Analytical Letters

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Coprecipitation of Trace Propineb in Water and

Food with Separation-Preconcentration Using
Cu(II)-8-Hydroxyquinoline (8HQ) Precipitate

Mustafa Soylak, Hassan Elzain Hassan Ahmed & Ozgur Ozalp

To cite this article: Mustafa Soylak, Hassan Elzain Hassan Ahmed & Ozgur Ozalp (15
Dec 2023): Coprecipitation of Trace Propineb in Water and Food with Separation-
Preconcentration Using Cu(II)-8-Hydroxyquinoline (8HQ) Precipitate, Analytical Letters, DOI:
10.1080/00032719.2023.2293203

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Published online: 15 Dec 2023.

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ANALYTICAL LETTERS
https://doi.org/10.1080/00032719.2023.2293203

SEPARATIONS

Coprecipitation of Trace Propineb in Water and Food

with Separation-Preconcentration Using Cu(II)-8-
Hydroxyquinoline (8HQ) Precipitate
Mustafa Soylaka,b,c, Hassan Elzain Hassan Ahmeda, and Ozgur Ozalpa
a
Faculty of Sciences, Department of Chemistry, Erciyes University, Kayseri, Turkey; bTechnology Research
and Application Center (ERU-TAUM), Erciyes University, Kayseri, Turkey; cTurkish Academy of Sciences
(TUBA), Çankaya, Ankara, Turkey

ABSTRACT ARTICLE HISTORY

A new coprecipitation procedure was improved for preconcentra­ Received 6 November 2023
tion-separation and detection of trace propineb. In order to copreci­ Accepted 6 December 2023
pitate propineb, 8-hydroxyquinoline (8HQ) and copper (II) were used
KEYWORDS
as a precipitating agent and a carrier element, respectively. Using
Copper (II); coprecipitation;
the stoichiometric relationship with zinc, propineb was determined. flame atomic absorption
The critical parameters on the quantitative recoveries of analyte such spectrometry (FAAS); 8-
as pH, mass of precipitating agent, mass of carrier element, and sam­ hydroxyquinoline; precon­
ple volume were studied. The influences of the matrix components centration; Propineb; zinc
were also tested. The preconcentration factor was 80. The limit of
detection (LOD), and the limit of quantification (LOQ) for propineb
were 0.114 mg L−1 and 0.38 mg L−1, respectively. Copper(II)-8-hydrox­
yquinoline coprecipitation was applied to determine propineb in
vegetable and fruit samples from Kayseri-Turkey with satisfactory
results. Flame atomic absorption spectrometry (FAAS) was utilized
for measurements of model and real sample solutions.

Introduction
Pesticides pose a serious threat to human and animal health due to their non-
biodegradable, toxic, and carcinogenic effects (Abbaci, Azzouz, and Bouznit 2014;
Hoseinzadeh et al. 2023; Kar et al. 2023; Ozalp, Gumus, and Soylak 2023). Fungicides are
used more in agriculture than insecticides and herbicides. Dithiocarbamates (DTCs) are
frequently preferred as fungicides especially in the Mediterranean region due to their bio­
logical and chemical properties, low production costs and broad antifungal activities.
DTCs have a strong chelating ability against inorganic species. The consumption of DTCs
is annually estimated at 30,000 metric tons (Szolar 2007; Ozalp et al. 2022). Some of these
DTCs are propineb, nabam, mancozeb, maneb, ziram zineb, metam, dibam, ferbam and
thiram (Capkin et al. 2010; Kanchi, Singh, and Bisetty 2014). In addition, direct exposure
to these compounds caused by long-term inhalation, or oral exposure may cause skin and
eye allergies, asthma, impaired organ activities, decreased sperm and egg counts, and can­
cer (FAO/WHO, 1993; Nordberg, Duffus, and Templeton 2004).

CONTACT Mustafa Soylak soylak@erciyes.edu.tr Faculty of Sciences, Department of Chemistry, Erciyes University,
Kayseri, Turkey
� 2023 Taylor & Francis Group, LLC
2 M. SOYLAK ET AL.

Propineb is zinc N-[1-(sulfidocarbothioylamino) propan-2-yl] carbamodithioate.

