,
and tebuconazole, using SFC and the Chiralpak AD column
at about 10 min. The condition utilized at their work con-
sisted of 35
C, 20 MPa, and a flow rate of 2 mL/min.[61]
The successful analyzing of pesticides spiked into the avo-
cado and papaya by SFC system has been reported by Pano-
Farias et al. in 2015. Their detection procedures included
the extraction of methyl parathion, ametryn, atrazine, carbo-
furan, and carbaryl spiked into the samples by QuEChERS,
injection of 10 mL extract into the column of SFC, the separ-
ation of pesticides by the SC-CO2 modified by methanol,
and the detection of pesticides by a photodiode array
detector. The LODs obtained for papaya and avocado sam-
ples ranged from 130 to 380 and <450 ng/g, respectively.
The conditions of chromatography applied were 30–50
C,
0.34–13.79 MPa, and the flow rate of 0.4–1.5 mL/min. Their
finding demonstrated 72.8%–94.6% and 50.0–94.2% recovery
for papaya and avocado, respectively.[62] In many studies,
researchers first extracted the pesticide residues by SFE, then
transported SC-CO2 along with pesticide compounds dir-
ectly (on-line) to the chromatography instruments to separ-
ate and measure the extraction or recovery yield. A simple
figure representing the online SFE-SFC-MS is shown in
Figure 2. The newest studies performed since 2017 about
the SFC of pesticides have been summarized in Table 4.
SFE application in recovery of pesticides
Extraction and identification of pesticides by supercritical
fluids has been focused by some of the studies. This interest
Table 4. The most recently applications of SFC to separate pesticides.
Relative standard Limit of
Origin Pesticides Modifier used with SC-CO2 Temperature Pressure Flow rate SFC column Detector deviation (RSD) detection (LOD) References
[149]
Tomato, apple, Fenbuconazole Ethanol 20–40
C 1.03–16.55 MPa 1.8 mL/min ACQUITY UPC2 Trefoil Tandem mass 11.5% 0.04  0.99 mg/kg
cucumber, peach, AMY 1 column coated spectrometer
rice, wheat with amylose tris
[150]
Not provided Sulfur-containing pesticides Methanol 25
C 15 MPa 3 mL/min Chlorinated
polysaccharide
stationary phases
[151]
Leafy vegetables Alkylphenol ethoxylates Methanol/acetonitrile 40
C 12 MPa 1.65 mL/min Viridis BEH Tandem mass 18.3% 0.02–0.27 lg/kg
spectrometer
[152]
Chrysanthemum Pyrethrin Not used 40
C 20 MPa and 0.8 kg/h Fused-silica GC-MS
flowers capillary column
[153]
Not provided Chiral sulfoxides Isopropyl Alcohol, 35
C 17.2 MPa 2 mL/min Amylose-based Photodiode array
methanol, ethanol polysaccharide column
[154]
Not provided 441 different pesticides Methanol containing 1 or 40
C ND 0.05, 0.1, 0.2, and Shim-pack FC-ODS GC-MS 20%
5 mM of 0.4 mL/min
ammonium formate
[155]
Not provided Fluazinam, cymoxanil, Methanol with 0.1% (vol/ ND 10–14.9 MPa 5 mL/min ODS-EP column Photodiode array 2%–3% 12.5 ng/kg
