Dispersive Solid Phase Extraction of Phthalate Esters in Fruit Juice PDF

Journal of Food Composition and Analysis xxx (xxxx) 107227 Contents lists available at ScienceDirect Journal of Food Composition and Analysis...

Journal of Food Composition and Analysis xxx (xxxx) 107227 Contents lists available at ScienceDirect Journal of Food Composition and Analysis journal homepage: www.elsevier.com/locate/jfca F Dispersive solid phase extraction of four phthalate esters as plastic packing plasticizers from fruit juice samples using ternary metallic-organic OO framework composite before their determination with gas chromatography Maryam Hosseini a, Babak Ghanbarzadeh a, ⁎, Akram Pezeshki a, Mohammad Reza Afshar Mogaddam b, c, d, ⁎⁎ a Department of Food Science, College of Agriculture, University of Tabriz, Tabriz 5166616471, Iran PR b Food and Drug Safety Research Center, Tabriz University of Medical Sciences, Tabriz, Iran c Research Center of New Material and Green Chemistry, Khazar University, 41 Mehseti Street, Baku AZ1096, Azerbaijan d Pharmaceutical Analysis Research Center, Tabriz University of Medical Sciences, Tabriz, Iran ARTICLE INFO ABSTRACT Keywords: Phthalate diesters are widely used as plasticizers in the preparation and manipulation of plastics. These diesters D Fruit juice degrade into phthalate, which is a global concern due their endocrine-disrupting properties in the human body. Phthalate ester Therefore, the accurate determination of phthalate esters in food samples is crucial for evaluating the potential Dispersive solid phase extraction risks associated with both phthalate monoesters and diesters. The main goal of this study is to utilize a ternary Gas chromatography metallic-organic framework composite (NiCoMn-MOF) as an efficient sorbent in dispersive solid phase extraction Flame ionization detector TE Metal organic framework of four common phthalate esters (DEP, DBP, DIBP, and DEHP) from fruit juice samples. To quantify the extracted analytes, gas chromatography equipped with a flame ionization detector was employed. To optimize the extrac- tion efficiency, various parameters such as sorbent amount, the type and volume of elution solvent, sorption agi- tation mode and time, and ionic strength were adjusted. Under the optimal extraction conditions, the calibration plots for phthalate esters showed linearity in the concentration range of 0.96–250 ng mL−1, with low detection limits ranging from 0.11 to 0.29 ng mL−1. The developed method was successfully applied to extract and deter- mine the phthalate esters in different fruit juices. The results demonstrated acceptable precision, with extraction EC recovery values in the range of 65–75 %, high enrichment factors (325−375), and relative standard deviations ≤ 6.8 %. After optimizing and validating of the method, it was applied to several fruit juices, all of which contami- nated by the phthalate esters. The effect of storage temperature and time was also investigated. 1. Introduction ing hepatotoxicity, carcinogenicity and reduced sperm production), RR PAEs such as di-ethylhexyl phthalate (DEHP), di-ethyl phthalate (DEP), Phthalate esters (PAEs) are global additives in various industries di-isobutyl phthalate (DIBP), and di-butyl phthalate (DBP), have been like plastics, pharmaceuticals, personal care, and cosmetics, due to identified as pollutants by the US Environmental Protection Agency their ability to enhance properties such as flexibility, transparency, (EPA) (Chang et al. 2021). For instance, the World Health Organization durability, and