Propineb is a nonspecific, multisite dithiocarbamate fungicide. Propineb also has a pro­
tective effect against germinating conidia. Propineb is used to control gray blight in
some ornamental plants, fruits such as grapes and apples, and vegetables and fruits such
as tomatoes, potatoes, and tobacco. The zinc ion is the central metal ion in the fungi­
cide. Both zinc and CS2 in propineb structure play an important role in neurotoxicity
(Banerjee et al. 2010; Jagirani, Ozalp, and Soylak 2022).
There are analytical methods to determine residues of carbamate pesticides including
propineb in food and agricultural samples including high-performance liquid chroma­
tography, absorption spectrometry, electrochemical sensor gas chromatography-mass
spectrometry, optical sensor, immunosensor, polarography and electrophoretic detection
techniques (Brezonik and Arnold, 2011; Ozdes et al. 2023; Soylak, Ahmed, and Ozalp
2022; Soylak and Murat 2014; Wang et al. 2019; Weingerl and Kerin 2000; Oflu et al.
2023; Zarnoushe Farahani et al. 2023). Due to lower level of analyte levels and high
matrix contents of real samples, separation-preconcentration methods such as cloud
point extraction, coprecipitation, solid phase extraction, and liquid-liquid extraction
(Farajzadeh et al. 2009; Kaplan et al. 2005; Mohamadjafari and Rastegarzadeh 2017;
Soylak and Kizil 2011; T€ urker and Sezer 2005; Wierucka and Biziuk 2014; Wan Ibrahim
et al. 2015) have been developed for the determination of metal-containing pesticides
and other analytes. The coprecipitation is one of the environmentally friendly, fast, sim­
ple separation and preconcentration procedures for trace species (Al-Alam et al. 2017;
Ramutshatsha-Makhwedzha et al. 2022; Soylak, Ahmed, and Coban 2023; Soylak and
Yigit 2015). Both organic and inorganic coprecipitating agents were used for the copre­
cipitation of the trace analytes (Soylak, Aydin, and Kizil 2016).
In the presented work, a new coprecipitation method for propineb at trace level was
developed. Cu(II) as a carrier element and 8-hydroxyquinoline (8HQ) as a precipitating
agent were used. Propineb levels in the vegetable and fruit samples were calculated after
flame atomic absorption spectrometric analysis using the stoichiometric relationship
between zinc and propineb.

Experimental
Instruments
A ContrAA 800 model continuum source atomic absorption spectrometer equipped
with a xenon arc lamp was used to determine the propineb concentrations as zinc (II).
Depending on the manufacturer’s standards, all measurements were carried out in the
atomic absorption spectrometer at an air-acetylene burner with a flame height of 6 cm.
Nuve NF400 model centrifuge (Ankara, Turkey) was used for the centrifugation of
solutions. Fisons WhirliMixer Vortex Shaker Cyclone Mixer model-12665 (Fisher
Scientific, MA, USA) was used to dissolve precipitates.

Chemicals
All chemicals used were of analytical reagent grade and were used as received without
any purification. Distilled water had been used in all experiments. 1000 mg/L of copper
 ANALYTICAL LETTERS 3

stack solution was prepared from copper (II) nitrate trihydrate. 8-hydroxyquinoline
(8HQ) (5% w/v) was prepared in ethanol-water mixture. Phosphate, acetate, and ammo­
nium buffer solutions were used for pH adjustments. For interference study, Kþ, Naþ,
Liþ, NH4þ, Mg2þ, Ca2þ, CO32−, NO3−, Cl−, and F− (1000 mg/L, E. Merck, Darmstadt)
solutions were used as matrix ion solutions. Zinc-1-methylethylen-bisdithiocarbamat
(propineb) was prepared at 100 mg/L. Nitric acid (1 mol/L) was used as a solvent for
dissolution of the Cu(II)- 8-hydroxyquinoline precipitate.

Test procedure
The presented coprecipitation method was tested by using model solutions before apply­
ing them to real samples. The schematic diagram of the presented coprecipitation pro­
cedure was given in Figure 1. 400 lL of 0.5% (2 mg) 8HQ was added to 40 mL of a
solution containing 5.0 lg propineb, 2.0 mL phosphate buffer solution of pH 6.0 in a
centrifuge tube. Next, 0.25 mg of Cu(II) (250 mL of 1000 mg/L Cu(II) nitrate trihydrate
solution) was added and was shaken by hand. The obtained mixture was put in a cen­
trifuge at 4100 rpm for 5 min. The tube content was decanted. In order to dissolve the
precipitate remaining in the tube, 1 mol/L nitric acid was added to the tube and vortex
mixedfor 10 s. The propineb level as the zinc equivalent was determined by flame
atomic absorption spectrometry (FAAS).

Application to real samples

The presented coprecipitation procedure was applied to free acid mineral water, water­
fall water and Erciyes University tap water. 2 mL from each sample was analyzed as
described above. The final solutions containing zinc ions were analyzed using FAAS.
Fresh vegetables and fruits were purchased from local market from Kayseri-Turkey.
Each sample was washed with distilled water (120 mL) in beakers for 10 min. 10 mL
from their washing water was taken to a tube and the same steps mentioned above
were applied to each sample.