pyraclofos, oxamyl, vol) containing polar-
etofenprox, teflubenzuron, ammonium formate embedded
chlorfluazuron, reversed particles
imazosulfuron,
cyclosulfamuron
CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY
7
8 M. YOUSEFI ET AL.
is due to the high capability of SFE in extraction and ana-
lysis of samples in a very short time and with high accur-
acy.[39] One of the most common techniques, evaluating the
efficacy of SFE is the extraction of pesticides spiked into a
special sample.[42] In such studies, a certain amount of one
or more pesticides are spiked into a plant, food, or other
sample. Then, the action of recovery and determining the
quantity of extracted pesticides are conducted by SFE technol-
ogy.[63,64] An overview on articles shows that most of them
with presentation of 70%–95% mean recoveries have hailed
SFE coupled with analytical instruments as an efficient
method to analyze pesticides in food and plant matrices. For
example, Rezaei et al. developed the combination of SFE with
supramolecular solvents-based micro-extraction (SSME) to
extract diphenylamine residues (DP) from apple, orange, and
pear peels. This method showed a yield of at least 90% in
extraction of DP.[65] Tao et al. succeeded in extracting the
flutriafol enantiomers as antifungal and pesticide agents from
tomato, cucumber, apple, grape, and soil by using SFE incor-
porated with tandem mass spectrometer. By using this instru-
ments, they reached to mean recoveries of 77.2%98.9% with
relative standard deviations (RSDs) 9.6% in all matrices.[66]
Extraction of three pyrethroid pesticides, including fenpropa-
thrin, fluvalinate, and fenvalerate by SC-CO2 is another work
conducted by O’Mahony et al. in 2003. Capillary electrochro-
matography (CEC) used in this study showed mean recov-
eries of >80%.[67] Some other studies concerning this issue
have been presented in Table 5.
Pesticidal effect of substances extracted by SCF
One of the most common ways for finding the best condi-
tions of SFE is the investigation on pesticidal strength of the
extracts separated by this technique on specific pests. In this
Figure 3. Effect of the SFE pressure on peak areas of spiked matrix at 35
C
and 5% methanol as modifier.[92]
Table 5. SFE (SC-CO2) applications in the recovery of pesticide residues in plant and food matrices.
Sample Pesticides
Papaya Methyl parathion, ametryn, atrazine, carbofuran and carbaryl
Olive oil samples Paraquat and diquat (polar pesticides)
Soybean oil Bendiocarb
Meat Carbofuran, procymidone, phorate and vinclozolin
regard, researchers extract the targeted pesticides at different
conditions. Then, they investigate the pesticidal activity of
the extracted components by offering them to one or several
pest. In conclusion, the extracts with the most pesticidal yield
show the best extraction conditions. For instances, Liang et al.
analyzed Stellera chamaejasme extracts by GC/MS coupled
with supercritical fluid producing equipment. In addition, they
investigated the acaricidal activities of S. chamaejasme extracts
on Tetranychus cinnabarinus mites. Results showed that, in an
optimum extracting temperature of 45
C, the yield of extrac-
tion was 3.7534%. Also the major compounds of extracts were
n-hexadecanoic acid, squalene, campestero, 9,12-octadecadie-
noic acid, and quinoline. S. chamaejasme likewise had the con-
tacting and systemic toxicity with LC50 value of 2.407 and
2.990 mg/mL, respectively.[68]
Machalova et al. extracted botanical pesticides from
Pelargonium graveolens using SC-CO2. The extract then was
offered to the larvae of Spodoptera litoralis. The assay exhib-
ited that obtained extract at 9 MPa, 50
C and 12 MPa, 40
C
had the highest chronic toxicity (LD50 ¼ 6 mg). Scapinello
et al. used Melia azedarach L. extracts as an insecticide
gained from SC-CO2 extraction against fall armyworm
(Spodoptera frugiperda). In their research, 50% mortality
(LD50) was observed at a concentration of 376.74 mg/kg
SC-CO2 and 100% mortality at 5000 mg/kg.
