Talanta Open 8 (2023) 100275

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Talanta Open
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Utilizing a newly developed carrier element free coprecipitation method for

preconcentration and quantification of Co(II), Cu(II), Ni(II), and Zn(II) in
environmental samples
Marmar Mabrouk a, Ahmed H. Moustafa b, Ayman A. Gouda b, *, Hager E. Mohamed b, Ali
M. Alshehri c, Mohannad M. Garoub c, Amal H. Al-Bagawi d, Mona A. El-Attar e
a
Water Resources Management Department, Nile University, Egypt
b
Chemistry Department, Faculty of Science, Zagazig University, Zagazig 44519, Egypt
c
Department of Environmental and Occupational Health, Faculty of Public Health and Health Informatics, Umm Al-Qura University, Makkah, Saudi Arabia
d
Department of Chemistry, College of Science, University of Ha’il, Ha’il City, Saudi Arabia
e
High Institute of Engineering & Technology, Tanta 31739, Egypt

A R T I C L E I N F O A B S T A R C T

Keywords: Co(II), Cu(II), Ni(II), and Zn(II) ions from food and water sample have been separated and preconcentrated using
Carrier element-free coprecipitation a novel, straightforward, and precise carrier element-free coprecipitation approach. The suggested procedure
Metal ions relied on the utilization of 4-(5‑bromo-2-hydroxybenzylideneamino)-N-(pyrimidin-2-yl)-benzenesulfonamide
Environmental samples
(BHBAPBS) as a novel co-precipitant at neutral medium and the flame atomic absorption spectrometry identi­
Certified reference materials
Flame atomic absorption spectrometry
fication of the studied metal ions under investigation. To obtain the metal ions for analysis, Several variables, like
pH, volume of the sample, co-precipitant amount, and the speed and duration of centrifugation, were examined
for their effects. The impact of coexisting ions was also being watched, but no interferences were discovered. The
validity of the recommended strategy was examined using tests using certified reference materials. Analyte ion
recovery values were calculated and found to be between 95 and 100 %. To assess the reliability of the suggested
approach, the relative standard deviation was calculated and discovered to be 3.5 %. The detection limits were
ranged between 0.3 and 0.6 μg L− 1. Preconcentration factor has been determined to be 100. Results for the
preconcentration and separation of trace levels of the investigated ions in environmental and certified reference
materials samples were satisfactory.

1. Introduction the limits of detection and the considerable interference affects of the
coexisting ions [4].
Cobalt (Co(II)), copper (Cu(II)), nickel (Ni(II)), and zinc (Zn(II)) are Numerous preconcentration methods [5–17] have been extensively
just a few examples of heavy metals that are essential non-biodegradable used for preconcentration and extraction of metal ions in order to
micronutrients in the ecosystem and can a negative impact on human overcome these restrictions.
health as well as the environment. Consequently, it is essential for Coprecipitation has a significant preconcentration factor, is fast, re­
analytical chemistry to monitor environmental pollutants to accurately quires little time, uses little organic solvent, and is a straightforward
quantify modest concentrations of metal ions in environmental mate­ preconcentration process for trace metal ions from varied materials
rials [1–3]. utilizing different inorganic or organic coprecipitants [1,2,18–28].
Flame atomic absorption spectrometry (FAAS) has proven to be a Coprecipitation calls for the inclusion of minute contaminants from a
helpful approach for detecting metal ions in different matrices because permeable liquid phase into a precipitate. Trace elements can be
of its excellent selectivity, speed, affordability, simple instrument concentrated or enhanced via precipitates due to their potential to
operation, and high specificity [3]. The precise measurement of metal absorb various contaminants [29]. Surface adsorption, surface precipi­
ions by FAAS is hindered by a lower concentrations of analyte ions than tation, and occlusion are few possible co-precipitation mechanisms [30].

