Food Chemistry 305 (2020) 125487

Contents lists available at ScienceDirect

Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Validation of ultrasonic-assisted switchable solvent liquid phase T

microextraction for trace determination of hormones and organochlorine
pesticides by GC–MS and combination with QuEChERS
⁎
Büşra Yilmaz Durak, Dotse Selali Chormey, Merve Firat, Sezgin Bakirdere
Yıldız Technical University, Department of Chemistry, 34220 İstanbul, Turkey

A R T I C LE I N FO A B S T R A C T

Keywords: QuEChERS and switchable solvent liquid phase microextraction (SS-LPME) were respectively used as pretreat-
QuEChERS ment and preconcentration tools to allow trace determination of selected organochlorine pesticides and hor-
Switchable solvent mones by gas chromatography mass spectrometry (GC–MS). The effects of principal SS-LPME variables and their
Endocrine disruptors interactions were evaluated with a Box-Behnken experimental design. The limits of detection obtained by direct
Pesticide
GC–MS determination were enhanced by about 33–115 folds under the optimized SS-LPME conditions. The SS-
Hormones
LPME method was applied to tap water, well water, lake water, medical wastewater and tea samples.
Satisfactory recovery results were obtained for all but the tea samples using the conventional calibration plot.
Matrix matched calibration standards were used to improve the percent recovery of analytes to almost 100% in
the tea samples. The combined QuEChERS and SS-LPME method was applied to tomato samples and matrix
matching was also used to significantly improve analyte recoveries.

1. Introduction
The late 1940's saw a rapid growth in the pesticide industry due to
the successful use of dichlorodiphenyltrichloroethane (DDT) to eradi-
cate pests such as mosquitoes that caused life threatening diseases
(Kousoulis et al., 2013). Besides disease prevention, pesticides are
greatly applied on agricultural fields, pre and post-harvest to increase
the quality, quantity and storage period of farm products (Damalas &
Eleftherohorinos, 2011). Organochlorine pesticides were the first major
chemical class of pesticides to be produced on large scale and these
included dieldrin, aldrin, heptachlor and chlordane (Gopalan &
Chenicherry, 2018). Despite their benefits, these chemicals came under
scrutiny due to reported poisoning incidents on environmental organ-
isms and humans (Chen, Liu, Yang, & Wang, 2008). In comparison to
the other chemical classes such as organophosphates and carbamates,
organochlorines persist for longer periods in the environment and pose
endocrine system disruptive risks to humans and other organisms
(Pleština, 2003). Estrogens are likely the most commonly affected part
of the endocrine system by these chemicals. The chemicals mimic or
hinder estrogens such as estrone and 17-β estradiol, thereby affecting
the development of primary and secondary sexual characteristics
(Królik & Milnerowicz, 2012). Both natural and synthetic estrogens are
released into environmental water bodies and these have the tendency
to harm aquatic organisms (Adeel, Song, Wang, Francis, & Yang, 2017).
Monitoring of these chemicals in environmental samples, foods and
beverages is therefore very crucial to protect humans and other or-
ganisms. Organic analytes are conveniently separated from each other
by different chromatography techniques, and coupling to an appro-
priate detector allows accurate and precise qualitative and quantitative
determinations (Coskun, 2016). Compounds that easily evaporate due
to high vapor pressure are well suited for gas chromatography (Sharma,
Rai, & Prasad, 2018) and can be detected via electron capture, flame
ionization, thermal conductivity and atomic emission (Milne & Morrow,
2009). Gas chromatography with mass spectrometry (GC–MS) is a
technique preferred by most scientists due to its selective and specific
analyte detection capacity, characterization of unknown compounds
and separation of compounds, even when they occur at the same re-
tention time by reason of different mass to charge ratios (Lynch, 2017).
Despite these benefits of GC–MS, its sensitivity for most compounds
only allows parts per million and upper parts per billion measurements.
The tandem system (GC–MS/MS) allows determination at trace and
ultra-trace levels of compounds, and allows greater selectivity and
specificity (Zabielski et al., 2013). However, its relatively high cost does
not make it readily available in all laboratories. The low sensitivity of
GC–MS can be boosted by employing sample preparation techniques
that also eliminate matrix effects blocking analyte signals and

