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Article

Fabrication of Spiny-like Spherical Copper Metal–Organic Frameworks for the Microextraction of Arsenic(III) from Water and Food Samples before ICP-MS Detection

by
Mohamed A. Habila
1,*,
Zeid A. ALOthman
1,
Mohamed Sheikh
1 and
Saleh O. Alaswad
2
1
Chemistry Department, College of Science, King Saud University, Riyadh 11451, Saudi Arabia
2
Nuclear Science Research Institute (NSRI), King Abdulaziz City for Science and Technology (KACST), P.O. Box 6086, Riyadh 11442, Saudi Arabia
*
Author to whom correspondence should be addressed.
Appl. Sci. 2023, 13(18), 10036; https://doi.org/10.3390/app131810036
Submission received: 13 August 2023 / Revised: 30 August 2023 / Accepted: 1 September 2023 / Published: 6 September 2023
(This article belongs to the Special Issue Applications of MOFs and COFs in Drug Delivery, Separation and Water Purification Purposes)
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Abstract

:
Spiny-like spherical copper metal–organic frameworks (SSC-MOFs) were prepared and characterized via SEM, TEM, EDS, XRD, FTIR and the BET surface area. The fabricated SSC-MOFs were applied to develop a procedure for the microextraction of trace arsenic(III) for preconcentration. The results show that a copper- and imidazole-derived metal–organic framework was formed in a sphere with a spiny surface and a surface area of 120.7 m2/g. The TEM confirmed the perforated network structures of the SSC-MOFs, which were prepared at room temperature. The surface functional groups were found to contain NH and C=N groups. The XRD analysis confirmed the crystalline structure of the prepared SSC-MOFs. The application for the process of microextracting the arsenic(III) for preconcentration was achieved with superior efficiency. The optimum conditions for the recovery of the arsenic(III) were a pH of 7 and the use of a sample volume up to 40 mL. The developed SSC-MOF-derived microextraction process has an LOD of 0.554 µg·L−1 and an LOQ of 1.66 µg·L−10. The developed SSC-MOF-derived microextraction process was applied for the accurate preconcentration of arsenic(III) from real samples, including food and water, with the promised performance efficiency.