Multipesticide residues
One of the most important features of SFE coupled with
analytical instruments is the extraction and identification of
multipesticide residues at the same time with high accuracy
and speed. Among various methods developed to extract
and analyze multipesticide residues, SFE has been intro-
duced as one of the fastest of them. Various surveys show
that the tendency to extract and identify OPP and OCP pes-
ticides is higher than other pesticides.[69,70] For instance,
Zuin et al. determined 13 multiresidue OPP and OCP pesti-
cides in Brazil’s medicinal plants using flame photometric
and electron-capture detection.[71] In another study, the
extraction and determination of 92 pesticides from apple
samples by SFE have been reported.[72] In addition, Rissato
et al. investigated the impact of SFE combined with GC
with MS and electron-capture detection on extraction of 33
multiresidue pesticides from honey samples. Different pesti-
cides consisting of OPP, OCP, organonitrogen, and pyreth-
roid were evaluated in this experiment. The recoveries
obtained in this study were ranged from 75% to 94%.[73]
Simultaneous determination of pesticides in some edible
plants and cereals is so important due to their role in con-
sumer’s health. In this regard, Ishibashi et al. separated and
determined 373 insecticide residues at 10 mg/kg level from
Mean recoveries of pesticides References
72.8  94.6% Pano-Farias et al.[156]
92  108% Zougagh et al.[157]
80-88% Murugaverl and Voorhees[158]
78  95% Juhler[159]

spinach extracts by SFE coupled with GC-mass within a few
days.[60] In other analogs work, Adou et al. achieved 80.5%
to 97.3% recovery of multipesticides from leafy vegetables by
SFE coupled with GC.[74] Also, the determination of 19 and
22 pesticides extracted by SFE from vegetable and rice,
respectively, has been reported.[75,76]
Parameters affecting the SFE of pesticides
SFE depends on several parameters, including sample prep-
aration, sample size and homogeneity, modifiers, tempera-
ture, drying agents, packing density, flow rate, trapping, type
of supercritical fluid, pressure, temperature, etc.[77–79] In
fact, all of these parameters, by changing the solubility of
the substance, lead to an increase or decrease in the effi-
ciency of SCF in the extraction of target compounds.[80,81]
The value of molecules solubility in SC-CO2 is influenced by
the molecular weight of analyte substance and the level of
interactions between SCF and analyte molecules.[82] For
example, the temperature and pressure of SCF affect the
density of the fluid that controls the number of interactions
between SC-CO2 and target molecules. Increasing these
interactions is the key to conquer binding forces between
sample matrix and analytes. In other words, the analyte
molecules are solubilized in SCF. In addition to the density
of SC-CO2, the flow rate of SCF is other parameter effective
on the amount of extraction. Increasing the flow rate of SCF
leads to the increase in the diffusion rate of SCF into the
matrix. Therefore, it improves the extraction amount of tar-
get analytes, but on the other hand, it wastes a lot of sol-
vents. Thus, choosing a proper limit of flow rates depends
on the factors of time and solvent costs. The optimum flow
rate will probably be in the region where diffusion and solu-
bility are significant factors.[83] Another crucial factor to
control the SFE is attention to the particle size of matrix.
Large particles may conclude in prolonged extraction due to
the problem in diffusion process.[84] In fact, grinding a sam-
ple matrix into fine powder can accelerate the extraction,
but it may also cause difficulty in preserving a proper flow
rate. One operative way to overcome the problem of flow
rate is to pack the sample matrix with glass beads or other
rigid materials such as sea sand. Such rigid particles could
prevent the sample from pressing into impermeable plugs
and therefore maintain a preferred permissibility of the sam-
ple bed.[85] Regarding the extraction of pesticides and insec-
ticides from food matrixes, regulating the temperature,
pressure, flow rate, drying agent, and modifier are the most
interesting issues among articles.
The effect of temperature and pressure
Regarding extraction of pesticides, investigations on studies
display that most of them have been separated in a tempera-
ture range of 35–90
C, pressure of 15–28 MPa, and flow
rate of <1–2 mL/min.
Zhao et al.[86,87] tested the three levels of temperature
including 50, 60, and 75
C and pressure range of 7–20 MPa
on extracting OCP pesticides from Angelicae sinensis and
CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY 9
Radix codonopsis using SFE technology. Their results dem-
onstrated that the best function of SFE was achieved when
the pressure was maintained at 12–20 MPa and the tempera-
ture was 50 and 60
C. They extracted at least 82.47% and
93.5% of pesticides at optimum conditions.
In other study related to the extraction of OCP pesticides
from ginseng, Quan et al.[88] found that the yield of the pro-
cess increased by increasing the temperature from 40 to
60
C when the pressure was maintained at 30 MPa.
Comparing with pressure, which affects the solvent density
and, thus, the solvent dissolving capacity, the alteration of
temperature influences solvent and solute properties.