⁎
Corresponding author.
E-mail address: bsezgin@yildiz.edu.tr (S. Bakirdere).

https://doi.org/10.1016/j.foodchem.2019.125487
Received 11 December 2018; Received in revised form 10 June 2019; Accepted 4 September 2019
Available online 05 September 2019
0308-8146/ © 2019 Elsevier Ltd. All rights reserved.
B.Y. Durak, et al.
preconcentration of analyte into quantifiable amounts (Marchi, Rudaz,
& Veuthey, 2009). Extraction is a popular sample preparation technique
broadly categorized into solid phase and liquid-liquid extraction
(Forbes, van der Wat, & Kroukamp, 2015). Recent trends in extraction
termed microextraction have been developed to reduce the labor in-
tensity, high time and chemical consumption associated with the con-
ventional methods (Padrón, Afonso-Olivares, Sosa-Ferrera, & Santana-
Rodríguez, 2014). These extraction methods give high enrichment
factors, high analyte recovery, rapid analysis period and utilizes low
volumes of toxic chemicals (Moreda-Piñeiro & Moreda-Piñeiro, 2017).
However, efforts have been made to introduce green extraction solvents
that pose little or no harmful effects without compromising the benefits
mentioned above. Switchable polarity solvent extraction is a relatively
new method which utilizes low polarity amines, protonated at the free
electron pair site of nitrogen to become water miscible and deproto-
nated after extraction to cause phase separation and extraction of
analytes into separated amine phase (Memon, Yilmaz, & Soylak, 2017).
The protonation process is accomplished with the addition of either
solid carbon dioxide or CO2 gas (Fırat et al., 2018; Phan et al., 2008). A
simple removal of carbon dioxide from the switchable polarity solvent
reverts it into the original non-polar amine with extracted analytes
(Mercer & Jessop, 2010). This is a green extraction method which uses
environmentally friendly solvents and the extraction procedure is
simple and rapid. Switchable solvent microextraction has been suc-
cessfully applied for the determination of environmental contaminants
including phenolic compounds, pesticides and hormones (Chormey,
Bodur, Baskın, Fırat, & Bakırdere, 2018). QuEChERS (quick, easy,
cheap, effective, rugged and safe) is a well-established sample cleaning
method based on dispersive solid phase extraction using specific sor-
bents (Wei et al., 2015). The common sorbents used are primary sec-
ondary amine (PSA) and graphitized carbon black (GCB), with the
former capable of removing polar organic acids, pigments and sugars,
and the latter removing pigments and steroids (Wilkowska & Biziuk,
2011).
The advantages spelled out in the acronym QuEChERS has made it a
widely used method for routine analysis of complex samples but it has a
drawback of analyte enrichment (Abdel Ghani, Alhewairini, &
Hrouzková, 2018). A portion of this study was therefore aimed at using
SS-LPME to augment QuEChERS method for the determination of or-
ganochlorine pesticides and hormones in food and environmental
samples by GC–MS. This is the first reported use of SS-LPME and
QuEChERS for the determination of hormones and organochlorine
analytes.
2. Experimental
2.1. Chemicals and reagents
A mixed standard stock solution (100 mg/L) of heptachlor (CAS#
76-44-8), aldrin (CAS# 309-00-2), dieldrin (CAS# 60-57-1), estrone
(CAS# 53-16-7) and 17-β estradiol (CAS# 50-28-2) was prepared and
stored at −18 °C. The standards were purchased from Dr. Ehrenstorfer
(GmbH, Germany). The stock solutions were prepared in acetonitrile
but working standard solutions and aqueous calibration standards were
prepared in ultrapure deionized water. Deuterated bisphenol A (CAS#
96210-87-6) was also purchased from Dr. Ehrenstorfer and used as
internal standard. N,N-dimethylbenzylamine was purchased from
Merck (Germany) and protonated with dry ice (solid CO₂) to produce
switchable solvent with water, and deprotonated with sodium hydro-
xide (Merck – Germany) back into the tertiary amine. The switchable