longevity (Godwin, 2017; Erythropel, et al. 2014). How- (WHO) has set a maximum contaminant level (MCL) of 6 μg L−1 for ever, the extensive production and use of plastics, coupled with the lack DEHP in drinking water (Abdar et al. 2023). To safeguard human CO of strong chemical bonds between PAEs and plastics, result in signifi- health, it is essential to develop a sensitive and accurate method for as- cant amounts of PAEs being released into the environment, leading to sessing of these compounds in various samples. The EPA has introduced environmental pollution (Kim et al. 2019; Zuccarello et al. 2018). Due gas chromatography (GC) based procedures to determine several PAEs to potential risks of PAEs to the environment and human health (includ- in municipal, and industrial discharges (https://www.epa.gov/sites/ Abbreviations: PAE, Phthalate ester; DSPE, Dispersive solid phase extraction; MOF, Metal organic framework; GC, Gas chromatography; LOD, Limit of detection; EF, enrichment factor; ER, Enrichment factor; FID, Flame ionization detector ⁎ Corresponding author. ⁎⁎ Corresponding author at: Food and Drug Safety Research Center, Tabriz University of Medical Sciences, Tabriz, Iran. E-mail addresses: [email protected] (B. Ghanbarzadeh), [email protected], [email protected] (M.R.A. Mogaddam). https://doi.org/10.1016/j.jfca.2025.107227 Received 16 April 2024; Received in revised form 27 December 2024; Accepted 10 January 2025 0889-1575/© 20XX Note: Low-resolution images were used to create this PDF. The original images will be used in the final composition. M. Hosseini et al. Journal of Food Composition and Analysis xxx (xxxx) 107227 F OO PR Fig. 1. Optimization of the sorbent weight. Extraction conditions: DSPE approach: aqueous solution volume, 5 mL deionized water spiked with 50 ng mL−1 of each analyte; agitation mode in adsorption step (time), vortex (2 min); desorption solvent (volume), acetone (100 µL); agitation mode in desorption step (time), vortex D (3 min); and centrifugation time (speed), 5 min (6000 rpm). The error bars show the minimum and maximum of three repeated determinations. TE EC RR CO Fig. 2. Selection of desorption solvent type. Extraction conditions: are the same as those used in Fig. 1, except 15 mg of NiCoMn-MOF was used as the optimum sor- bent amount. default/files/2015–09/documents/method_606_1984.pdf), as well as are the major disadvantages of these methods. Thus, significant efforts in aqueous and solid matrices such as groundwater, leachate, soil, are being made to develop new techniques for quantifying PAEs in dif- sludge and sediment (https://www.epa.gov/sites/default/files/ ferent samples in order to address these limitations (Guo et al. 2005; 2015–12/documents/8061a.pdf). These methods involve liquid-liquid Russo et al. 2012; Babu-Rajendran et al. 2018; Wu et al. 2020). extraction (LLE) and solid-phase extraction (SPE) steps, using relatively Likewise liquid-phase microextraction based techniques (Santana- high amounts of organic solvents (methylene chloride, acetone, and n- Mayor et al. 2020; Zakharkiv et al. 2020), various sorbent-based extrac- hexane) and Florisil cartridges. The high-cost of cartridges, high con- tion methods such as SPE (Ma et al. 2021), solid-phase microextraction sumption of toxic solvents, poor selectivity, and time-consuming nature (SPME) (Aghaziarati et al., 2021), magnetic solid phase extraction (Wu 2 M. Hosseini et al. Journal of Food Composition and Analysis xxx (xxxx) 107227 F OO PR D Fig. 3. (a) Optimization of agitation mode in the adsorption