Journal of Environmental Chemistry and Ecotoxicology Vol. 4(2), pp.

19-28, 22 January, 2012

Available online at http://www.academicjournals.org/JECE
DOI: 10.5897/JECE11.072
ISSN-2141-226X ©2012 Academic Journals

Full Length Research Paper

Pesticide residue analysis of fruits and vegetables

Rohan Dasika, Siddharth Tangirala and Padmaja Naishadham*
Department of Chemistry, Osmania University, Hyderabad, India.
Accepted 9 December, 2011

This project describes an efficient and effective analytical method to screen pesticides in fruits and
vegetable samples using liquid chromatography tandem mass spectrometry (LC-MS/MS). A quick, easy,
cheap, effective, rugged, and safe (QuEChERS) method with acetate buffering (AOAC Official Method
2007.01) was used for sample preparation, which has been previously shown to yield high-quality
results for hundreds of pesticide residues in foods.

Key words: Liquid chromatography/mass spectrometry (LC/MS), pesticide residues, pesticides, fruits,
vegetables.

INTRODUCTION

Plant protection products (more commonly known as earth and causing problems in human beings and wildlife,
pesticides) are widely used in agriculture to increase the the quantity of pesticide being consumed becomes a
yield, improve the quality, and extend the storage life of necessary knowledge. Analytical quality requirements like
food crops (Fern ndez-Alba and Garc a-Reyes 2008). trueness, precision, sensitivity and selectivity have been
Pesticide residues are the deposits of pesticide active met to suit the need for any particular analysis.
ingredient, its metabolites or breakdown products present Unfortunately, not all farmers follow legal practices and
in some component of the environment after its applica- due to the tremendous number of pesticides and crops in
tion, spillage or dumping. Residue analysis provides a production, a number of analytical methods designed to
measure of the nature and level of any chemical determine multiple pesticide residues (Food and Drug
contamination within the environment and of its Administration, 1999; Luke et al., 1975; Specht and
persistence. The pesticides must undergo extensive Tilkes, 1980; Lee et al., 1991; Andersson and Pålsheden,
efficacy, environmental, and toxicological testing to be 1991; Cook et al., 1999; General Inspectorate for Health
registered by governments for legal use in specified Protection, 1996; Fillion et al., 2000; Sheridan and Meola,
applications. The applied chemicals and/or their degrada- 1999; Lehotay, 2000). In 2003, the QuEChERS method
tion products may remain as residues in the agricultural for pesticide residue analysis was introduced
products, which becomes a concern for human exposure. Anastassiades et al. (2003), which provides high quality
Selected sampling programmes can be used to results in a fast, easy, an inexpensive approach. Follow-
investigate residual levels of pesticide in the environment, up studies have further validated the method for greater
their movement and their relative rates of degradation. than 200 pesticides (Lehotay et al., 2007).
The maximum residue levels (MRLs) (or „tolerances‟ in Technical developments always follow the way from the
the United States) limit the types and amounts of primitive via the complicated to the simple. The most
residues that can be legally present on foods are set by common techniques in modern multi-residue target
regulatory bodies worldwide. Pesticide residue analysis is pesticide analysis are gas chromatography, liquid
tremendously an important process in determining the chromatography coupled to mass spectrometry (GC-MS,
safety of using certain pesticides. Pesticides polluting the LC-MS) and/or tandem mass spectrometry (GC-MS/MS,
LC-MS/MS) with triple quadrupole mass analysers. The
numerous methods available for pesticide analysis show
the importance of this application and rapid pace of
*Corresponding author. E-mail: tapadmaja@gmail.com. Tel: developments in analytical chemistry. For example, Agu¨
9348405065. era et al. (2000) described a method (Splitless large-
20 J. Environ. Chem. Ecotoxicol.