Figure 1. Schematic diagram of the coprecipitation procedure.

4 M. SOYLAK ET AL.

Results and discussion

The innovation of this study lies in the development and optimization of a coprecipita­
tion technique for preconcentrating, separating, and detecting trace levels of propineb
in water and food samples. This coprecipitation technique employs 8HQ as a precipitat­
ing agent, and Cu(II) as a carrier element. The synergistic interaction between 8HQ and
copper (II) facilitates the selective coprecipitation of propineb from the sample matrices.
The coprecipitation process is driven by the formation of Cu(II)-8HQ complex.
Propineb is co-precipitated with Cu(II)-8HQ precipitation at same time. The stoichio­
metric relationship between propineb and zinc is utilized for quantification. The novelty
stems from the innovative combination of 8HQ and copper (II) for coprecipitation,
offering a reliable and sensitive method for determining propineb in water and food.

Effects of pH on the coprecipitation efficiency of propineb

The pH of the working solution is a critical factor to obtain quantitative recovery values
of the analytes at trace levels in separation-preconcentration studies including coprecipi­
tation studies (Soylak et al. 2005; Soylak, Kars, and Narin 2008; Olchowski et al. 2023;
Caliskan 2023; Conchado-Amado et al. 2023). The influence of pH on the recovery val­
ues of propineb for the presented coprecipitation work was studied in the range from
4.0 to 12.0 using buffer solutions. The results are shown in Figure 2. The quantitative
recoveries of propineb were obtained in the pH range from 4.0 to 8.0. The decrease in
the recovery of propineb in alkaline medium can be attributed to the formation of less
reactive Cu(II) hydroxyl complexes, the reduced availability of protonated 8HQ, and the
competition from Cu(II)-hydroxide precipitation (Konshina et al. 2022; Soylak, Kaya,
and Tuzen 2007). pH 6.0 was selected and used in subsequent experiments.

Figure 2. Influence of pH on the recovery values of propineb; buffer solution: 2 mL of phosphate buf­
fer; carrier element: 0.25 mg of Cu(II) ((250 mL of 1000 mg/L Cu(II)); precipitating agent: 400 lL of 0.5%
(2 mg) 8HQ; sample solution; 40 mL; 5 lg propineb; shaking: 10 s; centrifuge: 5 min; eluent: 0.5 mL of
nitric acid (1 mol/L); vortex: 10 s (N ¼ 3).
 ANALYTICAL LETTERS 5

Influences of mass of Cu(II) as carrier element

The mass of carrier element (Cu(II)) on the recovery values of propineb were also
studied using model solutions at pH 6.0 providing from 0.05 to 0.50 mg of Cu(II). The
results are shown in Figure 3. The recovery values for propineb were quantitative from
0.05 to 0.25 mg of Cu(II). 0.25 mg of Cu(II) as carrier element was used in further
work.

Influence of precipitating agent

The mass of 8-hydroxyquinoline (8HQ) as a precipitating agent on the recovery of pro­
pineb was studied between 0.2 and 2.5 mg of 8HQ using the optimal conditions. The
recoveries of the propineb increased with the quantity of 8-hydroxyquinoline.
Quantitative recovery was observed using from 1.5 to 2.5 mg of 8HQ. Subsequent
experiments were carried out using 2.0 mg of 8HQ as the precipitating agent.

Influence of sample volume

In order to obtain a high preconcentration factor, the sample volume is a critical par­
ameter (Armagan et al. 2002; Soylak 2004; Serkan Yalçın et al. 2020; Al-Wasidi et al.
2023). The effect of sample volume on the recoveries of propineb was studied for 10 to
50 mL of model solutions. The results are shown in Figure 4. The quantitative recovery
of propineb analyte was obtained from 10 to 40 mL. When the sample volume is 40 mL
and the final volume in this work is 0.5 mL, the preconcentration factor was
equal to 80.

Figure 3. Influence of the mass of carrier element (Cu(II) on the coprecipitation of propineb. Buffer
solution: 2 mL of phosphate buffer at pH 6.0; carrier element: 0.05 – 0.50 mg of Cu(II) (50 – 500 mL of
1000 mg/L Cu(II)); precipitating agent: 400 lL of 0.5% (2 mg) 8HQ; sample solution; 40 mL; 5 lg propi­
neb; shaking: 10 s; centrifuge: 5 min; eluent: 0.5 mL of nitric acid (1 mol/L); vortex: 10 s (N ¼ 3).
6 M. SOYLAK ET AL.