solvent was prepared according to the procedure reported by Fırat et al.
(Fırat et al., 2018).
2.2. Instruments
An HP-5MS column 30 m (250 μm × 0.25 μm) fitted in the oven
2
Food Chemistry 305 (2020) 125487
compartment of an Agilent 6890 gas chromatograph was used for
analyte separation according to the following temperature program:
50 °C/min ramp from 70 °C to 280 °C and held for 2.5 min. Eluting
analytes from the column were detected by an Agilent 5973 mass se-
lective detector operating in the scan mode (m/z 60–300). The quali-
fier/quantifier ions used for heptachlor, aldrin, dieldrin, estrone and
17-ß estradiol were 272/100, 66/263, 81/79, 146/270 and 160/272.
The temperatures of the transfer line, MS Quad and MS Source were
280, 150 and 230 °C, respectively. A Hettich Centrifuge (EBA 20) and
Nuve (NF 400R) bench-top cooled centrifuge were used to facilitate
phase separation. Sample agitation was performed using an ISOLAB
(M1010002) vortex and a HAPA (M-100) ultrasonicator.
2.3. Switchable solvent extraction procedure
The switchable solvent was stored at 4.0 °C in the refrigerator but
allowed to warm up to ambient laboratory temperatures before usage.
The switchable solvent was hand-shaken slightly to ensure homo-
geneity before pipetting 1.0 mL into the sample/standard solution for
extraction. The solution was vortexed for 5.0 s before adding 1.0 mL
sodium hydroxide (0.50 M) for deprotonation with the aid of 30 s ul-
trasonication. Separation of organic amine phase from the aqueous
sample/standard solution was hastened by 120 s centrifugation at
6000 rpm. Aliquots were placed in glass insert vials for automatic
GC–MS injections.
2.4. QuEChERS method procedure
The extraction and sample clean-up was performed according to the
AOAC QuEChERS method to obtain a dilution factor of one (Lehotay,
2007). This was achieved by adding 15 mL of 1.0% acetic acid in
acetonitrile to 15 g of blended fresh tomato sample in a 50 mL cen-
trifuge tube containing 6.0 g magnesium sulfate and 1.5 g sodium
acetate. The tube was hand-shaken in the up-down motion for 1.0 min
and centrifuged for 5.0 min at 4000 rpm and at 4.0 °C. Approximately
8.0 mL from the upper phase was transferred into a 15 mL centrifuge
tube containing 400.1 mg PSA, 400.1 mg C18EC and 1199.8 mg mag-
nesium sulfate. This was also shaken in the same manner as the pre-
vious and centrifuged at 4000 rpm for 3.0 min (4.0 °C). The supernatant
was filtered through 0.45 μm syringe filter.
3. Results and discussions
Calibration standard solutions (in acetonitrile) in the range of 0.10
and 100 mg/L were directly analyzed by the GC–MS system to de-
termine analytical performance for the analytes. In the method devel-
opment process, three extraction and measurement replicates were
performed for each parameter to determine the variance of the results,
and the optimum value selected based on the highest average peak
area. Isotopically labelled bisphenol A (BPA-D16) was used as internal
standard to enhance extraction and measurement precision.
3.1. Experimental design of SS-LPME
The aim of the experimental design was to determine optimum
values of extraction variables by evaluating their individual and inter-
action effects. A Box-Behnken experimental design was used in this
study and the parameters fitted into the model were switchable solvent
amount, sodium hydroxide amount and ultrasonication period. Prior to
the design experiment, the optimum concentration of sodium hydroxide
was determined in order to cut down the number of test variables. The
concentrations tested were 0.50, 1.0, 2.0, 3.0 and 5.0 M and a de-
creasing trend in integrated peak area was observed for increasing so-
dium hydroxide concentration. The volume of deprotonated amine after
phase separation increased with increasing concentration and this
caused the decreased peak areas via analyte dilution. Thus, the
B.Y. Durak, et al. Food Chemistry 305 (2020) 125487