Increase of temperature decreases solvent density, however,
it increases solute vapor pressure which could result in
higher extraction rate.[89,90]
In general, the researchers have indicated that increasing
the temperature will be in favor of SFE functionality, but in
higher temperatures than optimum conditions, the density
diminution of SCF causes a decrease in recovery and extrac-
tion of pesticides.[65] Also, it has been said that excessive
pressure owing to the reduction in diffusion rate of the
extracted substances from the sample into the SCF environ-
ment may reduce the functionality of the SFE of pesti-
cides.[91] In a similar result, Liu et al. realized that different
organotin pesticide compounds of trimethyltin chloride
(TMT), monobutyltin trichloride (MBT), dibutyltin tichlor-
ide (DBT), tributyltin trichloride (TBT), triphenyltin tri-
chloride (TPT), and monobutyltin trichloride (MBT) spiked
into the clam samples have optimum recovery yield at
30 MPa, but after that, the state of diagram for all pesticides
was almost linear (Figure 3).[92] Some instances indicating
the optimum conditions in recovery and extraction of pesti-
cides are given in the following examples. Fan et al.[93]
extracted three different pesticides, including diazinon,
chlorpyrifos, and parathion-methyl from rice by SC-CO2 in
an optimum condition of 50
C, 20.3 MPa, and 1 mL/min
flow rate. In other study, Pan et al. extracted the pyrisoxa-
zole pesticide from cucumber, tomato, and soil with recov-
ery yield of 84.0%–105.6%. The condition applied in this
research was using SC-CO2/MeOH (75:25) at 2.0 mL/min
flow rate with 35
C temperature and 1.6 MPa pressure in
5 min.[94] In another experiment, Halvorsen et al.[95] suc-
cessfully extracted the fenpyroximate pesticide from apple at
90
C and 20 MPa for 15 min using CO2 at a flow of
2 mL/min.
The effect of modifiers
In addition to the role of temperature and pressure, the
modifiers also have a decisive function in the extraction of
pesticides. Improving the recovery of pesticides, reducing
the time of extraction, the impact on the type of extracts
and better illustration of peaks in detector are some roles of
them.[96,97] SC-CO2 despite of many unique features has a
non-polar characteristic which limits its efficacy to separate
highly polar molecules. Thus, adding polar solvents as modi-
fier to SC-CO2 improves the performance of SFE. Methanol,
ethanol, 1-butano, 2-propanol, and acetonitrile are the most
10 M. YOUSEFI ET AL.
Figure 4. Comparison of different modifiers on recovery of pesticides
from ginseng.[88]
common modifiers used in SFE technique,[98] however
methanol and ethanol are the most widely utilized modifiers
in SFE of pesticides from edible samples.
In a study conducted on the efficacy of different modi-
fiers on separation of pyrisoxazole from tomatoes and
cucumbers, methanol provided a better separation, while the
other modifiers such as ethanol, acetonitrile, and 2-propanol
only showed a partial or no separation.[94] In addition to
methanol, the efficacy of ethanol also has been shown by
Quan et al., where they found that absolute ethanol or
10 wt% ethanol–H2O as modifiers had better recovery effi-
cacy of benzene hexachloride (BHC) and pentachloronitro-
benzene (PCNB) pesticides from ginseng than acetone,
hexane, and modifier-free samples (Figure 4).[88]
The effect of modifiers on SFE has been clearly demon-
strated in Campbell et al.’s[99] study, where they applied SFE
with or without methanol as a modifier to extract chlorpyri-
fos methyl pesticide spiked on a wheat kernel substrate.
Their results exhibited that in the presence of 2% methanol,
extraction recoveries increased from 65% to 97.8%.
Nevertheless, the amount of modifier added to SCF should
be optimal.
The higher amounts of modifiers decrease the extraction
efficacy by weakening the interactions between the solute
and SCF. In this regard, Rezaei et al.[65] displayed that
increasing of the methanol from 0 to 50 lL in SC-CO2
improves the recovery of diphenylamine residue in fruit
samples, but increasing the modifier from 50 to 75 lL
reduces the functionality of SFE.