Figure 4. Influence of precipitating agent mass on the coprecipitation of propineb. Buffer solution:
2 mL of phosphate buffer at pH 6.0; carrier element: 0.25 mg of Cu(II) ((250 mL of 1000 mg/L Cu(II));
precipitating agent: 40 - 500 lL of 0.5% (0.2 – 2.5 mg) 8HQ; sample solution; 40 mL; 5 lg propineb;
shaking: 10 s; centrifuge: 5 min; eluent: 0.5 mL of nitric acid (1 mol/L); vortex: 10 s (N ¼ 3).

Matrix effects
The presence of foreign ions at the microgram per milliliter (mg/mL) concentration in
real samples is recognized to impact the accurate determination of metal ions using
atomic absorption spectrometry (Soylak and Kizil 2013; Naseri et al. 2023; Soylak and
Altin 2014). The consideration of ions such as Naþ, Kþ, Liþ, NH4þ, Ca2þ, Mg2þ,
CO32-, F-, NO3-, and Cl- is important in the preconcentration and separation techniques
for food and natural water samples (Ahmed, Mohammed, and Soylak 2023a; Ahmed
and Soylak 2023b; Brezonik and Arnold 2011). Food samples can contain a high con­
centration of some of these ions, particularly Naþ, Kþ, Ca2þ, Mg2þ, and Cl- (Marles
2017). These ions have a significant influence on analytical process by modifying ioniza­
tion efficiency and the retention characteristics of the analytes.
The impact of these matrix ions are investigated for the analysis of natural water and
food samples to enhance the robustness and reliability of analytical methods. The matrix
effects on the presented coprecipitation system and on recovery values of propineb were
tested using these cations and anions. The coprecipitation method mentioned was sep­
arately applied to all matrix ions using the optimal conditions as shown in Table 1. The
matrix interferences may be ignored using optimal conditions.

Analysis of water and food

To evaluate the validation of this work, the presently developed method was applied to
the analysis of mineral water, waterfall water, tap water, apples, peaches, and courgette.
The recovery values of analytes added to the samples were charaterized. The results are
summarized in Tables 2 and 3. Good correspondence was received between the added
and recovered contents using the presented method. Using standard addition, the
 ANALYTICAL LETTERS 7

Table 1. Effects of matrix components on recoveries of the propineb (N ¼ 3).

Matrix ions Added as Concentration, mg L−1 Recovery, %
Naþ Na2CO3 400 91 ± 1�
Kþ KNO3 3000 94 ± 4
Liþ LiCl 1000 103 ± 2
NH4þ NH4Cl 2500 96 ± 1
Ca2þ CaCl2 50 96 ± 4
Mg2þ Mg(NO3)2 250 95 ± 5
CO32- Na2CO3 500 91 ± 1
F- NaF 500 88 ± 2
NO3- KNO3 4500 94 ± 4
Cl- NH4Cl 5000 96 ± 1
�Mean ± Standard deviation.

Table 2. The application of the presented coprecipitation method for propineb in water sam­
ples (N ¼ 3).
Sample Added, mg/L Measured, mg/L Recovery, %
Mineral water 0 0.005 ± 0.000� —
0.15 0.147 ± 0.002 95
0.30 0.298 ± 0.010 98
0.45 0.443 ± 0.015 97
Erciyes University tap water 0 0.012 ± 0.002 —
0.15 0.168 ± 0.007 104
0.30 0.327 ± 0.009 105
0.45 0.471 ± 0.020 102
Waterfall water 0 0.047 ± 0.002 —
0.15 0.183 ± 0.004 91
0.45 0.506 ± 0.011 102
�Mean ± Standard deviation.

Table 3. Application of the presented coprecipitation method for the determination of propineb in
food samples (N ¼ 3).
Added, mg/kg Measured, mg/kg Recovery, %
Peach 0 0.059 ± 0.002 —
0.15 0.199 ± 0.002 93
0.45 0.502 ± 0.000 98
Apple 0 0.030 ± 0.004 —
0.15 0.184 ± 0.006 103
0.30 0.337 ± 0.004 102
0.45 0.500 ± 0.009 104
Courgette 0 0.049 ± 0.002 —
0.15 0.207 ± 0.013 105
0.30 0.360 ± 0.006 104
0.45 0.530 ± 0.010 107
�Mean ± Standard deviation.

recovery was higher than 90% which confirms that the presented procedure is accurate
without matrix interferences.

Conclusions
A new method was improved for the coprecipitation of propineb with Cu(II)-8-hydrox­
yquinoline for its the preconcentration and separation. The impacts of the matrix in
this method were acceptable. Quantitative recovery values were obtained. Moreover, this
method offers simplicity, speed, and the use of fewer toxic chemicals. The correlation
 8
M. SOYLAK ET AL.