concentration of sodium hydroxide fitted into the design to determine

its optimum amount was selected as 0.50 M. Each variable was tested at
high (+1), mean (0) and low (−1) levels for 17 combinations and
summing up to 51 experimented data due to triplicate extractions/
measurements. The levels (low – mean – high) tested for switchable
solvent (A), sodium hydroxide (B) and ultrasonication period (C) were
1.0–2.0–3.0 mL, 1.0–2.0–3.0 mL and 15–30–45 s. The Design-Expert
7.0.0 software was used to develop the model and evaluation of ex-
perimented results. The variables in the experimental design showed
negative and positive main effects which signify the highest peak area
value obtained for the lowest and highest variable levels, respectively.
The expression below shows effects of variables and their interactions
on response (R).

R = 221400 − 39483.5A − 88826.17B + 161600AB − 123200BC + 137000

B2 (1)
Fig. 2. A residual plot showing the linearity between predicted and experi-
Both switchable solvent and sodium hydroxide showed negative
mental results.
main effects as can be seen in Eq. (1). The final volume of organic phase
after extraction was observed to be directly proportional to the amounts
of switchable solvent and sodium hydroxide used. The final volume of Table 1
the low level (−1) extractions were highly concentrated with analytes Analytical figures of merit for analytes using SS-LPME/GC–MS.
as supported by the principle of preconcentration, where enrichment Chemical LOD, LOQ, %RSD Linear Range, R2 E.D.P
factor increases with decreasing final volume. Variables significant to ng/mL ng/mL ng/mL
the experimental model were evaluated by analysis of variance
Heptachlor 0.96 3.2 3.4 2.0–500 1.000 115
(ANOVA) at 95% confidence level. An F-value of 22.90 and P-
Aldrin 1.5 5.1 5.6 5.0–500 0.9999 33
value < 0.0001 were statistically significant to the model. P-values Dieldrin 0.44 1.5 6.9 2.0–200 1.000 91
lower than 0.05 were significant to the model and these included Estrone 0.58 1.9 9.2 2.0–200 0.9999 103
switchable solvent (A: 0.0324), sodium hydroxide (B: 0.0004), 17-beta-Estradiol 0.54 1.8 4.6 2.0–200 0.9997 74
switchable solvent/sodium hydroxide interaction (AB: < 0.0001), so-
dium hydroxide/sonication interaction (BC: 0.0005) and quadratic ef-
fect of sodium hydroxide (B2: 0.0002). The AB interaction is given in for coefficient of determination (R2) values > 0.9996. Figures of merit
the response surface plot of Fig. 1 which shows an increase in response determined for the developed method were limit of detection (LOD)
with decreasing amounts of both variables. Ultrasonication was not and quantification (LOQ), linear dynamic range (LDR), percent relative
significant to the model according to its P-value of 0.0886. The lack of standard deviation (%RSD) and R2 (Table 1). The LOD and LOQ values
fit value of the model was 0.1732 and this indicated it to be insignif- were respectively determined using the expressions 3xLCSD/m and
icant. A coefficient of determination (R2) value of 96% established good 10xLCSD/m, where LCSD is the lowest concentration's standard devia-
correlation between experimented results and predicted values. Ad- tion value for 6 replicate measurements and m is the slope of linear
justment of the R2 resulted in a 92% value which showed about 4.0% calibration plot. The LOD values calculated for the analytes ranged
variation from the experimented data set. Fig. 2 is normal residual plot between 0.44 and 1.5 ng/mL. Comparing the LODs of direct GC–MS
showing a good correlation between predicted and experimented va- analysis with the SS-LPME method indicated 33–115 folds enhance-
lues. The model predictor was used to determine optimum values of the ment in detection powers. The %RSD values calculated for the lowest
extraction variables which were 1.0 mL switchable solvent, 1.0 mL so- calibration concentrations were all lower than 10%, a good indicator of
dium hydroxide and 30 s ultrasonication. high precision.