1. Introduction

Arsenic pollution is a critical problem for humans and animals. Sources of arsenic pollution in the environment may come from breaking rocks under air pressure, dust collisions or water flow [1,2,3,4]. An additional source of arsenic pollution may be incomplete combustion during industrial processes. The arsenic produced could contaminate water surfaces, food and air systems [5,6,7,8]. The World Health Organization (WHO) and the U.S. Environmental Protection Agency (EPA) have determined 10 μg·L−1 to be threshold for the arsenic limit in drinking water [9,10]. Short-term exposure to arsenic leads immediately to muscle cramps and abdominal pain and in some cases, diarrhea, while long-term arsenic exposure may cause skin pigmentation and diabetes, affect erythrocytes and cause an increase in blood pressure. In addition, arsenic is considered carcinogenic and may lead to death [1,11,12,13]. The main reasons for human contact with arsenic are polluted drinking water and contaminated food. Therefore, monitoring the traces of arsenic in food and drinking water is a critical international need [14,15,16]. Arsenic analysis can be achieved via atomic absorption spectroscopy and inductively coupled plasma instrumentation; however, the existence of arsenic below the limit of detection may reduce the accuracy of these measurements [17,18]. Moreover, the presence of a complex matrix in the sample extract may alter the analysis and cause interference, lowering the efficiency of the analytical methods [12,19].
Extraction and preconcentration via various methods, such as solid-phase extraction or dispersive liquid microextraction, enhance the isolation of a matrix and increase the concentration of the analyte [19,20,21,22,23,24]. For example, Santos et al. [25] determined arsenic via on-line preconcentration and reported limits of detection and quantification of 0.02 and 0.07 μg L−1, respectively. Wan et al. [26] conducted a comparison between different extraction methods, Tessier, Rauret and Shiowatana, and reported that Shiowatana is the best procedure for arsenic extraction. Nicholas et al. [27] identified the solid-phase sources and geochemical mechanisms of the release of arsenic, and their results confirmed that the glacial sediments at the interfaces between aquifers and aquitards are geochemically active zones for arsenic. Garcia et al. [28] used magnetic ferrite particles to study low concentrations of arsenic and reported a limit of detection of 0.02 µg·L−1 of arsenic for a sample volume of 10 mL. Lukojko et al. [29] applied a highly selective determination for an arsenic analysis, and the detection limit was 0.045 ng·m·L−1. In addition, the process can be successfully applied for the analysis of high-salinity water. Jabasingh et al. [30] used magnetic materials for the extraction of arsenic ions from contaminated aqueous streams, which proved to be effective and beneficial for the separation of the toxic arsenic ions, and demonstrated a process for efficient practical applications. Wen and Zhu [31] developed a simple and efficient method using dual-cloud point extraction (dual-CPE) with a detection limit for As(III) of 0.72 ng·mL−1. Pena-Pereira et al. [32] applied a method for arsenic speciation analysis based on a paper-based analytical device. The proposed method showed limits of detection and quantification of 1.1 and 3.6 ng·mL−1, respectively. Munonde et al. [33] prepared magnetic Fe3O4 nanocomposites to be applied in the preconcentration of arsenic, and under optimized conditions, the limits of detection and quantification were 8.6 and 28.5 ng·L−1, respectively. Lee et al. [34] used on-line sample preconcentration techniques and reported limits of detection in the range of 0.08–0.3 ppb for arsenic. Baranik et al. [35] prepared a novel nanocomposite suitable for the sorption of selected species of arsenic and chromium and indicated a limit of detection of 0.02 ng·mL−1 for arsenic and a limit of detection of 0.11 ng·mL−1 for chromium.
Solid-phase microextraction is preferred for sample purification due to its high efficiency in preconcentrating a wide range of pollutants, as well as the high sample volume that can be applied. The key to this technique is the preparation of suitable and superior adsorbent materials that exhibit the desired levels of porosity, dispersibility and stability [36,37,38,39]. The development of an efficient adsorbent is the key to applicable and effective separation, even for extraction and/or adsorptive wastewater treatments [40,41]. Nowadays, metal–organic-framework-based adsorbents have a magic ability to adsorb and separate materials for many purposes such as catalysis, energy and extraction techniques [42,43,44,45,46,47]. These categories of materials are constructed using inorganic parts, which may be metal oxide clusters and/or metal ions, which are able to co-ordinate an organic ligand moiety. The large possibility of varying the inorganic and organic constituents enable scientists to tune the materials’ structures at the molecular scale [48,49]. In addition, the porosity and functionalization of MOF-derived adsorbents can be easily developed. Furthermore, the co-ordination bonds produced during the formation of MOFs via linking metals with heteroatom-derived ligands produce high variations in electron-deficient metal sites on the adsorbent surfaces which act as attractive centers to enhance adsorption, photocatalysis, extraction and preconcentration applications [50,51,52]. The organic linkers can be obtained via chemical synthesis, extracted from natural products or collected from biomass or waste-derived materials. For example, Mahmoodi et al. applied a bioligand originating from eggshells to produce bio-nanocomposite-derived MOFs via ultrasonic assessed synthesis. The fabricated eggshell-derived framework exhibited a surface area of 1263.9 m2·g−1 and showed a high level of efficiency for the adsorption of heavy metals and dyes [53].
Copper-derived metal–organic frameworks have been intensely applied in separation applications with desired levels of efficiency [54,55,56]. This work aimed to prepare a copper-based metal–organic framework as an adsorbent for the separation and enrichment of arsenic(III) via microextraction. Imidazole was used as an organic linker to co-ordinate the copper ions and to provide the nitrogen centers in the final structure of the MOFs. The fabricated metal–organic frameworks were examined via SEM, TEM, EDS and XRD. The microextraction process was investigated to enhance the recovery% of the arsenic(III) by optimizing the pH, eluent type, sample volume and co-existing ions. In addition, the developed microextraction process was validated via spiking-based addition/recovery and inter- and intra-day investigations. Furthermore, arsenic(III) was extracted and preconcentrated from real field samples such as water and food collected from Riyadh City, Saudi Arabia.