* Corresponding author.
E-mail addresses: aymangouda77@gmail.com, aasallem@zu.edu.eg (A.A. Gouda).

https://doi.org/10.1016/j.talo.2023.100275

Available online 24 November 2023

2666-8319/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
M. Mabrouk et al. Talanta Open 8 (2023) 100275

Table 1
FAAS instumenatal conditions.
Parameter Conditions

Burner 10 cm
Flame Air (pressure 350 KPa, flow rate 11–20 L/min)-acetylene(pressure 75
KPa, flow rate 1.5–10 L/min)
Lamp Hollow cathode
Fig. 1. The chmical structure of 4-(5-bromo-2-hydroxybenzylideneamino)-N-
Wavelength Co (240.7 nm), Cu (324.8 nm), Ni (231.1 nm) and Zn (213.9 nm)
(pyrimidin-2-yl)benzenesulfonamide (BHBAPBS).

The term "carrier element-free coprecipitation" (CEFC) refers to a new bromosalisylaldehyde (0.005 mol) to (30 ml) ethanolic 4-amino-N-(pyr­
coprecipitation technique that was developed without the necessity for a imidin-2-yl)benzenesulfonamide (0.005 mol). The mixture has been
carrier element [1]. Since there is no background adsorption from a refluxed in a water bath for three hours. The solution evaporated on a
metal carrier element or pollution, and because fewer organic solvents rotary evaporator after being cooled to room temperature. The resulting
are used, the CEFC approach is environmentally beneficial and has solid product had a melting point of 246–248 ◦ C, was dried under air,
substantial value in separating and preconcentrating the metal ions filtered, and ethanolic recrystallization was carried out to produce 78 %
[18–28]. yield [32].
In this study, Co(II), Cu(II), Ni(II), and Zn(II) ions are separated and The following (%) information was obtained from the elemental
preconcentrated from some environmental materials using 4-(5‑bromo- analysis of the BHMAPBS (C17H13BrN4O3S; M.Wt. 433.28); C:47.12;
2-hydroxybenzylideneamino)-N-(pyrimidin-2-yl)-benzenesulfonamide H:3.02; Br:18.44; N:12.93 and found (%): C:47.22; H:3.00; Br:18.31;
(BHBAPBS) as coprecipitating agent without the use of a carrier element N:12.91. Fig. 1 depicts the novel reagent’s (BHBAPBS) chemical
before their detection by FAAS. The impacts of several analytical pa­ structure.
rameters, such as pH, BHBAPBS concentration, centrifugation condi­ A precise weight of BHBAPBS was dissolved in ethanol in a 100-mL
tions, and sample volume, on the metal recoveries were investigated. measuring flask to obtain a stock solution (0.2 % w/v and 1.0 × 10− 3
The proposed approach was examined using certified reference mate­ mol L− 1).
rials (CRMs) in order to validate it.
2.4. Coprecipitation procedure
2. Materials and method
Analyte ions have been separated and pre-concentrated using the
2.1. Apparatus CEFC process. For this reason, 50 mL of an aqueous solution containing
20 μg Co(II), Cu(II) or Ni(II), and 15 μg of Zn(II) was mixed with 2.0 mL
The Agilent 55B AA spectrometer (Agilent Technologies Inc., Santa of BHBAPBS solution (0.2 % w/v). Buffer solution usage The pH levels of
Clara, USA) was used to identify the metals under investigation. The the mixture were fixed at 7.0. After standing in the solution for ten
manufacturer’s guidelines were followed for configuring the instrument minutes, it was centrifuged for ten minutes at 4000 rpm. The superna­
specifications. The instrumental conditions are shown in Table 1. The tant was then disregarded. In the end, 1.0 mL of concentrated HNO3 was
sample was injected into the FAAS nebulizer using a microinjection used to dissolve the last of the precipitate in the centrifuge tube. The
method. AD1000 pH-meter with a glass electrode (Adwa Instruments solution’s concentration of analyte ions was determined by FAAS after
Kft., Szeged, Hungary) was used for pH measurments. Water that has being diluted with deionized water to 5.0 mL.
been deionized or bidistilled was obtained using the Milli-Q system
(Millipore, USA). Using a centrifuge (ISOLAB Laborgeräte GmbH, Ger­
many), the separation of the analyte from the sample solution has been 2.5. Analysis to real samples and CRMs
expedited.
The proposed CEFC method was effectively utilized to evaluate the
investigated metal ions in a range of water (tap, mineral, river and sea)
2.2. Chemicals and reagents samples in Egypt, which were preserved in prewashed polyethylene
bottles. The samples were acidified with dil. HNO3 and stored at 4.0 ◦ C
All the chemicals and reagents were of the highest caliber and were after being filtered using 0.45-µm cellulose membrane filters. The sug­
purchased from Merck (Darmstadt, Germany) and Sigma Aldrich (St. gested process was carried out after the samples’ pH was brought down
Louis, USA). Before the experiment, laboratory glassware was cleaned to 7.0 using phosphate buffer solution. FAAS was utilized to pre­
and cleansed numerous times with bidistilled water after being concentrate and identify the metal ions in CRMs (fortified water TMDA-
immersed overnight in a diluted HNO3 (1:9 v/v) solution. 52.3 and TMDA-53.3) using the recommended CEFC technique.
In order to prepare stock solutions (1000 mg L− 1) of the investigated The preconcentration CEFC procedure was applied to certified
metal ions, metal nitrate salts were dissolved in HNO3 (1.0 mol L− 1). reference materials, including spinach leaves (SRM 1570a) and CRM-
The pH of the solutions can be adjusted using various buffer systems SA-C Sandy Soil C Standard material (0.25 mg), and various solid
such as acetate buffer solution for pH (2.0–6.0), phosphate buffer so­ samples acquired from markets in Zagazig, Egypt. After drying at 90 ◦ C
lution for pH values of 6.0 and 7.0 and ammonia buffer solution for pH for 24 h in an electric oven, the 1.0 g triplicate samples of black tea,
(8.0–10) [31]. spinach, tomatoes, and cabbage were mixed together by pounding in a
The accuracy of the suggested approach was confirmed by examining mortar made of agate. For a wet digestion with acid method, 10 ml of
CRMs, including spinach leaves (SRM 1570a), sandy soil standard concentrated nitric acid and 3.0 ml of H2O2 were combined in a Teflon
(CRM–SA–C Sandy Soil C) (High-Purity Standard Inc.), fortified water beaker and heated at 150 ◦ C for 2 h on a hot plate until nearly dry. CRM-
TMDA-52.3 and TMDA-53.3 (National Water Research Institute, Bur­ SA-C Sandy Soil C Standard material (0.5 mg) was digested in a closed
lington, Canada). microwave digestion system using HCl, HNO3, HF, and H2O2 at a ratio of
(4.5:1.5:2:1). After being evaporated, the samples were combined with
2.3. Synthesis of 4-(5-bromo-2-hydroxybenzylideneamino)-N- 10 ml of deionized water. The resulting fluid was then poured into
(pyrimidin-2-yl)-benzenesulfonamide (BHBAPBS) Schiff base plastic bottles after being diluted to 50 ml with deionized water and
filtered through 0.45-µm cellulose membrane filter. The proposed
Shaking was used to introduce a 15 ml ethanolic solution of 5- method was utilized to preconcentrate the analyte ions, and FAAS