volume GC-MS injection for the analysis of organo- used for the sample preparation procedure. Analytical-grade
phosphorus and organochlorine pesticides in vegetables pesticide standards were ordered from Sigma- Aldrich.
Individual standard stock solutions were prepared by dissolving
using a miniaturised ethyl acetate extraction) for the
the crystalline standards in acetonitrile (or dimethyl formamide for
measurement of only ten organophosphorus and those insoluble in acetonitrile) to reach the final concentration of
organochlorine pesticides by GC-MS, but over the past 1000 to 4000 mg/ml. For method optimization, individual standard
decade, the number of pesticides typically included in solutions were used, which were prepared by diluting the stock
methods has increased dramatically. The sample solution to a concentration of 1 to 4 mg/ml. A standard mix solution
preparation techniques have also advanced to in acetonitrile for preparation of calibration standards was prepared
from the individual stock solutions to yield 10 mg/ml.
complement the analytical techniques depending on the
types of analytes and matrices monitored.
Anastassiades et al. (2003) described the „quick, easy, Sample preparation
cheap, effective, rugged, low solvent consumption, wide
pesticide range (Polar, pH – dependent compounds) and The acetate-buffered QuEChERS sample preparation method for
safe‟ (QuEChERS) method for pesticide residues in food pesticides (AOAC Official Method 2007.01) was applied to all the
samples. After homogenization with a house-hold mill (equipped
as an example of a method that takes advantage of the
with stainless steel knives), a 15 g portion of the homogenized
powerful features of nearly universal selectivity and high sample was weighed into a 50 ml polytetra fluoro ethylene (PTFE)
sensitivity of modern GC- and LC-MS(/MS) instruments. tube and 100 ml of 50 mg/ml triphenyl phosphate (TPP) surrogate
The QuEChERS approach has been extensively standard solution in acetonitrile was added followed by 15 ml of
validated for hundreds of pesticide residues in many acetonitrile containing 1% acetic acid (v/v not accounting for purity).
types of foods, and has become Association of Analytical Then, 6 g MgSO4 and 2.5 g sodium acetate trihydrate (equivalent
to 1.5 g of anhydrous form) were added, and the sample was
Communities (AOAC) Official Method 2007.01 (Lehotay shaken forcefully for 4 min. The sample was then centrifuged at
et al., 2007) and CEN (2008). The QuEChERS method 4000 rpm for 5 min and 5 ml of the supernatant were transferred to
has several advantages over most traditional methods of a 15 ml PTFE tube to which 750 mg MgSO4 and 250 mg PSA were
analysis. High recoveries (greater than 85%) are added. The extract was shaken using a vortex mixer for 20 s and
achieved for a wide polarity and volatility range of centrifuged at 4000 rpm again for 5 min. Approximately 3ml of the
pesticides, including notoriously difficult analytes. Very supernatant were filtered through a 0.45 mm PTFE filter (13 mm
diameter), and 800 ml portions were transferred to autosampler
rugged because extract clean up is done to remove vials. The extracts were evaporated to dryness under a stream of
organic acids. argon and reconstituted in 800 ml acetonitrile/water (20/80, v/v) for
The most common approach is to use matrix-matched the LC-MS/MS analysis.
calibration standards. However, it can be difficult to find a For the matrix-matched and standard addition calibrations, 4 to
blank matrix from which to prepare the calibration 80 ml of reconstituted samples were transferred into autosampler
glass inserts and 20 ml portions of 0, 250, 500 and 1250 ng/ml
standards and compensation from one sample to another
standard mix solutions containing pesticides in 25/75 acetonitrile/
(even for the same matrix) may not be the same. A water (v/v) were added to reach the final additional concentrations
method of standard additions in the sample extract may of 0, 50, 100 and 250 ng/ g equivalents, respectively.
be an alternative approach.