3.2. Analytical figures of merit of SL-LPME method 3.3. SS-LPME recovery tests for aqueous samples

The analytical figures of merit for the five analytes were determined
with mixed aqueous standard solutions (0.50–1000 ng/mL). Calibration
plots of each analyte were developed as a plot of concentration against
the ratio of standard peak area to internal standard peak area. The
internal standard improved the linearity of calibration plots as observed
Fig. 1. A 3D response surface plot showing the interaction effect of sodium
hydroxide and switchable solvent amounts on response.
Surface water sources such as lakes and rivers are easily con-
taminated by pesticides and other pollutants, but ground water can also
become polluted by soluble contaminants that leach down the soil bed.
Medical wastewater could contain high levels of estrogens which are
naturally excreted mainly by females. Determination of their levels in
influent and effluents is crucial for safe discharge into the environment
after treatment. The developed method was therefore tested on tap,
well, lake and medical wastewater matrices. Analytes of concern were
not present in the blank samples. Three replicates of tap, well and lake
water samples were spiked to 50 ng/mL final concentration, extracted
under the optimized conditions and their respective percent recoveries
calculated relative to aqueous calibration standards. The percent re-
coveries obtained are presented in Table S1 (Supplementary Material),
with well and tap water recording values close to 100%. The low %RSD
values obtained confirmed good repeatability for replicate extraction/
measurement but not the reproducibility.
Two reproducibility tests were performed using the medical was-
tewater sample by one analyst on different days (inter-day), and by four
different analysts on the same day. The inter-day reproducibility tests