step. Extraction conditions: are the same as those performed in Fig. 2, except that 100 µL TE dichloromethane was selected for the further steps. (b) Optimization of adsorption time. Extraction conditions: are the same as those performed in Fig. 3a, except that vortexing was used in the adsorption step. (c) Optimization of agitation mode in the desorption step. Extraction conditions: are the same as those performed in Fig. 3b, except that 3 min was opted as the adsorption time. (d) Optimization of desorption time. Extraction conditions: are the same as those performed in Fig. 3c, except that vortexing was chosen as the desorption mode. et al. 2021), and pipette tip SPE (Chu et al. 2023) approaches have been hance the performance of MOF and reinforce their structure, one poten- EC applied to qualify PAEs in beverages. One significant technique in this tial approach is the introduction of metal nodes through doping in MOF regard is dispersive solid phase extraction (DSPE), which stands out due or their derived structures through the synergistic effects of mixed to its simplicity, short extraction time, low usage of organic solvents as metal ions (Bai et al. 2021). Nevertheless, the design of ternary metal- well as its capability to achieve high enrichment factors and extraction lic-organic frameworks with hollow structures of precise chemical com- recoveries (Socas-Rodríguez et al. 2015; Chisvert et al. 2019; Kho- positions and shapes remains an ongoing challenge. dadadeian et al., 2024; Farajzadeh et al. 2022; Tuzen et al. 2021). Com- In this study, a DSPE procedure was developed for the simultaneous RR pared to conventional SPE, in DSPE as a clean-up/extraction approach, extraction of PAEs from various plastic packaged fruit juices before tiny amount of sorbent is directly in contact with the sample solution their quantification by GC- flame ionization detector (GC-FID) analysis. containing analytes and there is no need for the conditioning step A ternary MOF (NiCoMn- MOFs) was prepared using a hydrothermal (Keshavarzi et al. 2022). Sonication and vortexing are commonly used method and used as the adsorbent in the extraction step. The presence techniques to achieve efficient dispersion of the sorbent and enhance of multiple elements in the structure provides a large specific area, high the contact between the analyte and sorbent (Farajzadeh and Dabbagh, porosity, and good adsorption capacity favoring the extraction of ana- 2020). lytes with high efficiency. The synthesis of the desired MOF was con- CO However, it is worth mentioning that, in order to achieve high ex- ducted in the presence of a surfactant that induced the end-capping re- traction recoveries, the DSPE procedure requires porous structure sor- action and promoted anisotropic crystal growth. This synthesis method bents with high contact area such as molecularly imprinted polymers, was both time and cost-effective. The aromatic nature of the linker fa- metal-organic frameworks (MOFs), covalent organic frameworks and cilitated the π-π interactions for the effective extraction of analytes. Af- their composites (Fathi et al. 2023; Abbasalizadeh et al. 2022; Li et al. ter extracting of the target compounds, the elution solvent used for des- 2023; Kitagawa, 2014). MOFs, are synthesized by combining metal ions orption of the analytes from the adsorbent surface was vaporized to fur- with organic ligands (Zhu and Xu, 2014). These materials possess nu- ther enrich of the analytes, obtaining low detection limits. merous application due to their unique