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2.1 Methods used for the analysis of pesticides
Pesticides have become the part and parcel of modern day agriculture. The absence
of pesticides will jeopardize the health of plants, animals and humans. Pesticides are
not only an agricultural commodity but find use in non-agricultural regions. But the
very nature of the pesticides to kill renders them harmful for the humans and other
living beings. Their extensive use has contaminated our soil, water and food, thus
risking our wellbeing. Many persistent pesticides and their degradation products
penetrate into the plant tissues or stay in the water and soil thus appearing in our food
chain. The pesticide residues are magnified during food processing [1] thus making
even the processed foods, storage house of harmful chemicals. Taking into account
the rampant use of pesticides which has lead to the contamination of various strata,
continuous monitoring of environmental and food samples is of utmost importance.
Over the years, pesticides have been determined by many conventional as well as
modern day methods like spectrophotometry [2-43], Polarography [44-50], TLC
[51,52] FTIR [53], HPLC methods using different detectors [54-150], Gas
chromatographic technique, using various detectors or in combination with MS [151-
164], Capillary electrophoresis [165-169], Micellar electrokinetic chromatography
[170, 171]. Extensive research has been carried out on the analysis of pesticide
residues in foodstuffs and environmental matrices. [1,149,162,163,172-182]. The
effect of pesticide exposure on the agricultural workers and children has also been the
topic of research for many scientists [172-174].
2.2 Spectrophotometric methods for pesticide analysis
Spectrophotometry is a very valuable technique which has proven its worth in the
field of pesticide analysis over the years. It is particularly popular because of its
46
features like ruggedness, economical, suitable for wide range of pesticides by using
different reagents, detectors and techniques like flow injection, PLS (Partial least
square) etc.The spectrophotometric analysis of dithiocarbamate (DTC) fungicides has
been extensively carried out in literature [2-4]. Malik et al have developed several
methods for the determination of DTC fungicides spectrophotometrically [10, 12, 14].
Six DTC fungicides were analyzed in a method developed by Malik et al [10],
whereby the fungicides were converted into Se complex for analysis. In another
method three DTC fungicides were decomposed and converted into
diphenylcarbazone complexes for determination [12]. A sensitive spectrophotometric
procedure is mentioned by Jhangel and Pervez [17] for the analysis of acaricide;
kelthane. This method shows good sensitivity in sub parts per million levels. The
alkaline hydrolysis of kelthane produces chloroform which after a series of steps
forms a yellow-red complex with benzidine showing absorption maxima at 490 nm. A
spectrophotometric method for determination of carbamate pesticides; carbaryl,
bendiocarb, carbofuran, methiocarb, promecarb and propoxur has been proposed by
Rodriguez et al [18]. After hydrolysis the pesticides are coupled with diazotized
trimethylaniline (TMA) in a micellar medium. The micellar medium is used to
increase the solubility and sensitivity. The method was applied for carbaryl
determination in spiked tap, river and pond waters. Demibras [19] has described
another method for spectrophotometric analysis of carbaryl in soil and strawberries.
Carbaryl on hydrolysis gave 1-naphthol which reacted with diazotized sulphanilic
acid to form a product showing absorption maximum at 475 nm.Two new methods for
the determination of carbamate pesticide; carbendazim have been reported by workers
[20]. The first method involves the oxidation and complex formation with 2, 2-
Bipyridyl-Fe (III). The complex formed has λmax at 512 nm. In the second method the
pesticides reacts with potassium ferricyanide to form a complex absorbing at 478 nm.
47
Zanella et al [21] have reported a flow injection spectrophotometric method for the
analysis of carbofuran in commercial preparations. The pesticide after hydrolysis with
NaOH is complexed with diazotized 4-aminobenzoic acid and the resultant is
spectrophotometrically determined. Jan et al [22] describe a new spectrophotometric
method for carbofuran determination. The hydrolyzed product of this pesticide reacts
with sodium nitroprusside to make a purple colored complex having λmax at 530 nm.