The effect of drying agents
The existence of water even in small ratio in edible samples
can cause problems to SFE process owing to freezing the
water in restrictor tip.[100] Some methods such as freeze-dry-
ing the samples before SFE or adding silica gels or drying
agents are utilized to remove the water from foods or plant
materials. Aguilera et al.,[101] concerning the importance of
drying agents, indicated that changing the preparation step
variables such as adding drying agent (magnesium sulfate)
has the greater effect than other parameters affecting the
SFE. Also at their work, a noticeable increase in the recovery
of chlorpyrifos-methyl, chlorothalonil, and procymidone
pesticides was seen when the amount of magnesium sulfate
as drying agent in the mixture of gazpacho-magnesium sul-
fate was increased from 1:1 to 5:7.[101]
Hydromatrix, magnesium sulfate, and pelletized diatom-
aceous earth as the prevalent drying agents are used in SFE
technique. It seems that magnesium sulfate is the best dry-
ing agent applied among studies. For example, Schenck
et al.[102] in comparison between magnesium sulfate and
sodium sulfate have indicated that in opposition of magne-
sium sulfate (percentage of water remained in acetonitrile,
2.6%) which approved to be a very effective drying agent,
sodium sulfate (percentage of water remained in acetonitrile,
8.8%) was relatively ineffective and removed little or no
residual water from the solvent. Also, the same results were
found in Eller and Lehotay’s[103] study which compared the
functionality of magnesium sulfate and hydromatrix.
However, such results are not certain. For instance, the
application of hydromatrix in recovery of some pesticides,
including fipronil, pyridaben, and acrinathrin by SFE from
melon has been reported more effective than magnesium
sulfate.[96] It seems the conditions of extraction, type of
matrix, and the kind of target pesticides are important in
selecting the drying agent.
Some interesting works
Kamali et al. designed a system to extract Lavandula hybrida
essential oil, which contains linalyl acetate as a pesticide
agent. They used SFE system modified by adding a switch-
ing valve due to pumping the CO2 and liquid solvent, alter-
natively into the backpressure regulator and the extraction
vessel. By this modified system, the yield of linalyl acetate
recovery was higher than unmodified state.[104] In another
study, King et al. designed a binary mixture in addition to
SC-CO2 to separate pesticides from fatty foods without
extracting fat. They devised mixtures of nitrogen and HC-
134a conjugated with CO2 to selectively extract both OPP
and OCP pesticides from the samples. The results although
showed poor improvement for OCP pesticides, but they
were excellent for OPP ones (mean recoveries > 90%).[105]
Likewise, the combination of SFE and enzyme immunoassay
(EIA) as a screening technique for determining pesticide res-
idues has been developed. In this case, Lopez-Avila et al.
demonstrated the ability of SFE-EIA to analysis nine pesti-
cides existing in food samples.[106]
SFE differences with other extraction methods in
extracting pesticides and insecticides
The most important arguments in expressing the differences
of SFE with other techniques, especially traditional solvent
extraction methods, are related to time of extraction, insecti-
cidal strength of extracted component, being economic,
amount of solvent consumption, and selectivity.
It has been indicated that SFE has more selectivity and
efficiency to extract higher molecular weight and thermo-
labile pesticides. About this issue, Piras et al. compared the
efficacy of SFE and hydrodistillation (HD) on extracting the
components of Tanacetum vulgare L. essential oil, which are

used in the preparation of insecticides, foods, dyes, and anti-
microbial materials. Their results showed that essential oils
obtained by HD had a higher amount of hydrocarbon
monoterpenes (14.8% HD vs. 1.8% SFE). But heavier class
of compounds were extracted more by SFE (2.9% HD vs.
21.5% SFE).[107]
In a same work, Ali et al. reported the chemical compos-
ition of Schinus molle volatile oil obtained by HD and SFE
(40
C and 9 MPa). S. molle L. possesses biological activities,
including antifungal, antibacterial, and insecticidal activities.