Table 4. Comparison of separation-preconcentration methods for propineb in the literature.

Limit of Relative standard Preconcentration
Method Analysis technique Limit of detection quantification deviation (%) factor Reference
Dispersive liquid-liquid Gas chromatography-mass 150 mg/kg 520 mg/kg 9.4 — Bodur et al. 2020
microextraction spectrometry
Coprecipitation Flame atomic absorption spectrometry 15.2 mg/L 50.7 mg/L 3.1 15 Soylak, Ahmed, and
Coban 2023
Solvent extraction Gas chromatography-mass 15–17 mg/L 50 − 56.7 mg/L 2.4 − 2.9 — Kazos et al. 2007
spectrometry
Microsolid phase extraction Spectrophotometry 71.8 mg/L 239.3 mg/L 8.96 250 Giannoulis et al. 2014
Solvent extraction Gas chromatography-mass 1.0 mg/kg 2.5 mg/kg <20 — Kumar et al. 2020
spectrometry
Coprecipitation Flame atomic absorption spectrometry 114 mg/L 380 mg/L <6 80 Presented work
 ANALYTICAL LETTERS 9

coefficient, limit of detection, and limit of quantification were 0.9997, 0.114 mg L−1, and
0.38 mg L−1 respectively. The recovery values for real samples were quantitative and in
the range between 91 and 107%. The preconcentration factor for this study was 80 and
superior to some coprecipitation methods and other preconcentration techniques
(Table 4). The coprecipitation developed method can be successfully stratified to the
separation-preconcentration and determination of propineb.

Disclosure statement
No potential conflict of interest was reported by the author(s).

References
Abbaci, A., N. Azzouz, and Y. Bouznit. 2014. A new copper doped montmorillonite modified
carbon paste electrode for propineb detection. Applied Clay Science 90:130–4. doi: 10.1016/j.
clay.2013.12.036.
Ahmed, H. E. H., A. M. A. Mohammed, and M. Soylak. 2023a. A magnetic solid phase extraction
procedure for Pb(II) at trace levels on magnetic Luffa@TiO2 in food and water samples. Food
Chemistry 428:136794. doi: 10.1016/j.foodchem.2023.136794.
Ahmed, H. E. H., and M. Soylak. 2023b. Magnetic Luffa@metal-organic frameworks (MOF-199)
nanocomposite for the solid phase microextraction of some metal ions at trace levels from
food and water samples. Journal of Food Composition and Analysis 121:105396. doi: 10.1016/j.
jfca.2023.105396.
Al-Alam, J., L. Bom, A. Chbani, Z. Fajloun, and M. Millet. 2017. Analysis of dithiocarbamate fun­
gicides in vegetable matrices using HPLC-UV followed by atomic absorption spectrometry.
Journal of Chromatographic Science 55 (4):429–35.
Al-Wasidi, A. S., H. A. Katouah, F. A. Saad, and E. A. Abdelrahman. 2023. Functionalization of
silica nanoparticles by 5-chloro-8-quinolinol as a new nanocomposite for the efficient removal
and preconcentration of Al3þ ions from water samples. ACS Omega 8 (17):15276–87. doi: 10.
1021/acsomega.3c00413.
Armagan, F., M. Soylak, L. Elci, and M. Dogan. 2002. Solid phase extraction of some metal ions
on diaion HP-20 resin prior to flame atomic absorption spectrometric analysis. Journal of
Trace and Microprobe Techniques 20 (1):15–27. doi: 10.1081/TMA-120002457.
Banerjee, H., P. Ganguly, S. Roy, D. Banerjee, M. Paramasivam, T. Banerjee, and K. K. Sharma.
2010. Persistence and safety risk assessment of propineb in Indian tea. Environmental
Monitoring and Assessment 170 (1–4):311–4. doi: 10.1007/s10661-009-1234-9.
€ T. G€
Bodur, S., S. Erarpat, O. unkara, D. S. Chormey, and S. Bakırdere. 2020. A new derivatiza­
tion method for the determination of propineb in black tea and infant formula samples using
dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry.
Talanta 213:120846. doi: 10.1016/j.talanta.2020.120846.
Brezonik, P., and W. Arnold. 2011. Water chemistry: An introduction to the chemistry of natural
and engineered aquatic systems. ’’Oxford University Press, Inc, OUP USA.
Caliskan, C. E. 2023. Solid phase extraction of Co(II) using activated carbon obtained from grape
stalk prior to high-resolution continuum source flame atomic absorption spectrometric detec­
tion. Iranian Journal of Chemistry and Chemical Engineering 42:1282–93.
Capkin, E., E. Terzi, H. Boran, I. Yandi, and I. Altinok. 2010. Effects of some pesticides on the
vital organs of juvenile rainbow trout (Oncorhynchus mykiss). Tissue & Cell 42 (6):376–82.
doi: 10.1016/j.tice.2010.10.001.
Conchado-Amado, P., J. S�anchez-Pi~ nero, J. Moreda-Pi~ neiro, I. Turnes-Carou, P. L�opez-Mah�ıa,
and S. Muniategui-Lorenzo. 2023. Ultra-trace mercury determination in seawater after vortex-
assisted liquid-liquid micro-extraction. Spectrochimica Acta Part B: Atomic Spectroscopy 204:
106683. doi: 10.1016/j.sab.2023.106683.
10 M. SOYLAK ET AL.