2
M. Mabrouk et al. Talanta Open 8 (2023) 100275

Fig. 2. (a) FT-IR and (b) H-NMR spectra of BHBAPBS.

determined the results. 3.2. Optimization of analytical variables

3. Results and discussion 3.2.1. Impact of pH

When applying the suggested CEFC approach, pH is an important
3.1. BHBAPBS IR and 1H NMR spectra factor that influences analyte recovery values. By adding buffer solu­
tions and using the CEFC method on these solutions, it was examined at
The IR spectra υ (cm− 1) of the BHBAPBS Schiff base showed bands at the pH values between 2.0 and 10. The recoveries for metal ions rose
3430 cm− 1 (OH), 3210 (NH), 1617 (HC=N), 1334, 1090 (asym., S=O), significantly in the pH range of 2 to 6, showing that these pH values were
1208 (CN), 953 (S–N), 842 (C–S), 562 (C–Br) (Fig. 2a). The 1H NMR critical for the coprecipitation process. Fig. 3 displays the findings ob­
(DMSO–d6, δ, ppm) spectra of the BHBAPBS Schiff base showed bands at tained from this investigation. The findings indicated that in the pH
6.01 (s, 1H, Ar-H), 6.5 (s, 1H, Ar-H), 7.10 (m, 2H, Ar-H), 7.4–7.6 (m, 4H, range of 6.0–8.0, the analyte ions were reliably recovered (> 95 %). The
Ar-H), 8.5 (m, 2H, Ar-H), 8.82 (s, 1H, CH=N), 8.9 (s, 1H, SO2NH–), 10.2 phosphate buffer solution’s pH of 7.0 was selected as an ideal pH for all
(s, 1H, NH, exchange with D2O) (Fig. 2b). subsequent experiments as a consequence.