LC-MS analysis
MATERIALS AND METHODS
For LC analysis, an Agilent 1100 HPLC system was used. It
Sampling contained a binary pump, a degasser, column thermostat and an
autosampler. A reverse-phase C8 analytical column of 150mm x
For the present project random sampling was done from the various 4.6mm internal diameter (i.d.) and 5 µm particle size and a guard
markets in the twin cities of Hyderabad, Secunderabad and R. R. column of 125 x 4.6 and 5 mm particle size were coupled to the LC
District local fields and markets. Depending upon the nature of the system. Deionized water containing 0.1% formic acid (mobile phase
vegetation (size, shape, etc.), samples were enclosed in a clean component A) and acetonitrile (component B) were employed for
blotting paper and wrapped inside a clean, paper envelope. The the gradient programme, which started with 20% B for 3 min and
addition of a small sachet of silica gel to the envelope helps to was linearly increased to 100% B in 27 min (held for 3 min). The
reduce the moisture content of the system. However, samples were column was then re-equilibrated forr 12 min back to 20% B.
provided to the analytical laboratory to check for possible co- Thus, the total run time took 45 min. The flow rate was constant
extractives, which could interfere with the analysis. at 0.6 ml/min, and injection volume was 10 µl. For the MS/MS
analysis, an Applied Biosystems 3200 QTRAP system was used.
Applied Biosystems Analyst 1.4.2 software was used for instrument
Reagents and materials control and data processing. For the determination of pesticides,
the commercial method of Applied Biosystems (2005) and its library
High-performance liquid chromatography (HPLC)- grade was used.
acetonitrile; deionized water was obtained from a Milli-Q reagent
water system; dimethyl formamide; anhydrous magnesium sulfate
obtained from Merck and primary secondary amine (PSA)-bonded Statistical analysis
silica was obtained from Supelco, Sigma Aldrich. Each sample was
filtered through a 0.45 mm polyvinylidene difluoride (PVDF) filter 1. An Analysis Of Variance (ANOVA) test and a t-Test were
before injection. Acetic acid and sodium acetate from Merck were conducted between the 'no wash' and 'salted lukewarm water wash'
 Dasika et al. 21

results to check their statistical significance. The data is given in and 45% respectively.
Table 7. a. Chlorpyrifos was still shown high on Granny Smith and
2. The null hypothesis - there is “no correlation” between the
Gold Del apples.
pesticide‟s „no wash‟ residue values and 'salted lukewarm water
wash' residue values. It means the difference between the mean
values of „no wash‟ residual values and „salted lukewarm water
wash values‟ is insignificant”. Grapes
3. The alternative hypothesis (the opposite of the null hypothesis) -
there “is a correlation” between the two values. No Wash: The fungicides Imazalil and Thiabendazole
4. The α-value – Probability that the null hypothesis is valid. This is
assumed as 0.05. This means that 95% of the times the data was
remained approximately 70 and over 100% above the
not a result of chance (means good data). MRL respectively. Insecticide Phosmet, on an average
5. The 'p-value' is the α-value resulting at the end if statistical test. was found to be 50% above MRL. The data is given in
Should be much lower than 0.05. There is sufficient evidence to Table 2 and shown in Figures 2 and 3.
conclude that the mean of no wash values is significantly greater
than the mean of salted water wash values. The Null hypothesis
1. Black grapes had higher initial residual values than
was hence rejected. The t-Tests showed 'p-value' well under 0.05
for almost all results, thus, indicating that the data is statistically green grapes for all pesticides.
significant. 2. Lukewarm Water Wash: Phosmet was found to go
below MRL, but others were still present, but showed
decrease of about 20 to 25% in residual levels.
RESULTS AND DISCUSSION 3. Salted Lukewarm water wash: Green grapes showed
Imazalil closer to MRL, but Thiabendazole was still about
This study describes the combination of two parallel 50% more than MRL. Black grapes showed much higher
methods in the qualitative and quantitative screening of residual values of these 2 pesticides.
pesticide residues: (1) qualitative screening for target
pesticides by LC-MS/MS using MRM data and (2)
confirmation, quantitative determination of the frequently Pears
used /or previously detected pesticides using the MRM
method. Compared with other available methods, the All the seven tested pesticides on the green pear were
QuEchERS method is believe to give the best result. This initially present in relatively low quantities compared to
concept was believed to give the widest scope with the the residue levels on the apples. The only chemical
least effort and still give excellent qualitative and where the residue after cleaning with salted water,
quantitative results, particularly when using QuEChERS greater than the MRL was Thiabendazole. After
for sample preparation. lukewarm water wash, the residue level of Thiabendazole
was 78% above the MRL; after a salted lukewarm water
wash, it was 43% above. The data is given in Table 3.
FRUITS