FAO/WHO. 1993. Codex Alimentarius Commission, Codex Committee on Pesticide Residues,

Rome, Supplement 1, Vol. 2.
Farajzadeh, M. A., M. Bahram, S. Zorita, and B. G. Mehr. 2009. Optimization and application of
homogeneous liquid–liquid extraction in preconcentration of copper (II) in a ternary solvent
system. Journal of Hazardous Materials 161 (2–3):1535–43. doi: 10.1016/j.jhazmat.2008.05.041.
Giannoulis, K. M., D. L. Giokas, G. Z. Tsogas, and A. G. Vlessidis. 2014. Ligand-free gold nano­
particles as colorimetric probes for the non-destructive determination of total dithiocarbamate
pesticides after solid phase extraction. Talanta 119:276–83. doi: 10.1016/j.talanta.2013.10.063.
Hoseinzadeh, A., H. Heidari, A. A. Matin, and M. Soylak. 2023. Multi-response optimization of a
deep eutectic solvent-based microextraction method for the simultaneous extraction of twenty
organochlorine pesticides for monitoring in various water samples. Microchemical Journal 194:
109226. doi: 10.1016/j.microc.2023.109226.
Jagirani, M. S., O. Ozalp, and M. Soylak. 2022. New trend in the extraction of pesticides from
the environmental and food samples applying microextraction based green chemistry scenario:
A review. Critical Reviews in Analytical Chemistry 52 (6):1343–69. doi: 10.1080/10408347.2021.
1874867.
Kanchi, S., P. Singh, and K. Bisetty. 2014. Dithiocarbamates as hazardous remediation agent: A
critical review on progress in environmental chemistry for inorganic species studies of 20th
century. Arabian Journal of Chemistry 7 (1):11–25. doi: 10.1016/j.arabjc.2013.04.026.
Kaplan, M. M., S. Cerutti, J. A. Salonia, J. A. G�asquez, and L. D. Martinez. 2005.
Preconcentration and determination of tellurium in garlic samples by hydride generation
atomic absorption spectrometry. Journal of AOAC International 88 (4):1242–6. doi: 10.1093/
jaoac/88.4.1242.
Kar, A., S. Deole, B. G. Gadratagi, N. Patil, G. Guru-Pirasanna-Pandi, B. Mahapatra, and T.
Adak. 2023. Facile synthesis of novel magnesium oxide nanoparticles for pesticide sorption
from water. Environmental Science and Pollution Research International 30 (45):101467–82.
doi: 10.1007/s11356-023-29562-x.
Kazos, E. A., C. D. Stalikas, C. G. Nanos, and C. N. Konidari. 2007. Determination of dithiocar­
bamate fungicide propineb and its main metabolite propylenethiourea in airborne samples.
Chemosphere 68 (11):2104–10. doi: 10.1016/j.chemosphere.2007.02.006.
Konshina, D. N., I. A. Lupanova, S. E. Efimenko, and V. V. Konshin. 2022. A new derivative of
8-hydroxyquinoline. Features of distribution and complexation with Cu (II) and Zn (II) in
two-phase systems. Solvent Extraction and Ion Exchange 40 (3):236–50. doi: 10.1080/07366299.
2021.1910271.
Kumar, Y. B., T. P. A. Shabeer, M. Jadhav, K. Banerjee, S. Hingmire, S. Saha, and A. B. Rai.
2020. Analytical method validation, dissipation and safety evaluation of combination fungicides
fenamidone þ mancozeb and iprovalicarb þ propineb in/on tomato. Journal of Food Science
and Technology 57 (6):2061–9. doi: 10.1007/s13197-020-04240-9.
Marles, R. J. 2017. Mineral nutrient composition of vegetables, fruits and grains: The context of
reports of apparent historical declines. Journal of Food Composition and Analysis 56:93–103.
doi: 10.1016/j.jfca.2016.11.012.
Mohamadjafari, S., and S. Rastegarzadeh. 2017. A sensing colorimetric method based on in situ
formation of gold nanoparticles after dispersive liquid-liquid microextraction for determination
of zineb. Microchemical Journal 132:154–60. doi: 10.1016/j.microc.2017.01.021.
Naseri, A., Z. Abed, M. Rajabi, B. Lal, A. Asghari, O. Baigenzhenov, S. Arghavani-Beydokhti, and
A. Hosseini-Bandegharaei. 2023. Use of Chrysosporium/carbon nanotubes for preconcentration
of ultra-trace cadmium levels from various samples after extensive studies on its adsorption
properties. Chemosphere 335:139168. doi: 10.1016/j.chemosphere.2023.139168.
Nordberg, M., J. Duffus, and D. M. Templeton. 2004. Glossary of terms used in toxicokinetics
(IUPAC Recommendations 2003). Pure and Applied Chemistry 76 (5):1033–82. doi: 10.1351/
pac200476051033.
Oflu, S., S. Erarpat, B. T. Zaman, K. Ero�glu, O. € T. G€unkara, S. Bakırdere, and F. Turak. 2023.
Quantification of trace fenuron in waste water samples by matrix matching calibration strategy
and gas chromatography–mass spectrometry after simultaneous derivatization and
 ANALYTICAL LETTERS 11