Carbosulfan has been spectrophotometrically determined by Sao et al [23] by a
sensitive and extractive method. The alkaline hydrolysis of carbosulfan is followed by
its coupling with diazotized p-amino acetophenone, resulting in a red-brown dye
having λmax at 465 nm. The method has been applied to carbosulfan detection in
environmental samples. Rao et al [24] present a novel method for carbosulfan
analysis in environmental samples. The pesticide is hydrolysed and the resultant is
reacted with 2, 4-di-methoxy aniline. The formed dye is extracted into chloroform and
absorbance is measured at 430 nm. Murthy and co-workers [25] have come up with a
novel and sensitive method for the analysis of carbamate pesticide; carbosulfan. A
yellow complex is formed in this method; the procedure has been applied to the
carbosulfan detection in water and grains. Gouda et al [26] have developed three
methods for the analysis of OP pesticides; malathion and dimethoate in formulations
and vegetable samples. Two of the methods are based on the addition of excess Ce+4
in sulphuric acid and determination of unreacted oxidant. The third method involves
the oxidation of the two pesticides by N-bromosuccinimide (NBS) and using
Amaranth dye for unreacted oxidizing agent. A highly sensitive method has been
reported for cypermethrin determination [27]. The insecticide is hydrolysed and then
reacted with KI and leuco crystal violet. The dye formed has very high molar
absorptivity. Jan and co-workers [28] have performed analysis of OP pesticides. In
this method the pesticides are first hydrolysed and then reacted with molybdate
48
solution to yield a blue complex. Jhangel et al [29] developed a sub ppm method for
spectrophotometric analysis of dichlorvos. Hydrolysis of the insecticide is followed
by its coupling with diphenyl carbazide (DPC) resulting in a wine red dye with
absorption maxima 490 nm.
A flame atomic absorption spectrometric method for indirect determination of
dithiocarbamate fungicides; zineb and ferbam has been reported [30]. The fungicides
were decomposed and the metal content was analyzed and hence amounts of zineb
and ferbam were calculated from their stoichiometric composition. Sensitive
analytical methods have been reported for highly hazardous containing pesticide;
Endosulfan [31, 32]. Venugopal and Sumalatha describe a method for endosulfan
determination, whereby the SO2 liberated on its hydrolysis forms a violet dye with
diphenylbenzidine. The method was applied for endosulfan detection in water soil and
vegetable samples. Raju and Gupta describe an endosulfan analysis method whereby,
a pink dye is formed by using the reagents; malonyldihydrazide, p-aminobenzene and
formaldehyde. Tunceli et al [33] discuss a new method for preconcentration and
analysis of pesticides in river water samples. Column sorption technique was
employed for the preconcentration of the analytes. Skoworn et al [34] have performed
the spectrophotometric analysis of thiophanate-methyl has been carried out on the
basis of iodine-azide reaction. Jan et al [35] discuss a spectrophotometric method for
the determination of methyl-parathion by complexing it with different metal ions. Its
complex with Co+2
yielded lowest detection limit of 1.1 ppb and its absorbance was
measured at 345 nm. A sensitive catalytic kinetic spectrophotometric method has been
described for analysis of OP pesticides [36]. OP compounds act as catalysts in the
oxidation reaction of LCV with iodate in presence of HCl and a violet dye is produced
with λmax at 592 nm. A flow injection (FI) method has been studied for the analysis of
phenols and carbamate pesticides [37]. The analytes were detected when a dye was
49
formed on their coupling with diazotized 2,4,6-trimethyl aniline. The method was
applied for pesticides detection in pesticide formulations and water samples.
Derivative spectrophotometry (DS) is a very useful technique for the analysis of
pesticide residues in various matrices. DS increases the sensitivity of the simple
spectrophotometric method, enhances the resolution of zero order spectra and
eliminates the background noise in spectra. Baranowiska and Pieszko [38] discuss a
very useful method for the determination of phenylurea herbicides. Sharma et al [39]
discuss a fourth derivative spectrophotometric method for the analysis of fungicide
thiram. Sodium molybdate reagent has been used to form coloured complex with
thiram. The method has been applied for analysis of thiram in various food stuffs. A
pesticide Azinphos-methyl has been determined using first derivative
spectrophotometric technique [40]. A mixture of acetophenone and blue dye
erioglaucine was used for analysis of the pesticide in commercial formulations. A
simple first order derivative spectrophotometric method has been reported for the
analysis of insecticide imidacloprid [41]. The procedure was used for the
determination of the insecticide in commercial formulations and it yielded good
results.
2.3 HPLC methods for pesticide analysis
Chromatographic analysis is the most sought after technique for pesticide residue
analysis whether GC, LC or in combination with LC and applying from the wide
range of detectors available like UV, DAD, chemiluminescence, ECD, NPD, FD etc.
[184]. HPLC is a creditable method for the analysis of wide variety of pesticides.
Several heat unstable and polar pesticides show better detection with this technique. A
wide range of reviews are available [185-206] on HPLC methods and sample
50
preparation techniques used for pesticide residue analysis from different
environmental and food matrices.