3.2.2. Impact of amount of BHBAPBS

The effect of BHBAPBS concentration (0–8.0 mg) on the recoveries of
the tested metal ions was studied. Without addition of BHBAPBS

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M. Mabrouk et al. Talanta Open 8 (2023) 100275

Fig. 3. Effect of pH on the recovery of analyte ions (concentration of Co(II), Cu(II) or Ni(II): 20 μg and Zn(II): 15 μg; amount of BHBAPBS: (0.2 % w/v); final volume:
5.0 mL and N = 3).

Fig. 4. Effect of BHMAPBS quantity as a co-precipitating agent on the recovery of analyte ions (concentration of Co(II), Cu(II) or Ni(II): 20 μg and Zn(II): 15 μg; pH:
7.0; final volume: 5 mL and N = 3).

coprecipitating agent, the metal ions recoveries were not quantifiable were investigated for ranging from 25 to 1000 mL. The findings
(50 %) at optimum conditions. But as BHBAPBS dosage climbed till 4.0 demonstrated that all of the investigated metal ions had quantitative
mg, Fig. 4 shows that quantitative recoveries also increased. Therefore, metal recoveries up to 500 ml (Fig. 5). Preconcentration factors of 100
2.0 ml BHBAPBS (0.2 %, w/v), at 4.0 mg was the ideal dosage. Without were thus attained.
introducing any carrier element to prevent the formation of insoluble
complexes or salts, which pose a danger of contamination and inter­ 3.2.5. Impact of matrix ions
ference for analytes, the BHBAPBS agent produced an efficient and ac­ In solutions containing 20 μg mL− 1 of all analyte ions, different
curate measurment of metal ions on its own. concentrations of the foreign metal ions mentioned in Table 1 were
introduced to examine the impacts of coexisting ions on the effectiveness
3.2.3. Impact of centrifugation conditions of CEFC method. As shown in Table 1, the metal ions’ quantitative re­
The effectiveness of the CEFC process was evaluated for standing coveries were accomplished. The coexisting matrix ions had no
times between 1.0 and 20 min, centrifugation speeds between 1500 and discernible impact on the analyte ions’ recoveries. Eventually, samples
5000 rpm, and centrifugation times between 5.0 and 25 min. The out­ containing different foreign ions might be tested using the proposed
comes showed that at the standing time of 20 min, centrifugation con­ CEFC method at the permitted amounts listed in Table 2.
ditions were 4000 rpm for 10 min, the quantifiable metal recoveries
were resulted for all subsequent trials.
3.3. Method validation
3.2.4. Impact of volume of sample
The data obtained by FAAS measurements were used to evaluate the
A crucial metric for identifying a high preconcentration factor is
performance of the suggested method based on CEFC. The outcomes
sample volume. Using model solutions, the impacts of sample volume
displayed in Table 3 validated the accuracy of the provided CEFC

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M. Mabrouk et al. Talanta Open 8 (2023) 100275

Fig. 5. Effect of sample volume on the recovery of analyte ions (concentration of Co(II), Cu(II) or Ni(II): 20 μg and Zn(II): 15 μg; pH: 7.0; amount of BHBAPBS: (0.2 %
w/v); and N = 3).