2. Experiment

2.1. Chemicals and Instruments

All the reagents used in this work were of analytical-grade purity. Aluminum nitrate, potassium chloride, sodium fluoride, sodium carbonate, sodium sulfate, magnesium chloride, calcium chloride, sodium phosphate, iron(III) nitrate, nickel nitrate, cadmium nitrate, lead nitrate and copper(II) nitrate trihydrate were obtained from Sigma-Aldrich (St. Louis, MO, USA). Sodium hydroxide, disodium hydrogen phosphate, potassium dihydrogen phosphate, hydrochloric acid, nitric acid and ethanol were purchased from Merck (Darmstadt, Germany). An ICP-MS (PerkinElmer, Inc., Shelton, CT, USA) was used for the arsenic analysis.

2.2. The Preparation of Spiny-like Spherical Copper Metal–Organic Frameworks

For the preparation of the spiny-like spherical copper metal–organic framework (SSC-MOF)-derived adsorbent materials, 0.604 g of copper nitrate trihydrate was dissolved in 30 mL of deionized water and mixed with an imidazole solution (2.0 g in 25 mL of deionized water). The mixture was stirred using a magnetic stirrer for 30 min. Then, a sodium hydroxide solution of 0.1 M was slowly added drop by drop with continuous stirring until the reaction solution became pink. The mixture was continuously stirred at 100 °C for an additional 12 h; then, the formed spiny-like spherical copper metal–organic frameworks were separated via centrifugation and washed with deionized water and ethanol. The fabricated SSC-MOFs were characterized via TEM, XRD, SEM, EDS, the BET surface area and FTIR spectroscopy.

2.3. The Development of Solid-Phase Microextraction for Trace Arsenic(III) Preconcentration

A sample solution of 40 mL of arsenic(III) was taken in a 50 mL polypropylene tube, and the pH was adjusted to 7 using 2 mL of a phosphate buffer. The solution was then optimized by adding drops of HCl (0.01 M) or NaOH (0.01 M). Then, 0.05 g of the fabricated SSC-MOFs was added, and the mixture was continuously shaken at 150 rpm for 10 min to allow for the adsorption process and the mass transfer of the arsenic(III) ions from the aqueous solution to the surfaces and pores of the SSC-MOFs. The second step for the separation of the arsenic(III)-loaded SSC-MOFs from the aqueous liquid phase was achieved via the centrifugation of the mixture at 5000× g rpm for 2 min to separate the aqueous phase from the SSC-MOFs. After discarding the aqueous phase, the arsenic(III) was recovered from the SSC-MOFs via elution with 1.0 mL of 0.05 M nitric acid. The preconcentrated arsenic(III) trace content was then detected via ICP-MS. The efficiency of the developed solid-phase microextraction procedure was evaluated by calculating the recovery%, using Equation (1) as follows:
R e c o v e r y % = C f C 0 ∗ 100 ,
where Cf is the final concentration of extracted arsenic(III) detected, and C0 is the initial concentration detected in the primary arsenic(III) sample solution.
The adsorption kinetic of arsenic onto SSC-MOFs is studied as described in the Supplementary Materials. The developed solid-phase microextraction procedure using SSC-MOFs was repeated to study the influence of the most controlling parameters, such as the pH, eluent type and concentration, sample volume, shaking time and co-existing ions, for optimizing the microextraction process. In addition, the intra-day precision and inter-day precision were evaluated by using 0.01 mg·L−1, 0.03 mg·L−1 and 0.05 mg·L−1 of arsenic(III) with 8 replicates for different time intervals over three consecutive days [57]. For an investigation of the ability to recycle the applied SSC-MOFs after their use, the adsorbent was washed twice with ethanol and once with water and then dried in oven at 105 °C for 10 h. The adsorbent was then reused for subsequent solid-phase microextraction procedures. The preconcentration and recycling processes were repeated 8 times. Scheme 1 represents the experimental steps for preparing SSC-MOFs for solid-phase microextraction prior to ICP-MS detection.