2.3.1 HPLC-UV Methods
HPLC-UV is one of the most popular, efficient and cost effective methods of
detection for microanalysis and separation of pesticides in different environmental
matrices. The hyphenation of HPLC with UV is useful for a large number of
pesticides as most of these are amenable to UV detection. Basheer et al [90] analyzed
the carbamate pesticides by making use of an HPLC-UV method. Five pesticides;
simazine, fenulfothion, etridiazole, mepronil and bensulide were detected by He and
co-workers [91]. A multiresidue analysis of carbamate pesticides was carried out by
Sánchez-Brunete et al [97]. Work has also been done on the separation of N-methyl
carbamate [102] and carbamate pesticides [103]. A method was developed by Gou et
al [111] for the determination of six carbamate pesticides in water with HPLC. HPLC
with UV detection was used to study the extraction of organochlorine pesticides from
spiked seaweed samples [93]. Chen et al [98] employed the HPLC-UV technique for
analysis of organochlorine pesticides. Moreno et al describe procedures for analysis
of organochlorine pesticides [104, 112]. Moreno et al [112] determined
organochlorine pesticides in agricultural soils. HPLC-UV has been used for the
determination of 4 pesticides in tap water and well water [114]. A paper [99]
describes the use of an LC-LC method for the determination of acidic pesticides in
soil. Liu et al [100] describe a method for the separation of 12 pesticides using a C18
capillary column. Linuron and diuron have been determined in human urine on a poly
(methyloctylsiloxane) column [101]. In another work 11 phenylurea herbicides have
been determined with HPLC [115]. Four Organophosphorous pesticides (OP) were
analyzed in water by Salleh et al [105]. Another method [106] explains the
51
determination of 8 OP pesticides in soil using Methanol/Water mobile phase.
Lourencetti [108] used HPLC-UV for the analysis of three pesticides. A method was
developed to analyze cypermethrin from leaves of gingko biloba [117]. Mauldin et al
[118] developed a new method for chlorpyrifos analysis. OP pesticides were
quantified in water, fruit juices and fruits by Farajzadeh and associates [119]. Khan
and co-workers [121] developed a new method for the analysis of two pesticides. Five
pesticides were analyzed from river water by external standard method by Brondi et
al [122]. Sanagi and associates [124] describe a new method for pesticides
determination in water samples. He et al [125] have discussed a new HPLC-UV
method for the detection of four pesticides. One of the methods elaborates the method
for pesticides residue analysis from parts of eggplant [126], while in another method
18 herbicides are determined in tap water whereby they undergo a photochemical
reaction followed by HPLC-UV separation [127]. HPLC-UV analysis of pesticide
residues has been carried out in different vegetables by several workers [129,132,
133]. Brito et al [131] developed a procedure for the determination of pesticide
residues in coconut water. A method explains the quantification of ten pesticides in
egg samples with HPLC-UV detection [134].
2.3.2 HPLC-DAD Methods
HPLC analysis using a Diode Array Detector (DAD) is a very sensitive technique
which has been widely used for pesticide determination. Jeannot et al [66] used diode
array detector in conjunction with HPLC for the analysis of phenylurea herbicides. In
a method developed by Thompson et al [76], Azadirachtin (Az), the natural pesticide
derived from Neem has been determined by HPLC-DAD. Ferrer and co-workers [81]
analyzed phenylurea herbicides by HPLC technique using diode array detection.
HPLC-DAD of OP pesticides in bovine tissue was done by Valencia [92] et al. Five
52
OP pesticides (chlorpyrifos, chlorfenvinphos, diazinon, fenitrothion, parathion-
methyl) were analyzed in bovine liver muscle by Llasera et al [107]. HPLC-DAD has
been an important tool in detecting pesticide residues in various fruit and vegetable
samples. Melo et al [94] determined ten commonly used pesticides on lettuce with
LC-DAD. Kaihara et al [116] developed a new method for the analysis of 27
pesticides in various fruit and vegetable samples with photodiode array detection.
Liang et al [123] have determined phoxim in water. A new method was applied to the
pesticide determination in strawberries [130]. HPLC-DAD is instrumental in detecting
pesticides in water matrices also. HPLC-DAD of 16 pesticides in groundwater
samples was carried out by D’Archivio et al [95]. Salleh et al [109] detected 5
pesticides from water by using this technique. HPLC-DAD has been used to
determine pesticides in surface waters [113, 120].
2.3.3 HPLC-MS Methods
Mass spectrometry (MS) in conjunction with LC (Liquid Chromatography) provides
one of the most sensitive and selective methods for pesticide analysis. Ingelse et al
[78] determined polar OP pesticides in aqueous samples using liquid chromatography
tandem mass spectrometry. Lacorte et al [79] analyzed the OP pesticides with a very
sensitive method using LC-APCI-MS. (Liquid chromatography-Atmospheric pressure
chemical ionization- Mass Spectrometry). In one of the methods, pesticide residues of
17 pesticides were detected in agricultural products by LC/MS [80]. Ferrer et al [81]
analyzed pesticides with the help of an LC-APCI-MS method. Mattina et al [82]
developed a particle beam MS method for the analysis of phenylurea herbicides in
water matrices. Schaaf et al [83] performed analysis of Az and tetranortriterpenoids
from Neem parts. The method was based on the Reversed Phase HPLC and Atomic
Pressure Chemical Ionization (APCI) mass spectrometry. Barrek et al [84] analyzed
53
the content of Azadirachtin A (Az A) in Neem Oil by LC-MS/MS and studied the
chemical decomposition of Az A. Sarais et al [85] analyzed Az and azadirachtoid
substances; salanin and nimbin. Sannino [86] detected three natural origin pesticides
namely, abamectin, spinosad and azadirachtin in fruit and vegetable samples with LC
and tandem mass spectrometry. Ambrosino et al [87] determined Az A extracts from
neem seed kernels and Pozo et al [89] analyzed Az residues in oranges.