approach for identifying the examined metal ions within the specified
Table 2 linear ranges. The coefficient of determination (r2) was ≥ 0.9988. The
Influence of coexisting matrix ions on the recovery of the analyte ions (N = 3). recoveries and relative standard deviations (RSD%) acquired from ten
Ions Added as Concentration Recovery (%) replicate evaluations of the model solution of metal ions were used to
(mg L− 1) test the repeatability and accuracy of the recommended CEFC approach.
Co Cu Ni Zn
(II) (II) (II) (II) The RSDs% for Co(II), Cu(II), Ni(II), and Zn(II) ions were determined to
Na+ NaCl 10,000 96 97 95 96
be 3.50 %, 2.40 %, 2.70 %, and 2.20 %, respectively. The calibration
±2 ±3 ±4 ±2 curve’s slope (m) and the reagent blank signals’ standard deviation (Sb)
K+ KCl 10,000 97 96 97 97 were used to determine the limit of detection and quantitation (LOD = 3
±3 ±4 ±2 ±4 Sb/m and LOQ = 10 Sb/m, n = 10) which recorded in Table 3.
Ca2+ CaCl2 1000 96 95 95 96
By analysing certified reference materials (SRM 1570a spinach
±3 ±4 ±3 ±3
Mg 2+
MgCl2 1000 97 97 96 97 leaves, CRM-Sandy Soil C, and fortified water TMDA-52.3 and TMDA-
±2 ±2 ±3 ±4 53.3), the validity of the suggested CEFC procedure was confirmed
Cl− NaCl 10.000 98 95 98 98 (Table 4). The quantitative recovery values and the certified values have
±4 ±2 ±4 ±3
a good level of agreement.
PO3−
4 Na3PO4 1000 96 96 98 97
±2 ±4 ±4 ±2
SO2−
4 Na2SO4 1000 95 97 95 96 3.4. Applications to various samples
±4 ±3 ±4 ±2
NO−3 Na3NO3 10,000 97 98 97 97
±3 ±3 ±3 ±3
In order to evaluate the efficacy of the present CEFC technique,
Al3+, Mo6+, Nitrate 50 97 98 96 98 various concentrations of the investigated metal ions were spiked into
Hg2+, Cd2+, salts ±4 ±4 ±2 ±3 different water and food samples. Tables 5 and 6 present the findings.
Pb2+, Fe3+ and Then, under ideal circumstances, the procedure was applied to the
Bi3+
samples. The analyte ion recovery levels were generally acceptable and
Mixed a 96 98 98 97
±2 ±4 ±3 ±2 reasonable (≥ 95 %).
a
Mixed solution contains 10.000 mg L− 1 of Na+, K+, Cl− and NO−3 ; 1.000 mg
L− 1 of Ca2+, Mg2+, SO2− 3−
4 and PO4 ; and 50 mg L
− 1
of Al3+, Mo6+, Hg2+, Cd2+, 3.5. Analysis of the proposed method in comparison to existing methods
Pb2+, Fe3+ and Bi3+ ions.
In Table 7, the suggested CEFC approach is compared to the existing
published methods [1,2,18–28] for trace metal ions. The parameters
Table 3 that were obtained were comparable to those that had been written
Characteristics of the calibration graphs of the described CEFE method for about previously. When compared to existing approaches, the suggested
simultaneous determination of Co(II), Cu(II), Ni(II) and Zn(II) (n = 3.0). CEFC method has a comparatively low LOD or RSD and a relatively high
PF.
Parameters Co(II) Cu(II) Ni(II) Zn(II)

Linearity (µg L− 1) 1.0–200 1.50–300 1.20–240 1.80–300

4. Conclusion
Regression equation
Slope 0.0015 0.0009 0.001 0.001
Intercept − 0.00005 0.0013 0.002 0.0069 A new, simple, efficient, and quick CEFC method with a novel
Correlation coeffienet (r2) 0.9990 0.9996 0.9988 0.9989 coprecipitating agent (BHBAPBS) was developed and effectively utilized
RSDs% 3.50 2.40 2.70 2.20
to achieve excellent recoveries, a low LOD, high reliability, and accuracy
LOD (µg L− 1) 0.30 0.50 0.40 0.60
LOQ (µg L− 1) 1.0 1.50 1.20 1.80
for the separation and quantification of metal ions (Co(II), Cu(II), Ni(II),
and Zn(II)) in various environmental samples. The matrix was not

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M. Mabrouk et al. Talanta Open 8 (2023) 100275

Table 4
The analysis results of certified reference materials after application of the proposed procedure (n = 3.0).
Analyte SRM 1570A spinach leaves CRM-SA-C Sandy Soil C
a
Certified value Found Recovery, Certified value Found a Recovery,
(μg g− 1) (μg g− 1) % (μg L− 1) (μg L− 1) %