3
B.Y. Durak, et al. Food Chemistry 305 (2020) 125487

Table 2 Table 4
Inter-analyst reproducibility tests performed on medical wastewater spiked at MDL and matrix matched percent recoveries for tomato samples by QuEChERS
50 ng/mL. – SS-LPME.
Analyte Analyst 1 Analyst 2 Analyst 3 Analyst 4 %RSDa Analyte MDL 50 ng/mL 100 ng/mL 200 ng/mL
(ng/mL) (%) (%) (%)
Heptachlor 105.3 100.2 97.9 97.4 3.6
Aldrin 97.3 92.8 87.5 93.7 4.4 Heptachlor 9.6 102.4 ± 6.2 99.2 ± 8.2 101.2 ± 6.5
Dieldrin 98.9 97.0 96.6 95.4 1.5 Aldrin 15 99.7 ± 1.5 97.6 ± 2.1 103.3 ± 2.4
Estrone 98.8 100.1 101.2 100.5 1.0 Dieldrin 4.4 102.1 ± 6.1 98.4 ± 2.1 101.5 ± 2.1
17-beta-Estradiol 100.9 100.2 101.1 98.7 1.1 Estrone 5.8 98.8 ± 5.9 96.6 ± 3.5 104.8 ± 1.6
17-beta-Estradiol 5.4 94.5 ± 3.0 99.6 ± 3.2 101.7 ± 2.2
a
%RSD determined as percent ratio of standard deviation to average of the
four analysts. The %RSD of the analysts were below 7.0% for all analytes.
matrix matching calibration standards, which were prepared in similar
were performed at different times of the day to determine whether or sample matrices. The recovery results improved greatly as shown in
not laboratory conditions affected the method. Table S2 Table 3 for the analytes at the three spiked concentrations. This method
(Supplementary Material) shows the inter-day results for medical combined with matrix matching quantification overcame matrix effects
wastewater spiked at 50 ng/mL and the results obtained reflect high for trace determination of the analytes in tea samples.
precision irrespective of the time and day of analysis. Inter-analyst re-
producibility tests were performed by four analysts in succession and
3.5. QuEChERS – SS-LPME combination studies
the results given in Table 2 also indicate high precision. The SS-LPME
method was performed for the very first time by Analyst 3, who had no
The tomato extract from the QuEChERS process was spiked at 50,
prior experience with switchable solvents but applied the optimized
100 and 200 ng/mL by taking an appropriately low aliquot from a high
conditions by following basic instructions. The results obtained did not
concentration standard solution in order to observe the full effect of the
vary significantly from the other analysts and this confirms the sim-
sample matrix. The optimized SS-LPME procedure was then applied to
plicity and applicability of the method.
the spiked sample but the final step of sodium hydroxide addition did
not result in a distinct amine phase. The high content of acetonitrile in
the QuEChERS procedure could have resulted in complete dissolution of
3.4. SS-LPME recovery in tea samples
the amine, thereby resulting in no separate phase. In order to reduce the
effect of acetonitrile, the tomato matrix extract was diluted 10 times
Tea is only second to water as the most consumed beverage in the
before spiking to the three concentrations stated above. The method
world and farmers tend to use pesticides to control insects in order to
detection limit (MDL) of the analytes therefore increased by 10 folds as
meet the high demand. Development of insect resistance to some pes-
shown in Table 4, however, the high enrichment factor of the SS-LPME
ticides instigate some farmers to use excessive amounts beyond the
method ensured that all analytes could be determined below 20 ng/mL.
prescribed concentration or even use some forbidden pesticides.
A distinct but low volume upper phase was observed for the spiked
Developing an accurate and applicable method to tea samples is
samples and withdrawal into vials for injection had to be done in a
therefore very crucial. In this part of the study, about 1.5 g of chamo-
careful manner. When compared with their aqueous standard solution
mile tea and green tea were brewed in 100 mL pure water for 10 min
analogues, the spiked samples recorded very high peak area values as a
and filtered through 125 mm filter papers while warm, before allowing
result of low phase formed (concentrated analytes). Calibration stan-
to cool down to room temperature. The filtered tea solution was diluted
dards were therefore prepared in similar tomato extracts and the results
to 1.0 L and tested under the optimized extraction conditions. The
obtained were in proximity to 100% as given in Table 4. The matrix
samples were spiked at 20, 50 and 100 ng/mL after blank analysis had
matching calibration plots of the analytes showed high linearity with R2
proved the absence of analytes. Calibration standards prepared in ul-
values > 0.9994.
trapure deionized were used to calculate the percent recovery of spiked
tea samples but the results obtained were > 130%, even though the
analytes were not detected in the blank. Comparing the peak area va- 4. Conclusion
lues of the two different tea types also revealed slight differences due to
their different compositions and processing. A similar observation was This study reported the switchable solvent liquid phase micro-
reported by Turan et al., where the signal of N-butyryl-L-homoserine extraction for the determination of organochlorine pesticides and hor-
lactone was enhanced by 1.2 folds when tea was added to samples and mones from various samples by GC–MS and coupling of QuEChERS
standard solutions (Turan et al., 2018). An overlay chromatogram of with SS-LPME for the determination of same analytes in tomato sam-
50 ng/mL aqueous standard and the two tea samples spiked at 50 ng/ ples. The SS-LPME method was optimized, validated and applied to
mL as presented in Fig. S1 (Supplementary Material) shows the two tea various samples including environmental water samples (well and
samples with higher peak intensities than the standard solution. The lake), medical wastewater, and tea samples (chamomile and green tea).
percent recoveries of the tea samples were therefore determined using Satisfactory results were obtained for the aqueous samples and matrix

Table 3
Matrix matched percent recoveries for tea samples.
Analyte Chamomile tea (%) Green tea (%)