properties, such as adjustable pore size by changing the ligand, tunable surface area, diverse struc- 2. Experimental tural topologies, and high porosity (Redfern and Farha, 2019). The abil- ity to design and finely tune their pore structures makes MOFs highly 2.1. Materials and solutions promising for various applications including water purification, gas ad- sorption and storage, sensors, catalysts, and sample preparation The standard of studied PAEs (DEP, DBP, DIBP, and DEHP) were (Freund et al. 2021). However, their chemical and thermal stabilities supplied from Sigma-Aldrich (St. Louis, Missouri, USA). The used chem- remain a limitation in the field of separation (Ding et al. 2019). To en- ical compounds for synthesis of the ternary MOF consisting of nickel ac- 3 M. Hosseini et al. Journal of Food Composition and Analysis xxx (xxxx) 107227 F OO PR D Fig. 4. Influence of salt addition on ERs of the analytes. Extraction conditions: are the same as those used in Fig. 3d, except that 2 min was opted as the sufficient des- orption time. TE Table 1 Figures of merit of the suggested approach for the selected PAEs. a b c d e f Analyte LOD ) LOQ ) LR ) RSD % ) EF± SD ) ER ± SD ) –1 –1 –1 2 ng mL 25 ng mL 100 ng mL EC Intra–day Inter–day Intra–day Inter–day Intra–day Inter–day DEP 0.29 0.96 0.96–250 5.6 5.9 4.8 5.2 4.3 4.8 325 ± 20 65 ± 4 DBP 0.22 0.73 0.73–250 5.0 5.6 3.8 4.4 3.1 3.7 345 ± 15 69 ± 3 DIBP 0.16 0.53 0.53–250 4.9 5.3 3.9 5.4 3.2 4.2 355 ± 20 71 ± 4 DEHP 0.11 0.36 0.36–250 6.1 6.8 4.5 5.2 3.6 4.5 375 ± 20 75 ± 4 a) Limit of detection (S/N = 3) (ng mL–1). RR b) Limit of quantification (S/N = 10) (ng mL–1). c) Linear range. d) Relative standard deviation for intra– (n = 6) and inter–day (n = 4) precisions. e) Enrichment factor ± standard deviation (n = 3). f) Extraction recovery ± standard deviation (n = 3). etate tetrahydrate (NiC4H6O4·4H2O), manganese acetate tetrahydrate port using a Zebron capillary column (Phenomenex) with dimensions of CO (MnC4H6O4·4H2O), cobalt acetate tetrahydrate (CoC4H6O4·4H2O), ben- 30 m × 0.25 mm × 0.25 mm. The column oven temperature was ini- zene tricarboxylic acid (BTC), sodium dodecyl sulfate (SDS), and N, N- tially set at 60 °C for 1 min and then increased at a rate of 18 °C per min Dimethylformamide (DMF) were bought from Merck (Darmstadt, Ger- until reaching 300 °C. It was maintained at 300 °C for 5 min. Pure he- many). Acetone, chloroform, dichloromethane, and methanol were all lium gas (99.999 %, Gulf Cry, Dubai, UAE) was employed as both the from Duksan (Gyeonggi-do, South Korea). Also, deionized water was carrier gas (linear velocity of 30 cm s−1) and the makeup gas (flow rate procured from Ghazi Company (Tabriz, Iran). The stock solution of of 30 mL min−1). The FID and injection port were set at a constant tem- PAEs (at a concentration of 500 mg L−1 for each analyte) was prepared perature of 300 °C and the split ratio at the injection port was 1:10. The by dissolving suitable amount of each analyte in methanol. The diluted optimization and validation process were performed using a Hettich solution of the stock solution was then used as a working solution dur- centrifuge (ROTOFIX 32 A, Kirchlengern, Germany), and an L46 vortex ing the optimization step. (Labinco, Breda, Netherlands). Scanning electron microscopy (SEM) with a Mira 3 microscope and Energy dispersive X-ray (EDX) were em- 2.2. Apparatuses ployed to examine the morphology and elemental analysis of the syn- thesized product. The Brunauer- Emmett- Teller (BET) surface areas The separation of the studied analytes was achieved using an Agi- were calculated from N2 sorption isotherms at 77 K using a Micromerit- lent gas chromatograph coupled with FID and a splitless/split injection ics BET TriStar II 3020 surface area and pore size analyzer. 