2.4. Analyses of Real Water and Food Samples

Real samples, including tap water, ground water, lettuce, dill, coriander, parsley and tomatoes, were obtained from markets in Riyadh City. The water samples were filtered with Whatman filter paper No 3 before the developed solid-phase microextraction procedure using the fabricated SSC-MOFs was applied. For preparation of the food samples, including lettuce, dill, coriander, parsley and tomatoes, 1.0 g of each sample was digested using 15 mL of HNO3 via heat using a magnetic stirrer until the sample was nearly dry. Then, 3 mL of H2O2 was added, and the sample extract was maintained under continuous heating conditions until a clear extract was obtained. The obtained extract was filtered with Whatman filter paper No 3, and the final volume was adjusted to 10 mL using deionized water. [58,59]. The developed solid-phase microextraction procedure using SSC-MOFs was then applied as described above to preconcentrate the arsenic(III) prior to detection via ICP-MS. The water and food sample extracts were subjected to addition/recovery investigations by spiking them with 0.05, 0.5, 1.0 and 1.5 mg·L−1 of arsenic(III) prior to applying the developed solid-phase microextraction procedure using SSC-MOFs to assess the efficiency and the linearity of the developed microextraction process.

3. Results and Discussion

3.1. Morphological and Structural Investigations

The SEM analysis of the prepared spiny-like spherical copper metal–organic frameworks (SSC-MOFs) showed a uniform sample structure with a spherical shape which exhibited dimensions between 20 µm and 30 µm (Figure 1A,B). The EDS (Figure 1C) analysis confirmed the presence of C, Cu, N and O as the main surface elements on the formed SSC-MOFs owing to the rich presence of heteroatoms on the adsorbent surfaces, which were expected to enhance the separation application. The TEM analysis showed the structure of the formed SSC-MOFs to be parallel, as well as showing interconnected stalks with widths of about 40 nm and lengths between 300 nm and 400 nm (Figure 2A,B). In addition, pores and cavities between the interconnected stalks in the entire SSC-MOF structure were noted, indicating the porous structure of the formed adsorbent materials. The imidazole ligand possesses two nitrogen centers; thus, it can act as an effective interactive attraction site for the copper ions to form a framework during the synthesis process. It was reported that the imidazole-derived ligands enhance the formation of porous metal–organic framework structures [60,61,62]. The formation of SSC-MOFs with interconnected stalks and spiky, spherical surfaces is recommended to enhance the dispersion of the SSC-MOFs in an aqueous solution and provide efficient contact with the entire sample extract during the microextraction process for the adsorption and preconcentration of arsenic(III) from water and food sample extracts. The porous nature of the formed SSC-MOFs was confirmed via a BET surface area analysis via the adsorption/desorption of N2 (Figure 3), which indicated a BET surface area of 120.7 m2·g−1. Figure 3 shows an adsorption isotherm of mesoporous materials (type IV). The mesoporous structure of the fabricated SSC-MOFs plays an important role in facilitating the separation of pollutants via the adsorption/desorption mechanism during the microextraction process. The mesoporous structure enables the migration of the adsorbed analyte inside the pores, which improves the adsorption capacity of the material and enhances the applicability for preconcentration purposes [63,64]. The capacity of the fabricated SSC-MOFs to adsorb arsenic(III) is reported to be 187.3 mg·g−1, indicating their high level of efficiency for separating arsenic(III) from aqueous solutions.
The fabricated SSC-MOFs were analyzed via FTIR to identify the active sites on their surfaces, and the obtained spectrum is presented in Figure 4. A C=N peak was detected at around 1670 cm−1 due to the imidazole ligand. In addition, strong N-H stretching was detected between 3300 cm−1 and 3600 cm−1, which is believed to be derived from the free imidazole ends. Peaks relating to C-N stretching were found in the region between 1100 cm−1 and 1400 cm−1. The XRD analysis confirmed the crystalline structure of the formed SSC-MOFs, with peaks at 2θ of 10.8, 11.3, 15.6, 16.5, 18.7, 19.9, 20.3, 32 and 34, as presented in the inset graph (Figure 5), in addition to the patterns detected at 37.4, 43.5, 76.9 and 81.17 [65,66,67]. These results indicate that the copper ions inside the MOF structure may have more than one transition state, which may be due to the occurrence of a co-ordination with oxygen atom in water molecules simultaneously with bonding formed to nitrogen from the imidazole ligand [66,68].