Apples Guava
Residual levels for 15 different pesticides have been All the pesticide residues on the guava were well under
tested on apples. Fungicide Pyraclostrobin, Dodine etc, the prescribed level before any wash, excepting
insecticides Pirimicarb, Thiacloprid and Acetamip etc, Thiabendazole. After the wash with lukewarm water,
noted negative presence in comparison to the MRL even Thiabendazole residue was still above, while after salted
before any wash. The data is given in Table 1 and shown lukewarm water wash, the Thiabendazole residue went
in Figure 1. down to Non Detectable (ND) in comparison to MRL. The
data is given in Table 4.
1. No wash: Pesticides Diphenylamine, Chlorpyrifos,
Thiabendazole and Malathion were found to be extremely
persistent when tested with “no wash”. Vegetables
a. Chlorpyrifos was lower than MRL on Pink Lady Apples,
but was heavily persistent on Granny Smith and Gold Del Egg plant or Brinjal
Yellow apples.
2. Lukewarm water wash: Diphenylamine was low or No Wash: Eggplants showed the most pesticides that
nearly absent on Pink Lady apple, while others were still have residue levels over the MRL. They ranged from 100
present. On Granny Smith and Gold Del apples, to 500% above MRL.
Diphenylamine was between 50 to 90% above MRL. Lukewarm Water Wash: The overall residue levels of all
3. Salted Lukewarm water wash: Thiabendazole and pesticides tested showed significant improvement with
Malathion were still persistent on all the 3 varieties. values going down anywhere from 50 to 80% when
Average percentage deviation from the MRL was 165 compared against no wash readings. However, at this
22 J. Environ. Chem. Ecotoxicol.

Table 1. Pesticide residues in Apple.

Granny Smith Green Apple

Maximum residue limit
S/N Pesticide No wash Lukewarm water wash Salted lukewarm water wash
(mg/kg)
1 Pyraclostrobin 0.3 0.05 ND ND
2 Dithiocarbamates 3 2.2 1.9 1.7
3 Dodine 5 3.4 2.5 2.2
4 Acetamiprid 0.1 0.07 ND ND
5 Diphenylamine 5 7.8 3.4 2.8
6 Dithiocarbamates 3 2.2 1.3 1.2
7 Imazalil 5 3.8 2.7 2.4
8 Phosmet 10 9.2 7.5 6.4
9 Pirimicarb 1 0.06 ND ND
10 Chlorpyrifos 0.5 2.8 1.7 1.1
11 Captan 3 2.2 1.8 1.7
12 Dithiocarbamates 3 2.6 2.3 2.1
13 Malathion 0.5 1.2 1 0.8
14 Thiacloprid 0.3 0.2 0.18 0.18
15 Thiabendazole 10 43.2 37.4 31

Pink Lady Apple

S/N Pesticide Maximum residue limit No Wash Lukewarm water wash Salted lukewarm water wash
1 Diphenylamine 5 6 3.5 2
2 Phosmet 10 8 5 4
3 Chlorpyrifos 0.5 0.14 0.1 0.08
4 Malathion 0.5 0.9 0.7 0.6
5 Thiabendazole 10 36.8 29 27.3

Gold Del Michigan Yellow Apple

S/N Pesticide Maximum residue limit No Wash Lukewarm water wash Salted lukewarm water wash
1 Diphenylamine 5 9.6 5.4 4.2
2 Phosmet 10 12 9.5 8.6
3 Chlorpyrifos 0.5 3.4 1.9 0.8
4 Malathion 0.5 1.8 0.9 0.8
5 Thiabendazole 10 46.8 37.7 32.6

Figure 1. Average pesticide residues (Pink Lady, Granny Smith, Gold Del Apples).
 Dasika et al. 23

Table 2. Pesticide residues in grapes.

Green grapes
S/N Pesticide Max residue limit (mg/kg) No wash Lukewarm water wash Salted lukewarm water wash
1 Imazalil 5 8.6 6.9 5.4
2 Thiabendazole 10 21.4 17 14.7
3 Phosmet 10 11.8 8.9 7.6
4 Decamethrin 0.05 0.03 ND ND

Black grapes
S/N Pesticide Max residue limit (mg/kg) No wash Lukewarm water wash Salted lukewarm water wash
1 Imazalil 5 9.3 8.2 6.6
2 Thiabendazole 10 32 27.4 21
3 Phosmet 10 16.7 11.3 8.9
4 Decamethrin 0.05 0.05 0.04 0.02

Figure 2. Pesticide residues in green grapes.