2.3.4 Other HPLC Methods
The feature of HPLC technique can be enhanced to suit the different type of analytes
by using various modes of detection. Post column derivatization and
chemiluminescence detection are the viable options which can be put into use for
different pesticides. Nakazawa et al [57] analyzed the dithiocarbamate fungicides in
vegetable samples by using reversed phase ion pair liquid chromatography with
chemiluminescence detection. N-Methyl carbamates were analysed by post column
photolysis and chemiluminescence detection in water, apple and pears [110]. Patsias
et al 1 developed a photo diode array/post column derivatization with fluorescence
detection method for the analysis of pesticides. De la P na [77] analysed five
herbicides in river water with photochemically induced fluorescence detection. Koc
and associates [128] have come up with a novel method to analyze aldicarb, propoxur,
carbofuran, crabaryl and methiocarb in honey samples involving post column
derivatization and fluorescence detection.
2.4 Sample Preparation techniques
Sample preparation is an important and often the limiting step in the sensitive analysis
of pesticides from myriad range of matrices. A wide range of techniques are available
for sample preparation and pre-concentration of pesticides from complex matrices
54
prior to their detection. Sample preparation is often a multistep process involving
sampling, cleanup, elution etc.
The literature is replete with the examples of different kind of sample preparation
techniques used for the pesticide residue analysis from various matrices. A number of
useful reviews are available to study the different detection and sample preparation
techniques used in the pesticide determination [185-205]. Liquid liquid extraction
(LLE) is one of the earliest and most commonly used extraction techniques employed
for pesticide residue analysis in complex media. Lacorte et al [79] carried out liquid-
solid extraction of pesticides prior to their analysis. Sannino [86] extracted the
Figure 2.1: Steps in the pesticide residue analysis
pesticides from fruit and vegetable matrices using acetone followed by liquid-liquid
partitioning. LLE was used by workers [117,118,128] for extraction of pesticide
residues from plant parts. Khan et al [121] employed ethylacetate and hexane for the
LLE of pentachloronitrobenzene and hexachlorobenzene and its metabolites prior to
Sample Preparation
(Sampling, homogenization)
Extraction with solvents
Clean-up to remove interferences
Elution, concentration of analytes
Redissolving in solvent for
Chromatographic Analysis
55
their HPLC determination. Baig and co-workers [133] used this technique for
extraction of three pesticides from vegetable samples.
Sonication assisted extraction has been used by Sánchez-Brunete [97] for carbamate
pesticides. Koc et al [128] have successfully made use of florisil column and
subsequent elution with hexane/dichloromethane for pesticide extraction.
Solid Phase extraction is one of the most commonly used and preferred technique for
literature using SPE technique to extract pesticide residues of 5 herbicides from river
water [77]. Ingelse and co-workers [78] used SPE for the pre-concentration of polar
OP pesticides. Porous polypropylene membrane protected Micro-SPE technique was
used by Basheer et al [90] for carbamate pesticides detection from soil samples. SPE
cartridges with different sorbent materials were used for pre-concentration of
pesticides of which Oasis HLB and Strata-X were found to give better results [95].
Chen et al [98] presented an online SPE method subsequent to dynamic MAE for the
analysis of organochlorine pesticides. Quantitative determination of pesticides was
achieved with a 250 fold enrichment through SPE method developed by Liu et al
[100]. SPE was used as an extraction and sample preparation technique for the
analysis of pesticides in human urine [101]. Sugarcane herbicides were analysed by
Lourencetti and co-workers [108] using C18 SPE discs. Another paper discusses the
determination of N-methyl carbamate pesticides through the use of automated SPE
[110]. Bondelut PPL cartridges were used in the SPE procedure developed to detect
pesticides in the Macedonian lake waters [113]. Multivariate C-nanotubes were
employed for the SPE of highly leachable pesticide residues in water samples [114].
In another method phenylurea herbicides were determined in drinking water by using
C18 cartridges [115]. Another paper presents comparison between LLE, SPE and SFE
modes for pesticide residue determination [122]. Lee et al [127] used an online SPE
method for the pre-concentration and extraction of herbicides in water. Brito and co-
56
workers [131] used SPE with C18 cartridges to analyze pesticide residues in coconut
water. A useful review is resented by Picó et al [139] on the advances made in the
SPE technique for analysis of quaternary ammonium herbicides determination.