4 M. Hosseini et al. Journal of Food Composition and Analysis xxx (xxxx) 107227 Table 2 2.5. DSPE procedure Results of assays to check the investigated fruit juices matrix effect. Data are mean relative recovery ± standard deviation obtained from three repeated The DSPE approach was as follows: 15 mg NiCoMn-MOF s was in- determinations. troduced into 5 mL of deionized water/ diluted fruit juice spiked with Analyte Sample #1 Sample #2 Sample #3 Sample #4 Sample #5 analytes at a concentration of 50 ng mL−1 (each analyte) containing 1 –1 % w/v, NaCl. The obtained mixture was dispersed for 3 min with the Samples were spiked at a concentration of 5 ng mL of each analyte. aid of vortex. In this step the analytes adsorb onto the sorbent particles DEP 82 ± 4 106 ± 6 89 ± 4 105 ± 1 95 ± 3 via interactions such as surface adsorption, occlusion, van der waals, DBP 99 ± 2 101 ± 5 105 ± 4 103 ± 3 99 ± 2 and π- π interactions. Then, the sorbent containing the analytes isolated DIBP 91 ± 4 96 ± 6 94 ± 5 93 ± 3 91 ± 4 from the solution by centrifuging for 5 min at 6000 rpm and the super- F DEHP 96 ± 5 85 ± 2 85 ± 7 97 ± 6 98 ± 5 natant was discarded. In the following, 100 µL dichloromethane was –1 Samples were spiked at a concentration of 50 ng mL of each analyte. added to the sorbent as an elution solvent and vortexed for 2 min to ef- DEP 99 ± 2 101 ± 4 102 ± 3 89 ± 2 88 ± 4 fectively desorb the analytes and the organic phase was separated using OO DBP 98 ± 5 94 ± 4 106 ± 6 104 ± 5 102 ± 1 DIBP 95 ± 4 94 ± 4 99 ± 2 100 ± 5 104 ± 4 centrifuging (5 min at 6000 rpm). The elution phase was collected and DEHP 94 ± 6 101 ± 7 105 ± 6 104 ± 7 103 ± 5 evaporated under nitrogen atmosphere at room temperature and the residual was dissolved in 10 µL dichloromethane. Then, 1 μL of the ob- Table 3 tained phase was taken and injected into GC-FID for quantification the Concentration range of PAEs in the investigated fruit juice samples. PAEs. −1 Analyte Concentration range of the target compounds (µg L ) 2.6. Enrichment factor and extraction recovery calculation PR Orange juice Pomegranate juice Apricot juice a The enrichment factor (EF) is illustrating the preconcentration value DEP ND −1.23 ± 0.14 ND−1.29 ± 0.19 ND applied to the studied analytes. As shown in Eq.1, EF is computed by DBP 1.21 ± 0.11–2.98 ± ND−2.23 ± 0.22 1.06 ± 0.18–3.06 ± the ratio of the concentration of analyte in the sedimented phase (Csed) 0.27 0.26 DIBP 1.65 ± 0.16–3.56 ± 1.11 ± 0.12–2.09 ± 1.32 ± 0.10–5.21 ± to its concentration in the initial phase (C0). 0.24 0.17 0.17 DEHP 2.11 ± 0.09–7.56 ± 1.95 ± 0.11–6.98 ± 2.09 ± 0.12–9.84 ± 0.36 0.29 0.33 D a Not detect The extraction recovery (ER) represents the percentage of the ana- lyte transferred from the initial phase to the final phase. Based on to Eq. 2.3. Synthesis of NiCoMn-MOF 2, the ER is determined by comparing the number of analyte transferred TE in the final phase (nsed) to the number of analyte in the initial phase The synthesis of NiCoMn-MOF was carried out following the previ- (n0). ously reported method in a hydrothermal route (Xu et al. 2020; Wang et al. 2023). In brief, 0.135 mmol CoC4H6O4·4H2O, 0.045 mmol MnC4H6O4·4H2O, and 0.360 mmol NiC4H6O4·4H2O were dissolved in 15 mL deionized water placed into a 25-mL glass beaker to prepare so- EC lution