preconcentration. Environmental Monitoring and Assessment 195 (9):1063. doi: 10.1007/s10661-

023-11575-1.
Olchowski, R., B. Podko�scielna, B. Zawisza, K. Morlo, and R. Dobrowolski. 2023. U(VI) removal
from water by novel P-modified activated carbon derived from polymeric microspheres.
Environmental Nanotechnology, Monitoring & Management 20:100788. doi: 10.1016/j.enmm.
2023.100788.
Ozalp, O., F. Uzcan, Z. P. Gumus, and M. Soylak. 2022. Sample preparation methods for metal
containing pesticides in food and environmental samples. Critical Reviews in Analytical
Chemistry, in press. doi: 10.1080/10408347.2022.2106118.
Ozalp, O., Z. P. Gumus, and M. Soylak. 2023. MIL-101(Cr) metal-organic frameworks based on
deep eutectic solvent (ChCl: Urea) for solid phase extraction of imidacloprid in tea infusions
and water samples. Journal of Molecular Liquids 378:121589. doi: 10.1016/j.molliq.2023.121589.
Ozdes, D., C. Duran, H. Bektas, and E. Mentese. 2023. A facile and sensitive coprecipitation
method coupled with flame atomic absorption spectrometry for quantification of Cu (II) ions
in complex matrices. Journal of the Serbian Chemical Society 88 (3):301–12. doi: 10.2298/
JSC220122074O.
Ramutshatsha-Makhwedzha, D., R. Mbaya, M. L. Mavhungu, and P. N. Nomngongo. 2022.
Ultrasonic assisted dispersive-solid phase extraction for preconcentration of trace metals in
wastewater samples. Journal of Environmental Chemical Engineering 10 (5):108187. doi: 10.
1016/j.jece.2022.108187.
€
Serkan Yalçın, M., E. Kılınç, S. Ozdemir, U. Y€uksel, and M. Soylak. 2020. Phallus impudicus
loaded with c-Fe2O3 as solid phase bioextractor for the preconcentrations of Zn(II) and
Cr(III) from water and food samples. Process Biochemistry 92:149–55. doi: 10.1016/j.procbio.
2020.03.012.
Soylak, M. 2004. Solid phase extraction of Cu(II), Pb(II), Fe(III), Co(II) and Cr(III) on Chelex
100 Column prior to their flame atomic absorption spectrometric determinations. Analytical
Letters 37 (6):1203–17. doi: 10.1081/AL-120034064.
Soylak, M., A. Aydin, and N. Kizil. 2016. Multi-element preconcentration/separation of some
metal ions in environmental samples by using co-precipitation. Journal of AOAC International
99 (1):273–8. doi: 10.5740/jaoacint.11-0214.
Soylak, M., A. Kars, and I. Narin. 2008. Coprecipitation of Ni2þ, Cd2þ and Pb2þ for precon­
centration in environmental samples prior to flame atomic absorption spectrometric determi­
nations. Journal of Hazardous Materials 159 (2–3):435–9. doi: 10.1016/j.jhazmat.2008.02.034.
Soylak, M., and I. Murat. 2014. A new coprecipitation methodology with lutetium hydroxide for
preconcentration of heavy metal ions in herbal plant samples. Journal of AOAC International
97 (4):1189–94. doi: 10.5740/jaoacint.12-331.
Soylak, M., and N. Kizil. 2011. Determination of some heavy metals by flame atomic absorption
spectrometry before coprecipitation with neodymium hydroxide. Journal of AOAC
International 94 (3):978–84. doi: 10.1093/jaoac/94.3.978.
Soylak, M., and N. Kizil. 2013. Neodymium (III) hydroxide coprecipitation-FAAS system for the
speciation of chromium in natural waters. Atomic Spectroscopy 34 (6):216–20. doi: 10.46770/
AS.2013.06.003.
Soylak, M., and R. Altin. 2014. Membrane filtration of lead, cobalt and nickel in water and fertil­
izer samples for enrichment/separation and flame atomic absorption spectrometric determin­
ation. Atomic Spectroscopy 35 (2):163–7. doi: 10.46770/AS.2014.02.004.
Soylak, M., and S. Yigit. 2015. Coprecipitation of Fe (III), Mn (II), Cu (II), Pb (II), Co (II), and
Ni (II) with ytterbium hydroxide for separation and preconcentration prior to determination
by FAAS. Atomic Spectroscopy 36 (4):165–70. doi: 10.46770/AS.2015.04.003.
Soylak, M., B. Kaya, and M. Tuzen. 2007. Copper (II)-8-hydroxquinoline coprecipitation system
for preconcentration and separation of cobalt (II) and manganese (II) in real samples. Journal
of Hazardous Materials 147 (3):832–7. doi: 10.1016/j.jhazmat.2007.01.082.
Soylak, M., H. E. H. Ahmed, and A. N. Coban. 2023. Micro-solid phase extraction of cobalt at
trace levels as 1-nitroso-2-naphthol chelates on magnetic date palm fiber-WSe2 (mDPF@
12 M. SOYLAK ET AL.