20 ng/mL 50 ng/mL 100 ng/mL 20 ng/mL 50 ng/mL 100 ng/mL

Heptachlor 97.7 ± 6.4 98.7 ± 1.3 100.3 ± 6.9 90.2 ± 1.6 100.9 ± 3.2 100.0 ± 5.4
Aldrin 92.1 ± 6.3 101.6 ± 8.7 99.3 ± 2.8 91.0 ± 2.2 101.2 ± 1.9 99.5 ± 1.2
Dieldrin 93.8 ± 1.3 100.3 ± 1.6 100.4 ± 2.8 99.9 ± 1.5 98.0 ± 3.9 100.6 ± 1.1
Estrone 93.8 ± 3.6 102.7 ± 0.9 96.9 ± 0.7 91.4 ± 1.0 100.6 ± 5.6 99.3 ± 0.7
17-beta-Estradiol 104 ± 7.2 99.5 ± 5.3 100.2 ± 2.9 100.2 ± 1.6 98.1 ± 5.3 102.5 ± 6.1

± represents standard deviation for n = 3.

4
B.Y. Durak, et al.
matching was used to overcome poor recovery results for the tea
samples. Inter-day and inter-analyst reproducibility tests were also
performed to validate the methods precision and applicability. The
combined QuEChERS – SS-LPME method was applied to tomato matrix
by using matrix matching to enhance the accuracy of quantification.
The simplicity, rapidness and low cost of this method make it ideal for
routine analysis with high accuracy and precision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.foodchem.2019.125487.
References
Abdel Ghani, S. B., Alhewairini, S. S., & Hrouzková, S. (2018). A fast and easy QuEChERS-
DLLME method combined with GC-MS for ethion and bifenthrin residues determi-
nation and study of their dissipation dynamics in palm dates. Food Analytical Methods,
11(12), 3542–3550.
Adeel, M., Song, X., Wang, Y., Francis, D., & Yang, Y. (2017). Environmental impact of
estrogens on human, animal and plant life: A critical review. Environment
International, 99, 107–119.
Chen, J., Liu, C., Yang, Z., & Wang, J. (2008). Residues and characteristics of organo-
chlorine pesticides in the surface water in the suburb of Beijing. Earth Science
Frontiers, 15(5), 242–247.
Chormey, D. S., Bodur, S., Baskın, D., Fırat, M., & Bakırdere, S. (2018). Accurate and
sensitive determination of selected hormones, endocrine disruptors, and pesticides by
gas chromatography–mass spectrometry after the multivariate optimization of
switchable solvent liquid-phase microextraction. Journal of Separation Science,
41(14), 2895–2902.
Coskun, O. (2016). Separation techniques: Chromatography. Northern Clinics of Istanbul,
3(2), 156–160.
Damalas, C. A., & Eleftherohorinos, I. G. (2011). Pesticide exposure, safety issues, and risk
assessment indicators. International Journal of Environmental Research and Public
Health, 8(5), 1402–1419.
Fırat, M., Bodur, S., Tışlı, B., Özlü, C., Chormey, D. S., Turak, F., & Bakırdere, S. (2018).
Vortex-assisted switchable liquid-liquid microextraction for the preconcentration of
cadmium in environmental samples prior to its determination with flame atomic
absorption spectrometry. Environmental Monitoring and Assessment, 190(7), 393.
Forbes, P. B. C., van der Wat, L., & Kroukamp, E. M. (2015). Chapter 3 - Biomonitors. In P.
B. C. Forbes (Vol. Ed.), Comprehensive analytical chemistry. vol. 70. Comprehensive
analytical chemistry (pp. 53–108). Elsevier.
Gopalan, N. K., & Chenicherry, S. (2018). Fate and distribution of organochlorine in-
secticides (OCIs) in Palakkad soil, India. Sustainable Environment Research, 28(4),
Food Chemistry 305 (2020) 125487
179–185.
Kousoulis, A. A., Chatzigeorgiou, K.-S., Danis, K., Tsoucalas, G., Vakalis, N., Bonovas, S., &
Tsiodras, S. (2013). Malaria in Laconia, Greece, then and now: A 2500-year-old
pattern. International Journal of Infectious Diseases, 17(1), e8–e11.
Królik, M., & Milnerowicz, H. (2012). The effect of using estrogens in the light of scientific