Co(II) 0.39 ± 0.05 0.37 ± 0.08 95.0 12.4 ± 0.6 12.0 ± 0.40 96.80
Cu(II) 12.2 ± 0.60 11.80 ± 0.90 96.70 63.6 ± 4.0 62.0 ± 4.20 97.50
Ni(II) 2.14 ± 0.10 2.05 ± 0.07 96.0 48.4 ± 3.0 46.20 ± 2.60 95.50
Zn(II) 82.0 ± 3.0 79.50 ± 2.80 97.0 607 ± 30.0 585.0 ± 24.0 96.40

TMDA-52.3 fortified water TMDA-53.3 fortified water

Certified value Found a Recovery, Certified value Found a Recovery,

(μg L− 1) (μg L− 1) % (μg L− 1) (μg L− 1) %

Co(II) 136 132.0 ± 4.0 96.80 251 241.0 ± 3.0 96.0

Cu(II) 197 188.0 ± 5.0 95.50 308 300.0 ± 7.0 97.40
Ni(II) 274 268.0 ± 4.60 98.0 311 297.0 ± 5.0 95.50
Zn(II) 263 253.0 ± 3.80 96.20 385 370.0 ± 6.0 96.10
a
Mean±standard deviation.

Table 5
Spiked recoveries of analyte ions from water samples using the proposed method (n = 3.0).
Element Added Tap water Mineral water River water Sea water
(μg) a a a a
Found Recovery Found Recovery Found Recovery Found Recovery (%)
(μg) (%) (μg) (%) (μg) (%) (μg)

Co(II) 0 BDL b – BDL – BDL – 3.2 ± 0.1 –

10 9.54 ± 0.3 95.4 9.75 ± 0.3 97.5 9.63 ± 0.3 96.3 12.94 ± 0.4 98.0
20 19.56 ± 0.4 97.8 19.84 ± 0.5 99.2 20.2 ± 0.7 101.0 22.67 ± 0.6 97.7
Cu(II) 0 4.0 ± 0.2 – BDL – 3.0 ± 0.2 – 7.0 ± 0.4 –
8.0 8.08 ± 0.3 101.0 7.96 ± 0.2 98.3 7.97 ± 0.4 99.6 14.5 ± 0.3 96.5
16 15.44 ± 0.6 96.50 15.33 ± 0.5 95.8 15.71 ± 0.7 98.2 22.3 ± 0.8 96.9
Ni(II) 0 BDL – BDL – BDL – 2.5 ± 0.1 –
10 9.83 ± 0.5 98.3 10.05 ± 0.4 100.5 9.66 ± 0.5 96.6 12.4 ± 0.3 99.3
20 19.24 ± 0.7 96.2 19.5 ± 1.0 97.5 19.58 ± 0.8 97.9 21.9 ± 0.9 97.50
Zn(II) 0 BDL – BDL – BDL – 4.0 ± 0.2 –
10 9.8 ± 0.3 98.0 9.9 ± 0.2 99.0 9.75 ± 0.4 97.5 13.3 ± 0.5 95.0
20 19.0 ± 0.9 95.0 19.34 ± 0.6 96.7 19.64 ± 0.7 98.2 23.1 ± 0.8 96.3
a
Mean±standard deviation.
b
BDL: Below detection limit.

Table 6
The addition-recovery results for the analyte ions in food samples using the proposed method (n = 3.0).
Analyte Added Cabbage Black pepper Black tea
(μg L− 1) a a
Found Recovery Found Recovery (%) Found Recovery (%)
(μg) (%)b (μg) (μg)