Sanchiz-Mallos et al [141] developed an SPE-HPLC method for analysis of phenoxy
acid herbicides from drinking water. Vitali et al [143] used SPE for the HPLC-UV
analysis of triazines and dinitroanilines from real water samples. Many papers in
literature present SPE as a suitable enrichment technique for the Neem derived
pesticide; Azadirachtin [144-146].
Microwave assisted extraction (MAE) is an effective technique for extraction of
pesticide residues from several environmental and food samples. Chen et al [98] made
use of MAE for the followed by on-line SPE of organochlorine pesticides.
The conventional extraction methods are popular but they suffer from many
drawbacks like use of large volume of solvents, agitation or heating with the solvent
for long time thus increasing the risk of thermal degradation of many pesticides. But
the new innovations in the field of extraction address these concerns. The novel
methods of extraction like MAE, Pressurized fluid extraction, Supercritical fluid
extraction (SFE), Solid phase microextraction (SPME) etc. overcome these problems
as these are fast, use solvent economically, thus are environment friendly [206,207].
Moreno et al [93] performed Microwave assisted microextraction (MAME)-SPE and
MAME-SPME (solid phase microextraction) with organochlorine pesticides. SPME
with four different coatings of fibre like PDMS (poly dimethyl siloxane),
PDMS/divinylbenzene, Carbowax/Tempelated resin and polyacrylate was made use
of to determine 10 pesticides [94]. MAME-SPME was also used by researchers to
analyze organochlorine pesticides [104]. Salleh et al [105] used SPME and online
SFCO2 for OP pesticide analysis. Automated intube SPME analysis of carbamate
pesticides was performed by Gou et al [111]. Focused microwave assistance followed
57
by SPME was used by some researchers for pesticide residue analysis from
strawberries [130]. In another paper, authors focus on the optimization of conditions
for Headspace-SPME for the determination of seven OP pesticides in natural waters
[183].
Microwave assisted solvent extraction (MWASE) has been employed by Hogendoorn
et al [99] for multiresidue analysis of pesticides in soil. In one of the methods,
MAME and soxhlet extraction were used for the determination of OP pesticides from
soil [106]. Moreno and associates [112] employed MAE with surfactants for pesticide
residue analysis in soils. Singh, Foster and Khan [129] used MAE to determine
pesticide residues in cooked and raw vegetables.
Continuous flow microextraction (CFME) was used by He et al [91] whereby a single
drop of solvent is immersed in a continuous flowing sample solution in a 0.5 ml glass
chamber. Matrix Solid Phase Dispersion (MSPD) coupled with SPE has been used as
sample preparation technique by Valencia et al [92]. An MSPD method was validated
for the pesticide analysis from the bovine tissues, involving C18 extraction and silica-
gel cleanup [107].
A green extraction technique Supercritical fluid extraction (SFE) has also been used
for pesticide residue extraction from varied matrices. Ambrosino et al [87] used
SFCO2 and liquid CO2 as extracting agents. Carbamates were determined by Sun et al
[103] using MAE and their subsequent extraction with SFE. Kaihara and associates
[116] used SFE for multiresidue analysis in food stuffs.
Liquid phase microextraction (LPME) was employed by Liang et al [123] for phoxim
determination. Cunha et al [184] have discussed at length the current trends in the
liquid liquid microextraction (LLME) for the pesticide residue analysis in food and
water. Dispersive liquid liquid microextraction (DLLME) uses an extraction solvent
mixture made of a highly non-polar and a water soluble polar solvent. This method
58
fetches high pre-concentration in a short time [208]. In recent times DLLME is
gaining popularity as extraction technique for pesticide residue analysis in water
samples [119,120]. He et al [125] have employed DLLME with ionic liquid extraction
of pesticides from water samples. Liquid membrane microextraction is a relatively
new concept in pesticide extraction which leads to high enrichment factor. Hylton et
al [102] used barrier film protected, mixed solvent optimized micro-scale membrane
extraction for pesticide analysis. Double phase liquid liquid microextraction
(DPLMME) has been used for pesticide extraction by Sanagi et al [124] whereby,
polypropylene tubular membrane has been used. Soxhlet extraction followed by
membrane separation has also been used for high lipid containing matrices [134].
A new concept, molecularly imprinted polymers (MIPS) are being used up for
pesticide detection. The MIPs are inexpensive, easy to synthesize, highly selective
and very sensitive, these qualities make them very desirable for extracting various
pesticides from varied matrices. Linuron and isoproturon were used as templates for
MIPs in the analysis of phenyl urea herbicides from plant extracts [132].