research. Advances in Clinical and Experimental Medicine, 21(4), 535–543.
Lehotay, S. J. (2007). Determination of pesticide residues in foods by acetonitrile ex-
traction and partitioning with magnesium sulfate: Collaborative study. Journal of
AOAC International, 90(2), 485–520.
Lynch, K. L. (2017). Chapter 6 - Toxicology: Liquid chromatography mass spectrometry.
In H. Nair, & W. Clarke (Eds.). Mass spectrometry for the clinical laboratory (pp. 109–
130). San Diego: Academic Press.
Marchi, I., Rudaz, S., & Veuthey, J.-L. (2009). Sample preparation development and
matrix effects evaluation for multianalyte determination in urine. Journal of
Pharmaceutical and Biomedical Analysis, 49(2), 459–467.
Memon, Z. M., Yilmaz, E., & Soylak, M. (2017). Switchable solvent based green liquid
phase microextraction method for cobalt in tobacco and food samples prior to flame
atomic absorption spectrometric determination. Journal of Molecular Liquids, 229,
459–464.
Mercer, S. M., & Jessop, P. G. (2010). “Switchable water”: Aqueous solutions of switch-
able ionic strength. ChemSusChem, 3(4), 467–470.
Milne, G. L., & Morrow, J. D. (2009). Chapter 5 - Measurement of biological materials. In
D. Robertson, & G. H. Williams (Eds.). Clinical and translational science (pp. 69–86).
San Diego: Academic Press.
Moreda-Piñeiro, J., & Moreda-Piñeiro, A. (2017). Chapter seventeen-Recent advances in
the combination of assisted extraction techniques. In E. Ibáñez, & A. Cifuentes (Vol.
Eds.), Comprehensive analytical chemistry. vol. 76. Comprehensive analytical chemistry
(pp. 519–573). Elsevier.
Padrón, M., Afonso-Olivares, C., Sosa-Ferrera, Z., & Santana-Rodríguez, J. (2014).
Microextraction techniques coupled to liquid chromatography with mass spectro-
metry for the determination of organic micropollutants in environmental water
samples. Molecules, 19(7), 10320.
Phan, L., Andreatta, J. R., Horvey, L. K., Edie, C. F., Luco, A.-L., Mirchandani, A., ...
Jessop, P. G. (2008). Switchable-polarity solvents prepared with a single liquid
component. The Journal of Organic Chemistry, 73(1), 127–132.
Pleština, R. (2003). Pesticides and herbicides|Types of pesticide. In B. Caballero (Ed.).
Encyclopedia of food sciences and nutrition (pp. 4473–4483). (2nd ed.). Oxford:
Academic Press.
Sharma, A., Rai, P. K., & Prasad, S. (2018). GC–MS detection and determination of major
volatile compounds in Brassica juncea L. leaves and seeds. Microchemical Journal,
138, 488–493.
Turan, N. B., Chormey, D. S., Sari Erkan, H., Caglak, A., Saral, M., Bakirdere, S., & Engin,
G. O. (2018). Preliminary study testing the effects of tea and coffee on sludge char-
acteristics and N-butyryl-l-homoserine lactone in an MBR system. Environmental
Technology, 1–11.
Wei, J., Cao, J., Tian, K., Hu, Y., Su, H., Wan, J., & Li, P. (2015). Trace determination of
five organophosphorus pesticides by using QuEChERS coupled with dispersive li-
quid–liquid microextraction and stacking before micellar electrokinetic chromato-
graphy. Analytical Methods, 7(14), 5801–5807.
Wilkowska, A., & Biziuk, M. (2011). Determination of pesticide residues in food matrices
using the QuEChERS methodology. Food Chemistry, 125(3), 803–812.
Zabielski, P., Ford, G. C., Persson, X. M., Jaleel, A., Dewey, J. D., & Nair, K. S. (2013).
Comparison of different mass spectrometry techniques in the measurement of L-[ring-
(13)C(6)]phenylalanine incorporation into mixed muscle proteins. Journal of Mass
Spectrometry: JMS, 48(2), 269–275.