WSe2) nanocomposite from food, tobacco, and water samples. Journal of Food Composition
and Analysis 125:105716. doi: 10.1016/j.jfca.2023.105716.
Soylak, M., H. E. H. Ahmed, and O. Ozalp. 2022. Determination of propineb in vegetable sam­
ples after a coprecipitation strategy for its separation-preconcentration prior to its indirect
determination by FAAS. Food Chemistry 388:133002. doi: 10.1016/j.foodchem.2022.133002.
Soylak, M., S. Saracoglu, U. Divrikli, and L. Elci. 2005. Coprecipitation of heavy metals with
erbium hydroxide for their flame atomic absorption spectrometric determinations in environ­
mental samples. Talanta 66 (5):1098–102. doi: 10.1016/j.talanta.2005.01.030.
Szolar, O. H. J. 2007. Environmental and pharmaceutical analysis of dithiocarbamates. Analytica
Chimica Acta 582 (2):191–200. doi: 10.1016/j.aca.2006.09.022.
T€
urker, A. R., and B. Sezer. 2005. Indirect determination of dithiocarbamate fungicides (zineb
and ferbam) in some foodstuffs by flame atomic absorption spectrometry. Turkish Journal of
Pharmaceutical Sciences 2 (1):35–42.
Wan Ibrahim, W. A., H. R. Nodeh, H. Y. Aboul-Enein, and M. M. Sanagi. 2015. Magnetic solid-
phase extraction based on modified ferum oxides for enrichment, preconcentration, and isola­
tion of pesticides and selected pollutants. Critical Reviews in Analytical Chemistry 45 (3):270–
87. doi: 10.1080/10408347.2014.938148.
Wang, X., X. Meng, Q. Wu, C. Wang, and Z. Wang. 2019. Solid phase extraction of carbamate
pesticides with porous organic polymer as adsorbent followed by high performance liquid
chromatography-diode array detection. Journal of Chromatography. A 1600:9–16. doi: 10.1016/
j.chroma.2019.04.031.
Weingerl, V., and D. Kerin. 2000. Distribution of zinc in vineyard areas treated with zinc con­
taining phytopharmaceuticals. Acta Chimica Slovenica 47 (4):453–68.
Wierucka, M., and M. Biziuk. 2014. Application of magnetic nanoparticles for magnetic solid-
phase extraction in preparing biological, environmental and food samples. TrAC Trends in
Analytical Chemistry 59:50–8. doi: 10.1016/j.trac.2014.04.007.
Zarnoushe Farahani, T., G. Bagherian, M. Arab Chamjangali, and M. Ashrafi. 2023. On-line
determination of the trace amount of cobalt(II) in real samples by flame atomic absorption
spectrometry method after pre-concentration by modified polyvinyl chloride. SN Applied
Sciences 5:183.