Microextraction by packed sorbent (MEPS) is an innovative technique which is
miniaturization of SPE. This technique is quite advantageous as it is fast, uses less
solvent, requires small sample size and can be automated. Bagheri et al [209] mention
the use of reinforced MEPS syringe for the analysis of triazine, OP, organochlorine
and aryloxy phenoxy propionic acid pesticides in aquatic environment. MEPS
procedure for the analysis carbamate pesticide; aldicarb has also been described [210].
59
Table 2.1 Sample Preparation Methods used in the Analysis of Pesticides
S.
No.
Matrix Pesticide Cleanup
technique
Method Analysis Recovery
(RSD%)
Detection
Limits
Ref
1. Soil Carbamates (carbaryl,
propham, methiocarb,
promecarb, chlorprophan,
barban)
Micro spe,
Oasis HLB
cartridge
C18 disc in
polypropylene
membrane
HPLC-UV,
ACN/water 40/60,
225 nm
93-110(4-11%) LOD 0.01-
0.4 ng g-1
90
2. Natural
water
sample
Simazine, fensulforthion,
etridiazole, mepronil,
bensulide
CFME Single drop of
sample collected
in microsyringe,
injected to
HPLC
HPLC-UV,
ACN/water 50/50,
220 nm
86.9-106 LOD 0.6-3ng
mL-1
91
3. Bovine
tissue
Parathion-methyl,
fenitrothion, parathion,
chlorfenvinphos, diazinon,
ethion, fenchlophos,
chlorpyrifos, carbofenothion
MSPD
coupled
with SPE
C18, silica HPLC-DAD 89.7-99.9(0.7-
4.7)
0.04-.25
µg g-1
92
4. Seaweed
sample
4,4´DDD, dieldrin, 4,4´ DDT,
2,4´ DDT, 4,4´ DDE, aldrin
MAME-
SPME
MAME-
SPE
PDMS-DVB
Bond elut ENV,
C18, Oasis HLB
HPLC-UV,
MeOH/Water
84/16
87.4-101
(7.9-10.3)
78.8-107.7
(2.8-5.3)
138-348
ng g-1
2-38 ng g-1
93
5. Lettuce 10 pesticides (acetamiprid,
azoxystrobin, cyprodinil,
fenhexamid,
fludioxonil,folpet, iprodione,
metalaxyl,
primicarb,tolyfluanid)
SPME PDMS,
PDMS/DVB,
CW/TPR, PA
HPLC-DAD,
MeOH/Water
(0.1%
trifluroacetic acid),
224 nm
N. R. 0.28-1.54 mg
Kg-1
94
6. Ground
water
16 pesticides (aldicarb,
atrazine, desethylatrazine,
SPE C18, graphitised
carbon black,
HPLC-UV,
ACN/water(0.1%
Oasis HLB
71-111(1-10%)
0.003-0.014
µg L-1
95
60
desysopropylatrazine,
carbofuran, 2,4-D, dicloran,
fenitrothion, iprodione,
linuron, metalaxyl,
metazachlor, phenmedipham,
procymidone, simazine,
vinclozolin)
Oasis HLB,
Lichrolut EN,
Strata-X
phosphoric acid)
50/50, 200-400 nm
Stata X
71-113(1-10%)
7. Tomatoes Benomyl,
tebuthiuron,simazine,
atrazine, diuron, ametryn
SPE C18, aminopropyl HPLC-UV,
ACN/0.01%
aqueous NH4OH
(35/65), 235 nm
Commercial
NH2
81-106(0.7-41)
Commercial
C18
29-57(9.2-
55%)
14-28
µg Kg-1
96
8 Soil Oxamyl, methomyl,
Propoxur, carbofuran,
carbaryl, methiocarb
SAESC Ultrasonication,
MeOH
extsssraction
HPLC-Fl, 82.9-99.8
(0.4-10%)
1.6-3.7
µg Kg-1
97
9. Wheat, rice,
corn, bean
Pentachloronitrobenzene, p,p´
DDE, p,p´DDT, o,p´DDE,o,p
DDT, o,p´DDD
DMAE-SPE Online spe C18 HPLC-UV,
ACN/water,
238 nm
89-101(0.8-
6.5%)
Wheat
19-37
(ng g-1
)
98
10. Soil 10 pesticides (bentazone,
bromoxynil, metsulfuron-
methyl, 2,4-D, MCPA,
MCPP, 2,4-DP, 2,4,5-T, 2,4-
DB, MCPB)
MASE -- LC-LC 60-90(5-25%) 5-50
µg Kg-1
99
11. Tap water
and apples