Results showed that higher molecular weight compounds
were extracted more effectively by SFE than HD.[108] The
identification of diflubenzuron as a thermolabile insecticide
by SFE coupled with electron-capture negative ionization
has been reported, where the SFE showed the much better
selectivity than SPE-HPLC.[109]
Another great advantage of SFE is its less time and less
cost consuming properties. Anastassiades and Schwack
reported that the extraction of carbendazim, 2,4-dichloro-
phenoxyacetic acid, benomyl, and thiophanate methyl as
pesticides from fruits and vegetables are more cost-effective
and faster than traditional solvent extractions.[110] In other
research, Zhang et al. investigated on the separation of
neonicotinoid insecticides by HPLC and SFC. In comparison
with HPLC, a shorter run time by SFC to separate the insec-
ticides was achieved in their study.[111] Wigfield et al. com-
pared the SFE and Soxhlet efficiency in extraction of 22
OCP pesticide samples spiked in eggs. In this study, SFE
method was suggested as the efficient way in reducing time
and costs.[112]
Another difference that has been repeatedly mentioned in
various articles is the higher pesticidal and antifeedant
power of essential oil or pesticide extracted by SFE com-
pared to other methods. For instances, Mart
ın et al. per-
formed a comparative analysis on the function of SFE and
traditional extraction techniques, including HD and Soxhlet
on insect pests (Rhopalosiphum padi, Spodoptera littoralis,
and Myzus persicae). Their study demonstrated that SFE had
up to eight times stronger antifeedant activity than conven-
tional methods.[113] Yao et al. investigated the contact tox-
icity of extracted Acorus calamus L. (an insecticide) on
Sitophilus zeamais. They extracted the A. calamus with four
extraction methods of Soxhlet, soakage, ultrasonic, and SC-
CO2. After several experiments, it was shown that LD50 of
extracted insecticide by SC-CO2 against S. zeamais was
27.26 mg/cm2 which was lower than other methods.[114]
Mart
ın et al. measured the performance of HD and
organic Soxhlet extraction with SFE on the extraction of the
most effective pesticide from wormwood (Artemisia
absinthium L.). They offered the extract of wormwood
obtained by traditional and SFE method to S. littoralis L., a
polyphagous pest of the Mediterranean crops. Their finding
represented that none of the conventional obtained extracts
caused the death of the larvae, while supercritical extracts
provoked a mortality of up to 40%, depending on the condi-
tions of the extraction. The highest pesticide activity of
extract was observed when the supercritical fluid was at
18.0 MPa and 50
C condition.[115] Pavela et al. evaluated the
CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY 11
insecticidal effect of extracts obtained by SFE, HD, and
Soxhlet from savory and thymus on larvae Leptinotarsa
decemlineata. In all experiment, yields of extraction by
Soxhlet with hexane as solvent were higher than others.
However, concerning LD50, HD and SFE extracts showed
lower amount.[116] In 2010, Pavela et al. indicated that the
antifeedants and growth inhibitor activity of Tanacetum par-
thenium L. essential oil obtained by SFE was stronger than
those obtained by HD. Also, their results showed that deter-
rent doses (DD50) for SFE and HD methods were 0.25 and
0.31 mL/cm2, respectively.[117]
Consuming low solvent is other characteristic feature of
SFE. For example, El-Saeid and Khan evaluated the efficien-
cies of SFE and MAE on extraction of pyrethroid insecti-
cides in mixed vegetables and whole and peeled potatoes.
Their results suggested that both techniques showed higher
recoveries of pyrethroids. But, SFE offered the advantages,
including greater resolution, high sensitivity, and minimal
use of organic solvents.[118] Also, requiring less organic solv-
ent and time by SFE compared with GPC has been shown
by Norman and Panton in 2001.[119]
In terms of the recovery of pesticides from plants and
foods, there are conflicting data in the literatures, so that it
is hard to achieve a decisive result. For example, Lanças
et al., in a comparison between Soxhlet and SFE in extrac-
tion of dicofol (a pesticide) from Astyanax bimaculatus schu-
barti (a characteristic fish species), presented that the SFE
recoveries at temperatures lower than 80
C were lower than
Soxhlet.[120] However, SFE had 11% more recoveries than
Soxhlet at temperatures higher than 80
C. In other work
conducted by Valverde et al., the same amount has been
recovered by different methods. Valverde et al. in an experi-
ment on the efficacy of SFE and solvent extraction/gel per-
meation chromatography (GPC) indicated that both
methods had similar results in mean recoveries of pesticides
from wheat samples.[121] But also according to the results
reported by Pavela et al., the recovery value of Soxhlet from
savory and thymus was higher than SFE.[116] It seems that
more precise judgment about differences between various
methods needs considering several conditions such as tem-
perature, pressure, type of pesticide, etc. Some newest stud-
ies worked on same pesticide with different extraction
methods are given in Table 6.