3.2. Optimizing the Developed Solid-Phase Microextraction onto SSC-MOFs

The promised features of the metal–organic frameworks, such as their porosity and high adsorption capability, have led to efficient microextraction applications [45,46,69,70,71,72,73]. Herein, a microextraction method for the separation of arsenic(III) traces was established using the prepared SSC-MOFs. The process of the microextraction procedure was enhanced by the ability of the adsorbent (a solid support material) to disperse in the sample extract solution and attract the targeted analyte species during the adsorption process to achieve the complete transfer of mass and settlement on the surfaces and pores of the SSC-MOFs. The pH of the sample extract was reported to be a highly influencing factor in the adsorption process and the control efficiency of the microextraction procedures [74,75,76]. Therefore, in this work, the effect of pH was studied in the range between two and eight. The recovery% of the pH investigation is presented in Figure 6A. A low recovery% was achieved in the acidic medium; however, a higher recovery% was obtained in the pH range between six and eight. This may be because the lower-pH medium was rich with H ions, which resulted in the protonation of the functional group, including a reduction in the interaction with the arsenic(III) ion species. A pH of 7 was selected as the optimum condition for the further optimization of the microextraction of arsenic(III) using the formulated SSC-MOFs. The effectiveness of the microextraction procedures applied in this work is illustrated in Scheme 1, which showed the porosity structure and the active surface functional groups such as C=N and N-H. These active groups enhance Vander Waals forces and dipole–dipole interaction and facilitate the collection and attraction of arsenic from the aqueous sample solution during the microextraction process.
In addition, the effect of the shaking time during the adsorption stage on the recovery% was studied for the microextraction mixture, including the sample extract and the SSC-MOFs. The tested time intervals included 1, 3, 5, 8, 10, 12 and 15 min, as presented in Figure 6B. After 10 min, the recovery% was 99%, indicating the efficiency of the process for preconcentrating arsenic(III) from aqueous samples. The contact time of 10 min during the adsorption stage was demonstrated to be the optimum time for the mass transfer of trace arsenic(III) from the aqueous sample solution to the adsorbent’s surface. The next step for optimizing the microextraction process was to determine a suitable eluent solution for the desorption stage. For this purpose, solutions of 0.1, 0.3 and 0.5 M of HCl as well as 0.05, 0.1 and 0.3 M of HNO3 were applied, and the recover% values are shown in Figure 6C. The HCl-derived solutions exhibited the lowest efficiency for eluting the arsenic(III) from the SSC-MOFs; however, the diluted nitric acid solutions were the most efficient for the elution process, reporting recovery% values of 99, 98 and 99 for 0.05, 0.1 and 0.3 M of HNO3, respectively.
The crystalline structure of the fabricated SSC-MOFs, as well as the surface functional groups, enable the adsorbent to be used multiple times after it is regenerated by being washed with ethanol and water. The regeneration process was repeated eight times with an efficient performance of the microextraction of arsenic(III), with a recover% of about 98 (Figure 6D). These results indicate the sustainable nature of the fabricated SSC-MOFs, which serve to save materials via recycling and reduce the waste produced from the entire microextraction process. The sample volume of the primary arsenic(III) sample solution was investigated to assess the capacity of the developed microextraction procedure using SSC-MOFs. The results presented in Figure 6E indicate that up to 40 mL of the developed microextraction procedure exhibited a recovery% of about 98. In addition, the rate of adsorption of arsenic(III) onto the SSC-MOFs is investigated using the pseudo-first order and the pseudo-second order kinetic models (Figure 7). The data for the adsorption process tend to follow the pseudo-second order kinetic model with a correlation factor of 0.996, compared to 0.936 in case of the pseudo-first order model, indicating a fast adsorption process.