Simazine, fensulfothion,
isoprocarb, fenobucarb,
chlorothalonil, etridiazole,
mepronil, pronamide,
mecoprop, bensulide,
isofenphos, terbutol
SPE Octyl bonded
silica
Capillary HPLC 85-107
(4.1-10.7%
apples,
4.1-8.4 water)
0.15-0.8
µg mL-1
100
61
12. Urine Diuron, linuron SPE Microwaved
PMOS on silica
HPLC-UV
ACN/water
(40/60) 254 nm
85-103(0.37-
1.8%)
14 µg L-1
(diuron)
2.8 µg L-1
(linuron)
101
13. Methanol Carbamate pesticides
(Aldicarb, propoxur,
carbofuran, carbaryl,
methiocarb)
Barrier film
membrane
extraction
Octanol barrier
film used
HPLC-UV,
ACN/water/MeOH
214 nm
(1.9-9.5%) 0.001-5.5
µg L-1
102
14. Soil Carbamate pesticides
(propoxur, chlorpropham,
propham, methiocarb)
MAE
SFE
OAD
Methanol
CO2 + Methanol
HPLC-UV,
ACN /water
(40/60)
225 nm
81.8-
102(4.9%)
66-98(5.5%)
N. R. 103
15. Agricultural
soil
Organochlorine pesticides
(4,4´-DDD, dieldrin, 4,4´-
DDT, 2,4´-DDT, 4,4´-DDE)
MAME-
SPME
POLE
PDMS/DVB
HPLC-UV,
MeOH/Water
(85/15)
(5.5-8.4%) 56-96
ng g-1
104
16. Water Organophosphorous
pesticides (bensulide,
diazinon, EPN, chlorpyrifos)
SPME-
SFCO2
PA(spme) HPLC-UV,
MeOH/Water
(80/20)
(8.6-13.5%) 40-600 µgL-1
105
17. Soil 8 OP pesticides (dimethoate,
methidathion, parathion-
methyl, malathion,
ethoprophos, parathion-ethyl,
diazinon, chlorpyrifos)
MAME
Soxhlet
extraction
POLE, Genapol
X-080
Hexane/Acetone
HPLC/UV,
MeOH/Water(35/6
5)
20.5-82 (0.8-
2.1%) with
Genapole-
X080
0.2-11.3
ng mL-1
(Genapol-
X080)
106
18. Bovine
muscle,
liver
5 OPPs (chlorpyrifos,
chlorfenvinphos, diazinon,
fenitrothion, parathion-
methyl)
MSPD C18 extraction,
silica gel clean-
up
HPLC-DAD,
MeOH/Water,
gradient flow, 244-
287 nm
55-100
(1.9-5.2%) in
liver samples
50-100
ng g-1
(liver),
25-50 ng g-1
(muscle)
107
62
19. Soil, soil-
vinasse
Diuron, hexazinone,
tebuthiuron
SPE C18 HPLC-UV,
MeOH/water
(45/55), 247 nm
78-120 (>10%) 0.025-0.05
mg Kg-1
108
20. Water Simazine, chlorothalonil,
bensulide, thiobencarb, EPN
SPME/SFE PA/
SFCO2
HPLC-PDA,
ACN/water(60/40)
(7.4-12%) 0.07-0.219
mg L-1
109
21. Water,
Apple, pear
N-methyl carbamate
pesticides (Propoxur,
bediocarb, carbaryl,
promecarb)
SPE C18 HPLC-CL 99-96
(0.49-0.81%,
water)
80-89(fruits)
3.9-36.7
ng L-1
110
22. Water Carbamate pesticides
(carbaryl, propham,
methiocarb, promecarb,
chlorpropham, barban
SPME In-tube spme HPLC-UV,
ACN/water
(50/50)
220 nm
97.3-100
(1.7-5.3%)
1-15 µg L-1
111
23. Agricultural
Soil
Oraganochlorine pesticides
(4,4’-DDD, Dieldrin, 4,4’-
DDT, 2,4’-DDT, 4,4’-DDE,
Aldrin)
MAE (POLE+Polyoxy
ethylene10 Cetyl
ether),
(POLE+Polyoxy
ethylene 10
Stearyl ether),
surfactant
mixtures used
HPLC-UV,
MeOH/Water
(85/15) at 220 and
238 nm
44.7-99.1
(Cetyl
mixture)
44.8-103.6
(Stearyl
mixture)
(0.275-
0.655%)
86.4-806.4
ng g-1
(cetyl
mixture)
150.8-734
ng g-1
(stearyl
mixture)
112
24. Surface
waters
Dimethoate, 2,4-D, linuron
and MCPP
SPE Bond Elut PPL
cartridges
HPLC-UV-DAD,
ACN/Water/
Acetic acid
(39/59/2)
229,249 nm
64-92%
(2.6-8.3%)
0.01-0.31
µgL-1
113
63
25. Tap Water
Well water
Atrazine, dicloran,
metazachlor, simazine