A. Simultaneously, solution B was provided by dissolving In this equation, Vsed refers to the volume of the final organic phase, 0.395 mmol BTC in 30 mL of mixture of anhydrous ethanol and DMF and V0 represents the volume of the initial aqueous phase in which the (1:1, v/v). Then, under the condition, the solution A was added to solu- analytes were spiked. tion B under stirring, and then 25 mg SDS was introduced to the ob- tained solution. In the following, the mixture was stirred for 2 h to 3. Results and discussion achieve the homogenous solution. Eventually, the obtained mixture was transferred to autoclave and heated for 24 h at 160 ̊C. The resulting 3.1. Characterization of NiCoMn-MOF RR sediment was then eluted with DMF and absolute ethanol (3 × 10 mL) and dried at 80 ̊C for 12 h to obtain a deep purple sorbent. The synthesis In this study, the constituent elements of NiCoMn-MOF were identi- mechanism of the MOF is schematically shown in Fig. S1. fied using EDX analysis, which helps detect impurities or unwanted ele- ments and provides information about the percentage of present cations 2.4. Real sample preparation and ligand elements. According to the results obtained in Fig. S1a, the elements that make up the MOF, such as carbon, oxygen, nitrogen, CO Thirteen commercially available fruit juices (orange, pomegranate, cobalt, nickel, and manganese are present in the MOF structure with and apricot juices) were randomly purchased from local supermarkets weight percentages of 1.75 % manganese, 9.67 % cobalt, 20.62 % in Tabriz (East Azerbaijan Province, Iran). All samples were packaged nickel, 33.24 % carbon, 32.04 % oxygen, and 2.68 % nitrogen that veri- in polyethylene terephthalate plastic bottles with a production date no fying its successful synthesis. Additionally, SEM analysis is a valuable longer than two weeks prior. Furthermore, fresh orange, pomegranate, technique for studying the morphology, dimensions, and shape distrib- and apricot fruits were prepared, their juices obtained using a pulper utions of the sorbent constituents. Figure S1b displays the SEM image of and then filled into polyethylene terephthalate plastic bottles. These the synthesized sorbent, showing the sorbent possesses a uniform one- samples were used to investigate the effect of storage time and tempera- dimensional micro scale rod shape structure. The XRD pattern (Fig. ture on the migration of analytes. Each of the collected samples under- S1c), shows the peaks of the MOFs synthesized at 9.24° and 13.1°, re- went centrifugation at 4000 rpm for 5 min to remove any suspended alted to diffractions from 101 and 002 lattice planes, respectively. The compounds. The resulting liquid phases were subsequently diluted with use of surfactant shifted the diffraction angles to slightly higher value deionized water at a ratio of 1:3 (v/v) before being applied in the ex- compared to NiCoMn-MOF without the surfactant. To confirm the traction procedure. porous structure of the MOF, it was analyzed by BET and the obtained curve is shown in Fig. S1d. The pore volume of 0.3317 cm³ g−1 and a BET surface area of 374.52 m² g−1 were determined for the MOF. 5 M. Hosseini et al. Journal of Food Composition and Analysis xxx (xxxx) 107227 Table 4 Study of the concentration of the target compounds in different storage conditions. −1 Mean concentration of the target compounds (µg L ) ± standard deviation (n = 3) Stored at room temperature (25 °C) Stored in a refrigerator (4 °C) Stored at 40 °C Storage.days→ 1 2 5 10 30 45 1 2 5 10 30 45 1 2 5 10 30 45 Analyte Orange