3.3. Interference Investigations and Analytical Merits for the Application of the Fabricated SSC-MOFs

The efficiency of a microextraction procedure is strongly dependent on the whole sample’s matrix and on competition, which may occur if the sample extract contains foreign ions. In this study, different ions were studied to assess their competition with arsenic(III) and their influence on the final recovery% of the developed microextraction process using SSC-MOFs (Table 1). The tested ions included NO3−, Cl−, F−, CO32−, SO42−, K+, Mg2+, Ca2+, Na+, Fe3+, Zn2+, Cd2+, Pb2+, Ni2+ and Cu2+. The obtained recovery% was above 91% for all the tested ions, indicating a high-tolerance ability of the fabricated SSC-MOFs to sustain the efficiency of the microextraction process even in a model solution and/or real samples with various matrices. The higher recovery% is correlated with the ability of the fabricated SSC-MOFs to attract the targeted analyte in the presence of various interference ions, which may be due to the MOFs’ porous structure and surface functional groups such as N-H and C=N.
The preconcentrating factor is estimated as the ratio of the calibration curve when the microextraction procedure is applied to the absence of the microextraction procedure. The developed microextraction procedure exhibited a preconcentration factor of 63.1, an LOD of 0.554 µg·L−1 and an LOQ of 1.66 µg·L−1. The RSD% of the developed microextraction of arsenic(III) using the fabricated SSC-MOFs was investigated for intra-day and inter-day analyses of arsenic(III) concentrations of 0.01, 0.03 and 0.05 mg·L−1 (Table 2). The RSD% was reported between 1.38 and 2.56 for all experiments, even for the intra-day or inter-day investigations (Table 2), indicating the effectiveness and reproducibility of the microextraction procedure using SSC-MOFs.
The most common routes of human exposure to arsenic(III) are due to the consumption of water and food. Previous studies indicated that arsenic(III) extensively contaminates drinking water and foodstuffs [77,78,79,80,81]. Therefore, the microextraction procedures developed using the SSC-MOFs were applied to the preconcentration of arsenic(III) from some water and food samples collected from Riyadh City markets in the Kingdom of Saudi Arabia. The applied samples included tap water, ground water, lettuce, dill, coriander, parsley and tomatoes. The detected arsenic(III) concentrations are presented in Table 3, indicating that only the ground water sample contained a trace arsenic(III) concentration of 0.005 mg L−1, and the other tested samples were below the limit of detection. The addition of a known arsenic(III) concentration and an evaluation of its recovery from the tested real samples were carried out, and the applicability of the developed arsenic(III) microextraction procedure based on the fabricated SSC-MOFs to the extraction of arsenic(III) from various matrices was investigated. The arsenic(III) spiked in the concentration range of between 0.005 and 1.5, and the recovered concentrations are reported in Table 3. The recovery% was in the range between 92 and 100 for all the tested samples. The effective application of the developed microextraction procedures with the successful recovery of arsenic(III) from food extracts and water samples make them suitable for arsenic(III)-monitoring service applications in a broad range of environmental samples. However, in this study, the arsenic(III) concentration in most of the food samples was within the limits permitted by the FAO and the WHO, and some previous investigations reported arsenic(III) contamination in various environmental samples from the Kingdom of Saudi Arabia [82,83,84,85,86].

4. Conclusions

Spiny-like spherical copper metal–organic frameworks (SSC-MOFs) were fabricated as spheres with interconnected stalks and porous, crystalline structures. The developed SSC-MOFs possess rich surface functional groups, including N-H from an imidazole ligand. The porous structure of the fabricated SSC-MOFs leads to its high level of efficiency in microextracting arsenic(III) from various sample matrixes at a pH of 7, with a contact time of 10 min and using 0.05 M of HNO3 as an eluent. The developed arsenic(III) microextraction procedure based on the fabricated SSC-MOFs exhibited high performance, with a recovery of no less than 90%, even in competitive environments including various ions such as NO3−, Cl−, F−, CO32−, SO42−, K+, Mg2+, Ca2+, Na+, Fe3+, Cr3+, Zn2+, Cd2+, Pb2+, Ni2+ and Cu2+. The successful application of the synthetized SSC-MOFs for the microextraction of arsenic(III) will encourage further future research studies on the synthesis and evaluation of metal–organic framework-derived adsorbents for the microextraction of other pollutants including dyes, pesticides and/or heavy metals.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/app131810036/s1.