Figure 3. Pesticide residues on black grapes.

stage more washing will be required to bring the residue significantly reduced, but still 22% above MRL.
levels closer to MRL. Chlorpyrifos, Thiabendazole, Acephate residues were
Salted Lukewarm water wash: Chlorothalonil residues also very high suggesting another round of wash, which
showed 300% above MRL. Diphenylamine residues was out of scope for the project. The data is given in
24 J. Environ. Chem. Ecotoxicol.

Table 3. Pesticide residues in pear.

Pear
Max residue Deviation from MRL Deviation from Salted lukewarm Deviation
S/N Pesticide No wash Lukewarm water wash
limit (mg/kg) (%) MRL (%) Water Wash from MRL (%)
1 Diphenylamine 5 6.1 22 4.3 -14 3.4 -32
2 Imazalil 5 3 -40 2.1 -58 1.8 -64
3 Phosmet 10 11 10 8.9 -11 8.8 -12
4 Pirimicarb 1 1.8 80 1.2 20 0.6 -40
5 Chlorpyrifos 0.5 0.6 20 0.3 -40 0.2 -60
6 Captan 3 0.06 -98 ND ND ND ND
7 Thiabendazole 10 26.4 164 17.8 78 14.3 43

Table 4. Pesticide residues in guava.

Guava
Name of the pesticide Max residue limit (mg/kg) No Wash Lukewarm water wash Salted lukewarm water wash
Diphenylamine 5 4.8 2.2 1.2
Imazalil 5 4.2 3.6 3.4
Phosmet 10 9.3 7.9 7.2
Chlorpyrifos 0.5 0.43 0.28 0.18
Thiabendazole 10 0.02 ND ND

Table 5 and shown in Figure 4. level on Red pepper. Conclusions

3. Salted Lukewarm water wash: Diphenylamine
Bell Peppers is still persistent 25 to 44% above MRL, while The developed combination of the two methods
others have shown great reduction. The data is described above permitted the fast and easy
1. No Wash: Bell Peppers, both green and red given in Table 6 and shown in Figures 5 and 6. qualitative screening of target pesticides in a 45
had Chlorpyrifos, and Diphenylamine residues All fruits and vegetables had great disparity min LCMS/ MS run.
present from 75 to 100% above MRL. between the maximum Thiabendazole levels Although the manual evaluation of the given
Thiabendazole was found but in comparison to instituted by the EPA and the levels found on the chromatograms increased the analysis time by an
other vegetables, this was relatively in smaller produce. This was especially evident on apples additional 15 min per sample, very little time, cost
levels. and Indian eggplants. Even after washing the fruit and labour was spent on sample preparation. In
2. Lukewarm water wash: Chlorpyrifos and or vegetable, the Thiabendazole residue still the case of dirty samples, some false indications
Diphenylamine persist and are about 40 to 60% remained higher than the tolerable levels. The were observed, but these were caught by the use
above MRL. Thiabendazole was 23% above MRL only exceptions to this pattern are Red bell of the MRM confirmatory and quantitative method
on green one, while it was just about the MRL peppers and guavas. for the more common pesticides. The construction
 Dasika et al. 25

Table 5. Pesticide residues in eggplants or brinjal.

Indian Egg Plant

S/N Pesticide Maximum residue limit (mg/kg) No Wash Lukewarm water wash Salted lukewarm water wash
1 Diphenylamine 5 9.8 5.3 4.4
2 Imazalil 5 4.2 2.5 1.8
3 Phosmet 10 9 8.4 6.8
4 Chlorpyrifos 0.5 1.4 1 0.8
5 Thiabendazole 10 44.1 29.3 14.3
6 Chlorothalonil 0.1 0.5 0.3 0.19
7 Endosulfan 2 2.2 1.9 1.5
8 Acephate 2 5.2 4.2 3.6
Chinese Egg Plant
S/N Pesticide Maximum residue limit (mg/kg) No Wash Lukewarm water wash Salted lukewarm water wash
1 Diphenylamine 5 9.8 7.3 6.1
2 Imazalil 5 3.8 2.9 2.4
3 Phosmet 10 9.3 6.9 6.4
5 Chlorpyrifos 0.5 2.1 1.7 1.3
6 Thiabendazole 10 33.2 24.1 21
7 Chlorothalonil 0.1 0.6 0.45 0.38
8 Endosulfan 2 2.8 2.3 1.8
9 Acephate 2 7.8 5.7 4.7