SPE Multi-walled
carbon nano
tubes
HPLC-UV,
ACN /Water
230 nm
92.7-95.3 (tap
water) (2.5-
4.6)
5-15 ng L-1
114
26. Drinking
Water
Phenylurea herbicides (11
pesticides)
SPE C18 HPLC-UV,
ACN/Phosph-ate
buffer (35/65)
32.6-150
(1.1-6.7%)
3.8-43.6
µg L-1
115
27. Fruits and
vegetables
27 pesticides SFE Extrelut NT +
Bond Elut C18,
Elution with
CAN
HPLC-PDA,
230 nm
49.3-103.6
(30.5-0.4%)
for cucumber
0.005-0.1
ppm
116
28. Ginkgo
biloba
leaves
Cypermethrin LLE Hexane/Ocatne(
99:1)
HPLC-UV,
Hexane/THF
(99/1)
254 nm
81 (3.2%) 0.1 mg Kg-1
117
29. Black oil
sunflower
seeds
Chlorpyrifos LLE Acetonitrile/
Phosphate buffer
(90:10)
HPLC-UV,
ACN /Phosphate
buffer (75/25)
230 nm
>95(0.81-
4.1%)
0.221 µg g-1
118
30. Water
samples,
fruit juice
and fruits
Organophosphorous
pesticides (fenitrothion,
diazinon, ethion)
DLLME Chloroform,
methanol
HPLC-UV,
Methanol, 210 nm
54.9-69.4
(2.2-4.1)
2-3 ng mL-1
119
31. Surface
water
sample
Carbamate pesticides
(metolcarb, carbofuran,
carbaryl, isoprocard,
diethofencard)
DLLME Water/ACN/Tric
hloromethane
HPLC-DAD,
MeOH/Water
(60/40)
86-97.2
(3.5-8.7%)
0.1-0.5
ng mL-1
120
32. Soil PCNB and HCB LLE Ethyl acetate and
hexane
HPLC-UV,
MeOH/Water
(96/4),
300 nm
97.8-99.2
(1.4-2.9%)
0.0001-
0.0003
µg mL-1
121
64
33. River Water Tebuthiuron, hexazinone,
diuron,2,4-D, ametrine
LLE
SPE
SFE
External
standard method
HPLC-UV,
ACN/Water
(28/72)
238 and 254nm
94%(LLE)
98%(SPE)
28-58%(SFE)
10-30 µg L-1
122
34. Water Phoxim LPME HPLC-DAD (8.4%) 10 ng mL-1
123
35. Water Parathion, phoxim, phorate,
chlorpyrifos
DLLME Ionic liquid
extraction
HPLC 101.8-113.7 at
200 µg L-
1(>4.7 %)
0.1-5 µg L-1
125
36. Eggplant Diazinon, malathion,
sumithion,
LLE Ethylacetate,
hexane
HPLC-UV
ACN/Water
(70/30)
254 nm
88.53-119.59
(11.2-12.8%)
0.02 mg kg-1
126
37. Tap water 18 herbicides SPE Photochemical
reaction
HPLC-UV
detection after
photochemical
reaction,
phosphate buffer/
CAN
77-103
(0.8-2.6%)
0.1-2.3x10-10
M
127
38. Honey Aldicarb, propoxur,
carbofuran, carbaryl,
methiocarb
Florisil
column
Elution with
hexane/dichloro
methane
HPLC-PCD, FD,
water/ACN
(90/10)
77.3-85.1
(1.7-2.3%)
4, 5 ng g-1
128
39. Strawberries Carbendazim, diethofencarb,
azoxystrobine, napropamide,
bupirimate
Focussed
microwave
assisted
extraction
SPME HPLC-DAD
(3-7.3%) 0.05-1
mg Kg-1
130
40. Coconut
water
Captan, chlorothalonil,
carbendazim, lufenuron,
diafenthiuron
SPE C18, methanol
elution
HPLC-UV, 254
nm
75-104
(1.4-11.5%)
≥2 mg Kg-1
131
65
41. Vegetables Triazophos, profenofos and
chlorpyrifos
LLE Ethylacetate HPLC-UV (>20%) N. R. 133
42. Egg samples 10 pesticides Soxhlet
extraction,
membrane
separation
---
HPLC-UV 60-98% 0.002-0.018
mg/kg
134
43. Citrus
samples
diflubenzuron, flufenoxuron
hexaflumuron and
hexythiazox,
MSPD C-8, silica
sorbent,
Dichloromethane
eluent
HPLC-UV,
200 nm
74-84% 0.15-0.25
µg/g (LOQ)
135
44. Water 8 Organophosphorous
pesticides
CPE Polyoxyethylene
10 lauryl ether
and GenapolX-
080
HPLC-UV 27-105% >30 µg L-1
136
66
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