Author Contributions

Conceptualization, M.A.H.; formal analysis, M.A.H., M.S. and S.O.A.; investigation, M.A.H. and Z.A.A.; methodology, Z.A.A., M.S. and S.O.A.; resources, Z.A.A.; validation, M.A.H., Z.A.A., M.S. and S.O.A.; writing–original draft, M.A.H.; writing–review and editing, M.A.H. and Z.A.A. All authors have read and agreed to the published version of the manuscript.

Funding

This work was funded by the Deputyship for Research & Innovation, Ministry of Education in Saudi Arabia for funding this research work through the project no. IFKSUOR3–446-2.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Samples of the compounds are available from the authors.

Acknowledgments

The authors extend their appreciation to the Deputyship for Research & Innovation, Ministry of Education in Saudi Arabia for funding this research work through the project no. IFKSUOR3–446-2.

Conflicts of Interest

The authors declare no conflict of interest.

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Applsci 13 10036 sch001
Scheme 1. Preparation of SSC-MOFs for solid-phase microextraction prior to ICP-MS detection.
Scheme 1. Preparation of SSC-MOFs for solid-phase microextraction prior to ICP-MS detection.
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Figure 1. The SEM images of the fabricated SSC-MOFs at magnifications of (A) 200 and (B) 1000 and the (C) EDS analysis.
Figure 1. The SEM images of the fabricated SSC-MOFs at magnifications of (A) 200 and (B) 1000 and the (C) EDS analysis.
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Figure 2. The TEM images of the fabricated SSC-MOFs at magnifications of (A) 50,000 and (B) 30,000.
Figure 2. The TEM images of the fabricated SSC-MOFs at magnifications of (A) 50,000 and (B) 30,000.
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Figure 3. The porosity investigation using an adsorption/desorption nitrogen isotherm.
Figure 3. The porosity investigation using an adsorption/desorption nitrogen isotherm.
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Figure 4. The FTIR spectrum of the fabricated SSC-MOFs.
Figure 4. The FTIR spectrum of the fabricated SSC-MOFs.
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Figure 5. The XRD pattern for the fabricated SSC-MOFs.
Figure 5. The XRD pattern for the fabricated SSC-MOFs.
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Figure 6. The optimization of the developed solid-phase microextraction of the arsenic(III) onto the SSC-MOFs; (A) effect of pH, (B) shaking time investigation, (C) effect of eluent type, (D) recycling and reuse investigation and (E) effect of sample volume.
Figure 6. The optimization of the developed solid-phase microextraction of the arsenic(III) onto the SSC-MOFs; (A) effect of pH, (B) shaking time investigation, (C) effect of eluent type, (D) recycling and reuse investigation and (E) effect of sample volume.
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Figure 7. (A) The pseudo-first order and (B) the pseudo-second order kinetic models for adsorption of arsenic(III) onto the SSC-MOFs.
Figure 7. (A) The pseudo-first order and (B) the pseudo-second order kinetic models for adsorption of arsenic(III) onto the SSC-MOFs.
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Table 1. An evaluation of the ions interfering effect on the recovery%.