Co(II) 0 3.50 ± 0.2 – 2.70 ± 0.1 – < LODc –

10 13.03 ± 0.3 96.5 12.45 ± 0.3 98.0 9.90 ± 0.4 99.0
20 23.03 ± 0.6 98.0 22.13 ± 0.5 97.5 20.0 ± 0.8 100.0
Cu(II) 0 4.20 ± 0.1 – 5.0 ± 0.2 – 6.30 ± 0.2 –
8.0 11.71 ± 0.2 96.0 12.45 ± 0.4 95.8 14.4 ± 0.4 101.0
16 20.0 ± 0.6 99.0 20.58 ± 0.6 98.0 21.56 ± 0.7 96.7
Ni(II) 0 2.50 ± 0.2 – 3.8 ± 0.2 – 4.0 ± 0.1 –
10 11.95 ± 0.4 95.6 13.46 ± 0.4 97.5 13.48 ± 0.3 96.3
20 21.6 ± 0.8 96.0 22.61 ± 0.7 95.0 23.64 ± 0.6 98.5
Zn(II) 0 < LOD – < LOD – < LOD –
10 9.5 ± 0.2 95.0 9.6 ± 0.3 96.0 9.76 ± 0.3 97.6
20 20.2 ± 0.7 101.0 19.7 ± 0.8 98.5 19.0 ± 0.6 95.0
a
Mean±standard deviation.
b
Recovery% = [Observed value of analyte ion/Expected value of analyte ion] × 100.
c
LOD: limit of detection.

affected in any manner by any foreign ions. An analysis of the approved Resources, Writing – original draft, Writing – review & editing. Ahmed
reference materials was used to confirm the proposed method’s accuracy H. Moustafa: Conceptualization, Methodology, Writing – review &
and precision. editing, Supervision. Ayman A. Gouda: Conceptualization, Methodol­
ogy, Writing – original draft, Writing – review & editing, Supervision.
CRediT authorship contribution statement Hager E. Mohamed: Software, Validation, Formal analysis, Investiga­
tion, Resources, Writing – original draft. Ali M. Alshehri: Conceptual­
Marmar Mabrouk: Conceptualization, Software, Formal analysis, ization, Software, Formal analysis, Resources, Writing – original draft,

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M. Mabrouk et al. Talanta Open 8 (2023) 100275

Table 7
Comparison of the proposed method with some reported CEFC methods of heavy metal ions.
Coprecipitating agent Studied elements pH PF LOD RSD Refs.
− 1
(μg L ) (%)

BNBATT Cd(II), Cu(II), Ni(II) 7.0 100 0.3, 0.5, 0.6, <5.0 [1]
Pb(II) 80 0.8
APSAL Cr(III), Cu(II), Fe(III), Pb(II), Zn(II) 7.0 100 0.2, 0.5, 0.8, 1.2, 0.7 <5.0 [2]
MEFMAT Cu(II), Cd(II) 6.8 50 1.49, 0.45 3.2, 2.0 [3]
HMDTC–HMA Cu(II), Ni(II), Fe(III), Cd(II), Pb(II), 6.0 500 Cu(II),Co(II) 19.5, 28.5, 36.1, 5.9, 61.0, <10 [18]
Co(II) 250 Ni(II), Fe(III), Cd 23.4
(II), Pb(II)
BPNBAT Fe(III), Pb(II), Cu(II), Zn(II), Cr(III) 7.0 150 0.3–2.0 1.6–6.0 [19]
POHBAT Cr(III), Fe(III), Pb(II), Zn(II) 7.0 150 Cr(III), Fe(III), Zn 0.5, 0.7, 2.0,0.3 3.0–7.0 [20]
(II)
50 Pb(II),
CTAB Cd(II), Cr(III), Co(II), Cu(II), Fe 10 10 0.61, 16.8, 12.7, 1.36, <5.0 [21]
(III), Pb(II), Mn(II) 2.08, 4.30, 0.22
BCP Cu(II), Pb(II), Zn(II), Fe(III), Cr(III) 9.0 25 0.8, 3.08, 0.28, 0.91, 1.82 8.0 [22]
ICOTPA Ni(II), Cd(II) 7.5 125 0.27, 0.58 <4.0 [23]
ICOTMA Pb(II), Cr(III), Cu(II) 7.0 50 0.86, 2.06, 0.56 3.6, 4.1, 2.8 [24]
Cadion Fe(III), Cr(III), Pb(II), 8.0 – 300, 90, 60 <5.0 [25]
3-(4‑tert-butylphenyl)- Pb(II), Cd(II) 6.0 50 2.0, 0.2 5.7, 4.8 [26]
5-phenyl-4-(2‑hydroxy-5-
methoxybenzylidenamino)-
4H-1,2,4-triazole
IMOTPA Co(II), Cu(II), Ni(II) 6.5 100 0.4, 0.16, 0.17 2.7, 1.9, 2.4 [27]
MITA Pb(II), Cu(II) 7.0 125 1.32, 0.47 3.25, 2.96 [28]
BHBAPBS Co(II), Cu(II), Ni(II), Zn(II) 7.0 100 0.3, 0.5, 0.4, 0.6 3.50, 2.40, 2.70, This
2.20 work