SFE of insecticides
Although many of the pesticides studied in articles are also
considered as insecticides, but SFE of insecticides from
plants and foodstuff is not as well-known as this technique.
However, extraction of insecticides has become of great
interest among studies in recent years. Generally, investiga-
tions performed about this issue are in two types. In the first
type, researchers are trying to find one or more insecticides
in a sample.[122] In this case, the term “yield” is usually
used. The yield is defined as a weight to weight ratio of
extracted insecticide to previously charged materials in the
extractor. For instance, Scapinello et al. extracted the insecti-
cidal components from M. azedarach L at a condition of
 12
M. YOUSEFI ET AL.

Table 6. SFE differences with other extraction methods in extraction of pesticide.

Source Time of
Extraction method Pesticide of extraction Supercritical fluid Temperature Pressure Flow rate Modifier Recovery RSD whole process References
[160]
SFE Triticonazole Cucumber CO2 35
C 24 MPa 2.5 mL/min 20% ethanol 81.62–106.21% 7.30% 21 min
and tomato
[161]
SPE-HPLC 88.3–95.1% 2.6–7.4% 30 min for
preparation step
and about
18 min for HPLC
[162]
SFE combined with GC-MS/MS Propiconazole Wheat straws CO2 26–36
C 1.5 MPa 2.0 mL/min Ethanol 80.9–97.7% 2.3–8% 22–23 min
and gains
[163]
QuEChERS cleanup technique 86.3–96.3% 3.1–12.1% >30 min
combined with LC–MS/MS.
[164]
SFE Multiresidue Banana CO2 60
C 35 MPa 11.86–100% About 30 min
pesticides
[164]
Soxhlet 37.50–100% 8h
[165]
SFE-MSPE-HPLC Cyhalothrin Several vegetable 39.8–49.5
C 18–33 MPa 0.5–1 mL/min 92–98% 3.8–5.7% 10–60 min
and fruit samples
[166]
MAE-SPE-RTL–GC/MS 92% 4.1–13.5% >40 min
[167]
SFE combined with GC-MS/MS Isofenphos- Corn CO2 30
C 1.5 MPa 0.1 mL/min 84.8–100.7% 3.3–10.3% 23 min
Methyl
[168]
Surface-Enhanced Raman 89.7–112.5% >40 min
Spectroscopy
[169]
SFE combined with GC-MS/MS pyrisoxazole Tomato CO2 35
C 1.6 MPa 2.0 mL/min 25% methanol 84.5–98.2% 1.2–4.5% 27 min
[170]
SPE coupled with HPLC- 74.7–88.1% 3.7–7.3%
MS/MS
 CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY 13

Table 7. Insecticide recovery by means of SFE (SC-CO2).