sample a b DEP ND ND ND NQ 1.35 1.65 ND ND ND ND NQ NQ ND ND ND 1.05 1.95 2.85 ± ± ± ± ± 0.02 0.04 0.01 0.03 0.07 F DBP 1.21 1.91 2.23 3.60 5.93 7.02 NQ 1.56 2.04 2.91 5.52 6.90 1.81 2.36 2.73 3.95 6.84 8.89 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 015 ± 0.04 0.03 0.09 0.10 0.10 0.27 0.03 0.05 0.10 0.19 0.15 0.03 0.06 0.11 0.15 0.20 OO DIBP 1.71 2.31 3.15 4.90 6.55 7.53 1.24 2.11 2.52 4.01 6.11 6.25 2.11 2.73 3.62 5.26 6.92 7.97 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 0.05 0.09 0.14 0.19 0.25 0.27 0.05 0.11 0.10 0.18 0.13 0.27 0.10 0.09 0.12 0.18 0.18 0.20 DEHP 2.75 3.76 5.35 7.05 7.85 8.23 2.32 2.83 4.89 6.55 7.26 8.05 3.25 3.95 5.82 7.49 8.62 9.56 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 0.12 0.17 0.20 0.25 0.23 0.30 0.10 0.09 0.12 0.10 0.15 0.25 0.15 0.15 0.22 0.25 0.27 0.30 Pomegranate sample DEP ND ND ND NQ 1.09 1.26 ND ND ND ND NQ NQ ND ND ND ND 1.89 2.06 ± ± ± ± PR 0.02 0.02 0.03 0.05 DBP 1.04 1.92 2.18 3.26 5.90 6.82 0.95 1.59 2.00 3.02 5.34 6.35 1.46 2.54 2.77 3.75 5.98 7.67 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 0.03 0.05 0.05 0.11 0.17 0.16 0.03 0.05 0.05 0.08 0.15 0.13 0.05 0.05 0.12 0.15 0.23 0.25 DIBP 2.05 2.34 2.92 3.81 4.97 7.02 1.95 2.21 2.75 3.52 4.20 6.78 2.56 2.74 3.35 3.96 5.35 7.98 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 0.11 0.10 0.15 0.19 0.22 0.18 0.05 0.10 0.10 0.13 0.11 0.25 0.10 0.13 0.20 0.20 0.28 0.32 DEHP 2.25 3.06 3.75 4.23 5.85 6.23 2.03 2.81 3.38 3.96 5.55 5.93 2.76 3.54 4.15 4.66 6.25 6.78 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± D 0.11 0.10 0.14 0.15 0.20 0.23 0.06 0.10 0.12 0.09 0.11 0.17 0.18 0.20 0.25 0.20 0.25 0.26 Apricot sample DEP ND ND ND ND NQ NQ ND ND ND ND ND ND ND ND ND ND NQ 1.21 ± TE 0.03 DBP 1.27 1.70 1.98 3.92 4.87 5.21 1.05 1.29 1.67 3.57 4.61 5.75 1.68 1.97 2.39 4.58 5.45 5.94 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 0.03 0.03 0.07 0.15 0.15 0.13 0.03 0.04 0.05 0.12 0.10 0.13 0.04 0.03 0.10 0.18 0.20 0.18 DIBP 1.32 2.21 3.03 3.23 4.96 5.79 1.29 2.08 2.86 3.01 4.69 5.06 1.65 2.68 3.45 3.65 5.34 6.28 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 0.05 0.08 0.10 0.12 0.16 0.20 0.06 0.09 0.12 0.09 0.12 0.15 0.08 0.11 0.15 0.21 0.25 0.28 EC DEHP 2.42 3.55 4.85 6.08 7.11 8.06 1.91 3.21 4.35 5.76 6.89 7.67 2.69 3.89 4.97 6.68 7.51 8.86 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 0.11 0.19 0.21 0.18 0.25 0.24 0.07 0.15 0.11 0.15 0.18 0.27 0.15 0.23 0.25 0.18 0.30 0.32 a Not detected b Not quantified (LOD < the obtained concentration < LOQ) 3.2. Optimization of sorbent weight in compared to other solvents tested. It is important to note that RR dichloromethane has the lowest boiling point, which make its evapora- In DSPE procedures, the weight of the sorbent is an important para- tion process easier and requires less temperature for complete evapora- meter in determining its adsorptive efficiency. The effect of NiCoMn- tion, making it a cost-effective and suitable choice. MOF weight on the extraction of PAEs from an aqueous sample was in- Next, the impact of eluent volume was examined within the range of vestigated in the range of 5–25 mg. Fig. 1 demonstrates that increasing 75–200 µL. Results indicated that using 100 µL of dichloromethane the weight of NiCoMn-MOF up to 15 mg improves the ERs due to pro- produces the highest ERs. Inadequate desorption of analytes due to the viding a higher surface area for the adsorption of the studied analytes. lower volumes of dichloromethane results in reduced ERs. Similarly, CO However, the ER values for all analytes