PF: preconcentration factor; LOD: limit of detection; RSD: relative standard deviation.
BNBATT: 3-benzyl-4-p-nitrobenzylidenamino-4,5-dihydro-1,2,4-triazole-5-thiol.
APSAL: 4-(2-hydroxybenzylideneamino)− 1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one.
MEFMAT: 2-{[4-(4-fluorophenyl)− 5-sulphanyl-4H-1,2,4-triazol-3-yl]methyl}− 4-{[(4-fluorophenyl) methylene]amino}− 5-(4-methylphenyl)− 2,4-dihydro-3H-1,2,4-
triazol-3-one.
HMDTC-HMA: hexamethylene-dithiocarbamic acid hexamethyleneammonium salt; BPNBAT: 3-benzyl-4-p-nitrobenzylidenamino-4,5-dihydro-1,2,4-triazole-5-on;
POHBAT: 3-phenly-4-o-hydroxybenzylidenamino-4,5-dihydro-1,2,4-triazole-5-one;.
CTAB: N-cetyl N,N,N-trimethyl ammonium bromide.
BCP: 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline.
ICOTPA: 2-{4-[2-(1H-Indol-3-yl)ethyl]− 3-(4-chlorobenzyl)− 5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl}-N′-(pyrrol-2-ylmethyliden)acetohydrazide.
ICOTMA: (2-{4-[2-(1H-indol-3- yl)ethyl]− 3-(4-chlorobenzyl)− 5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl}-N-aryl methylidene acetohydrazid)
IMOTPA: 2–{4–[2–(1H–indol–3–yl)ethyl]–3–(4–methylbenzyl)–5–oxo–4,5–dihydro–1H–1,2,4–triazol–1–yl}–N’–(pyridin–2–yl methylidene)acetohydrazide.
MITA: 2-f3-(4-Methylbenzyl)− 4-[2-(1H-indol-3-yl)ethyl]− 5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-ylg -N’-(phenylmethylene) acetohydrazide.
BHBAPBS: 4-{[(E)-(5-Bromo-2-hydroxyphenyl)methylidene]amino}-N-(pyrimidin-2-yl)benzene sulfonamide

Writing – review & editing. Mohannad M. Garoub: Conceptualization, [3] C. Duran, D. Ozdes, D. Sahin, V.N. Bulut, A. Gundogdu, M. Soylak,
Preconcentration of Cd(II) and Cu(II) ions by coprecipitation without any carrier
Software, Formal analysis, Resources, Writing – original draft, Writing –
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review & editing. Amal H. Al-Bagawi: Conceptualization, Methodol­ [4] A. Gonzalvez, S. Armenta, M.L. Cervera, M. Guardia, Elemental composition of
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Conceptualization, Software, Formal analysis, Resources, Writing – [5] A.A. Gouda, R. El Sheikh, H.M. El Sayed, A.A. Khedr, S.H. Abo Al Ezz, W. Gamil,
M. Hamdy, Ultrasound-assisted dispersive microsolid-phase extraction for
original draft, Writing – review & editing. preconcentration of trace cobalt and nickel in environmental samples prior to their
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Declaration of Competing Interest [6] R. El Sheikh, W.S. Hassan, A.M. Youssef, A. Alharbi, A.M. Hameed, A. Subihi, A.
A. Gouda, Eco-friendly ultrasound-assisted ionic liquid-based dispersive liquid-
liquid microextraction of nickel in water, food and tobacco samples prior to FAAS
The authors declare that they have no known competing financial determination, Int. J. Environ. Anal. Chem. 102 (4) (2022) 899–910.
interests or personal relationships that could have appeared to influence [7] Z. Li, Y. Zhang, R. Wang, D. Jiang, Separation, preconcentration, and
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