Table 1. An evaluation of the ions interfering effect on the recovery%.
Interfering IonsAdded asConcentration (mg·L−1)Recovery%
NO3−Al(NO3)350098.2 ± 0.1
Cl−KCl150099.5 ± 0.5
F−NaF40094.2 ± 1.1
CO32−Na2CO350096.0 ± 0.6
SO42−Na2SO480092.9 ± 0.9
K+KCl100093.3 ± 1.0
Mg2+MgCl2800100.0 ± 0.2
Ca2+CaCl250099.5 ± 0.1
Na+Na3PO4500094.2 ± 0.8
Fe3+Fe(NO3)31596.0 ± 0.2.3
Zn2+Ni(NO3)22093.3 ± 0.5
Cd2+Cd(NO3)21091.1 ± 0.9
Pb2+Pb(NO3)21095.6 ± 0.5
Ni2+Ni(NO3)21097.0 ± 1.5
Cu2+Cu(NO3)22097.8 ± 1.1
Table 2. Evaluation of intra-day and inter-day precision for arsenic(III) microextraction using SSC-MOFs (N = 8).
Table 2. Evaluation of intra-day and inter-day precision for arsenic(III) microextraction using SSC-MOFs (N = 8).
Concentration of Standard Solution
(mg·L−1)		Intra-Day Validation Inter-Day Validation
First DaySecond DayThird Day
Detected Concentration (mg·L−1)Precision (RSD%)Detected Concentration (mg·L−1)Precision (RSD%)Detected Concentration (mg·L−1)Precision (RSD%)Detected Concentration (mg·L−1)Precision (RSD%)
0.010.01001.590.00991.910.01012.220.00992.46
0.030.03001.380.02991.920.03002.470.02992.56
0.050.04992.320.04951.970.04972.140.04992.92
Table 3. The addition of certain concentrations of arsenic(III) and its recovery from some food and water samples (N = 3).
Table 3. The addition of certain concentrations of arsenic(III) and its recovery from some food and water samples (N = 3).
Real Sample KindDetected Arsenic(III)
(mg·L−1)		Additions/Recovery Investigations
Spiking of
0.05 mg·L−1		Spiking of
0.5 mg·L−1		Spiking of
1.0 mg·L−1		Spiking of
1.5 mg·L−1
DetectedRecovery%DetectedRecovery%DetectedRecovery%DetectedRecovery%
WaterTap WaterBDL *0.049 ± 0.002980.495 ± 0.001990.999 ± 0.0201001.486 ± 0.01599
Ground Water0.005 ± 0.0010.050 ± 0.0051000.491 ± 0.009980.984 ± 0.015981.487 ± 0.02099
FoodLettuceBDL *0.048 ± 0.001960.499 ± 0.0101000.987 ± 0.005991.49 ± 0.01899
DillBDL *0.048 ± 0.005960.489 ± 0.005980.957 ± 0.014961.489 ± 0.00599
CorianderBDL *0.049 ± 0.004980.475 ± 0.008950.953 ± 0.002951.499 ± 0.009100
ParsleyBDL *0.046 ± 0.004920.495 ± 0.001990.94 ± 0.009941.5 ± 0.012100
TomatoesBDL *0.050 ± 0.0061000.496 ± 0.010990.972 ± 0.010971.482 ± 0.02599
* Below detection limits.
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MDPI and ACS Style

Habila, M.A.; ALOthman, Z.A.; Sheikh, M.; Alaswad, S.O. Fabrication of Spiny-like Spherical Copper Metal–Organic Frameworks for the Microextraction of Arsenic(III) from Water and Food Samples before ICP-MS Detection. Appl. Sci. 2023, 13, 10036. https://doi.org/10.3390/app131810036

AMA Style

Habila MA, ALOthman ZA, Sheikh M, Alaswad SO. Fabrication of Spiny-like Spherical Copper Metal–Organic Frameworks for the Microextraction of Arsenic(III) from Water and Food Samples before ICP-MS Detection. Applied Sciences. 2023; 13(18):10036. https://doi.org/10.3390/app131810036

Chicago/Turabian Style

Habila, Mohamed A., Zeid A. ALOthman, Mohamed Sheikh, and Saleh O. Alaswad. 2023. "Fabrication of Spiny-like Spherical Copper Metal–Organic Frameworks for the Microextraction of Arsenic(III) from Water and Food Samples before ICP-MS Detection" Applied Sciences 13, no. 18: 10036. https://doi.org/10.3390/app131810036

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