Figure 4. Average pesticide residues (Indian and Chinese eggplants).

of standard addition calibration was carried out with the fungicides, insecticides and pesticides have been
same extract that was previously injected for screening washed away with the lukewarm water wash.
the compounds. A large calibration database in different Pink Lady Apples showed no residue of Chlorpyrifos
matrices was collected to show the consistency of the and showed only Malathion and Thiabendazole before
average calibration slope, which helped us check the wash and have greatly reduced after lukewarm water wash.
accuracy of the calculated results from the method of However, Granny Smith Apples and Gold Del Apples
standard additions. showed higher residue of Chlorpyrifos after the lukewarm
water wash.
Apples
Grapes
Test revealed increased residue levels of Chlorpyrifos,
Thiabendazole, Malathion and Diphenylamine. Most Imazalil is among the persistent pesticides on grapes with
26 J. Environ. Chem. Ecotoxicol.

Table 6. Pesticide residues in bell peppers.

Red Bell pepper

Max residue limit No Deviation from Lukewarm water Deviation from Salted lukewarm Deviation from
S/N Pesticide
(mg/kg) Wash MRL (%) wash MRL (%) water wash MRL (%)
1 Chloropyrifos 2 3.5 75 2.7 35 2.2 10
2 Imazilil 5 4.8 -4 3.7 -26 3.3 -34
3 Thiabendazole 10 11.4 14 10 0 9.7 -3
4 Diphenylamine 5 8.7 74 6.9 38 6.3 26

Green Bell pepper

Max residue limit No Deviation from Lukewarm water Deviation from Salted lukewarm Deviation from
S/N Pesticide
(mg/kg) Wash MRL (%) wash MRL (%) water wash MRL (%)
1 Chloropyrifos 2 4.1 105 2.9 45 2.3 15
2 Imazilil 5 3.5 -30 2.4 -52 1.8 -64
3 Thiabendazole 10 14.6 46 12.3 23 11.5 15
4 Diphenylamine 5 9.8 96 7.9 58 7.2 44

Figure 5. Pesticide residue analysis on red bell pepper.

 Dasika et al. 27

Figure 6. Average pesticide residue analysis (green and red bell peppers).

Table 7. Statistical analysis.

Statistical Tests
Standard deviation for salted
Pesticide tested α-value Degrees of freedom t-value Look-up t-value p-value Statistically significant?
lukewarm water wash
Diphenylamine 0.05 15.86 4.05 1.753 0.00097 2.04 yes
Chlorpyrifos 0.05 12.56 1.88 1.782 0.085 0.83 yes
Imazalil 0.05 18.74 2.13 1.74 0.046 1.64 yes
Thiabendazole 0.05 17.4 2.31 1.74 0.033 8.5 yes
Phosmet 0.05 12.96 3.45 1.771 0.0043 1.55 yes

allowed MRL of 5mg/kg. When consumed over present above MRL values before wash, but go under MRL even before any wash, except slightly
longer periods, i.e. 2 to 5 times (50 mg/kg/day) down after lukewarm water wash. Their residual higher Thiabendazole, which is non-toxic. After
more than MRL showed some mortality issues values drop further after salted lukewarm water salted lukewarm water wash, all the pesticides
and significant brain enzyme depression. wash. were well under MRL, even Thiabendazole.

Green pears Guava Green and red bell peppers

Chlorpyrifos, Phosmet, and Diphenylamine are The residue levels of most toxic pesticides were Chlorpyrifos and Diphenylamine are significantly
28 J. Environ. Chem. Ecotoxicol.

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