Matrix Pesticide type SFE condition Recovery % References
Date Dimethoate, chlorpyrifos 7.7 MPa, 40
C, and 1 mL/min in first step 91.1–98.3 El-Saeid and AL-Dosari[171]
and pyrethroid then 23.9 MPa, 80
C and 2.5 mL/min in
second step
Apple, peach cucumber Pyrethroids 28 MPa, 49.5
C, 0.5–1.0 mL/min and 89.2–106.8 Bagheri et al.[165]
and tomato methanol as a modifier
Ginseng Organochlorine pesticides 30 MPa and 40
C Quan et al.[172]
wheat, corn, peanut Isofenphos-methyl 1.5 MPa, 30
C, and 0.1 mL/min 75.7–111.4 Chen et al.[167]
Bee Dinotefuran 13.8 MPa, 26.0
C, 1.9 mL/min 78.3–100.2 Chen et al.[173]
Dried plants Six pyrethrins insecticide 11.1–24.3 MPa, 110
C and 0.2 mL/min Wenclawiak and Otterbach[174]
Strawberries Organochlorine insecticides 27.5 MPa and 50
C 74–126 Pearce et al.[175]
Cabbage Atabron 12 MPa, 70
C, 98.7 Lanças et al.[176]
Neem seeds Azadirachtin 20.6 MPa, 55
C, 1.5–3 mL/min and methanol Huang and Morgan[177]
as a modifier
Meat Propoxur 32.9 MPa and 60
C 95 Argauer et al.[178]
Clam Organotin 30 MPa, 45
C, 1.2 mL/min and 5% methanol Liu et al.[179]
as a modifier

15–25 MPa, 39.8–49.5
C and the yield of extraction was as the validated and precise techniques have been intro-
0.48–5.12. They also used M. azedarach L. extracts as an duced. The high recovery potency of SFE in dealing with
insecticide against fall armyworm (S. frugiperda). In their pesticide and insecticide residues along with characteristics
research, 50% mortality (LD50) was observed at a concentra- such as selectivity, saving in time, environment-friendly and
tion of 376.74 mg/kg SC-CO2 and 100% mortality at so on has led to the widespread utilization of this method,
5000 mg/kg.[123] particularly in food analysis. However, there are still some
Another interesting technique in this regard is related to limitations. The non-polarity nature of CO2, requirement
supercritical antisolvent fractionation (SAF) technique. SAF for a high purity of supercritical fluid, the need for high-
is obtained by the continuous contact between the SC-CO2 input investments, the necessity of having experienced per-
and a polar liquid mixture in a pressurized vessel.[124] In sons, the need for clean-up steps frequently are the main
this regard, Mart
ın et al. succeeded in fractionating Persea disadvantages of SFE and SFC. A lot of researches, concern-
indica (a Canarian endemic plant) and extract ryanodol (an ing the preparation of ideal conditions for this purpose,
insecticidal compound). Their work resulted in obtaining including the attentions to parameters of temperature, pres-
37.7% ryanodol from a liquid extract containing 7.5% wt/wt sure, modifier, drying agent, and so on have been carried
of this compound.[125] Also in another work, Mart
ın et al. out. As mentioned, the temperature range of 35–90
C, pres-
extracted ryanodol from P. indica with the yield of sure of 15–28 MPa and flow rate of <1–2 mL/min have been
0.31%–1.13% by SC-CO2.[126] introduced as the optimum setting for extraction and separ-
The conditions used in their study were 10.0–20.0 MPa, ation of pesticides from plant materials and foodstuff.
40–50
C and 0.8–1.4 mL/min. In the second type, which
aims to evaluate the efficiency of the SFE, a certain amount
of one or more insecticides are spiked into a plant or food, Abbreviations
then it is subjected to extraction with a supercritical fluid. EPA Environmental Protection Agency
The comparison between the amounts of spiked and NPIC National Pesticide Information Center
extracted insecticides indicates the “recovery” efficacy of SFE WHO World Health Organization
method. Some experiments about the recovery of insecti- DALYs Disability Adjusted Life Years
LLE Liquid–liquid extraction
cides are given in Table 7. PLE pressurized-liquid extraction
MAE microwave-assisted extraction
UAE ultrasound-assisted extraction
Conclusion SPE solid-phase extraction
QuEChERS quick, easy, cheap, effective, rugged and safe
It would definitely be said that the hourglass sands for the LC liquid chromatography
effectiveness of pesticides are running out. The resistance of GC gas chromatography
pests has forced the consumers to use pesticides more than ECD electron capture detection
ever. Therefore, the residue of such substances has raised in NPD nitrogen–phosphorus detection
FPD flame photometric detection
plants and subsequently in food samples. On the other DAD diode-array detection
hand, the presence of these residues in human food chain SFE supercritical fluid extraction
could cause chronic diseases such as cancers, diabetes, SFC supercritical fluid chromatography
Parkinson, Alzheimer, atherosclerosis, chronic nephropa- RSD relative standard deviation
LOD limit of detection
thies, coronary artery disease, etc. For these reasons, the LOQ limit of quantification
methods for analyzing and controlling the pesticide residues LC/MS/MS liquid chromatography tandem mass spectrometry
have gain special importance. In this regard, SFE and SFC GC–MS gas chromatography coupled to mass spectrometer
14 M. YOUSEFI ET AL.

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