decreased with an increase sor- higher volumes of dichloromethane also lead to decreased ERs, as there bent amount from 15 to 25 mg. The decrease in ER values in higher is a lack of subsequent dissolution of residues. Therefore, 100 µL of amounts of sorbent (˃15 mg) may be related to the accumulation of sor- dichloromethane was selected for the frequent experiments. bent particles or incomplete elution of the studied analytes from the sorbent surface (Pezhhanfar et al. 2023). Therefore, 15 mg of NiCoMn- 3.4. Selection of sorption agitation mode and time MOF was selected for the following extraction process. The extraction of PAEs from the aqueous samples onto the sorbent 3.3. Study of elution solvent type and its volume was accelerated with the aid of sonication and vortexing to reduce the extraction time and enhance the surface area between the sorbent and To improve the desorption process, various low boiling point or- the studied analytes. Therefore, the effect of agitation mode on the effi- ganic solvents with high potential for efficient elution, including ace- ciency of the proposed method was evaluated by sonicating and vortex- tone, methanol, chloroform, dichloromethane, and n-hexane (150 µL ing the mixture of the sample solution and sorbent for 2 min. The out- each) were individually added to the NiCoMn-MOF sorbent to maxi- comes in Fig. 3a illustrated that vortexing resulted in the maximum ERs mize the transfer of adsorbed analytes from the sorbent surface to the and was opted as the sorption agitation mode. Consequently, to investi- organic phase. Fig. 2 shows that dichloromethane provides higher ERs gate the efficacy of the sorption time, the solution containing the target 6 M. Hosseini et al. Journal of Food Composition and Analysis xxx (xxxx) 107227 Table 5 Comparison of the developed method with the previously reported ones utilized in the quantification of selected PAEs. b c d e Sample Analyte RSD LOD ) LOQ ) LR ) ER% ) Extraction Sample Method Ref. a (%) ) time amount (min) (mL) f Bottled drinking water DEHP ≤ 6.4 1.52 5.02 5.02–500 65 ⁓ 10 5 DµSPE-TAE-GC-FID ) (Pezhhanfar et al. 2023) g Environment DEP 4.3 0.006 0.18 1–200 - ⁓ 20 50 MSPE/GC-MS ) (Zhang et al. 2020) water DBP 5.1 0.005 0.015 1–200 - DEHP 5.7 0.015 0.045 1–200 - F h Water and human plasma DEP 4.6 0.08 0.3 0.5–200 - ⁓ 23 5 DMSPE-GC-MS ) (Dargahi et al. 2018) DBP 7.2 0.1 0.3 0.5–200 - Aqueous samples DIBP 4 0.5 1.5 1.5–1000 57 ⁓9 5 MDSPE-DLLME-GC- (Aghdam et al. 2022) i FID ) OO j Water samples DEP 4.9 1.52 5.06 5.0–250 - ⁓5 5 SPME-GC-FID ) (Wu et al. 2020) DBP 4.3 0.4 1.33 1.0–500 - Water and juice DEP ≤ 4.1 0.027 0.093 0.1–500 87 ⁓ 20 10 HF-SPME-DES-HPLC- (Jafari et al. 2023) k DBP ≤ 4.6 0.058 0.184 0.2–500 91 UV ) l Bottled water, cola, orange DEP < 5.8 0.3 1.0 1–200 - ⁓ 11 8 SVA-LLME-GC-MS ) (Mohebbi et. al. juice DBP < 6.2 0.15 0.5 0.5–200 - 2018) DEHP < 6.5 0.15 0.5 0.5–200 - m Water and beverage samples DEP < 9.13 1.0 2.5 4–800 62 ⁓ 10 10 DES-DLLME-GC-FID ) (Niu et al. 2023) PR DBP < 6.8 0.5 1.0 1–400 93 n Fruit juices DEP ≤ 5.6 0.29 0.96 1–250 65 ⁓ 10 5 DSPE- GC-FID ) Present work DBP ≤5 0.22 0.73 1–250 69 DIBP ≤ 4.9 0.16 0.53 1–250 71 DEHP ≤ 6.1 0.11 0.36 1–250 75 a) Relative standard deviation b) Limit of detection (µg L–1) c) Limit of quantification (µg L –1) d) Linear range (µg L–1) D e) Extraction recovery f) Dispersive micro solid phase extraction-temperature assisted evaporation-gas chromatography-flame ionization detection g) Magnetic solid-phase extraction - gas chromatography-mass spectrometry h) Dispersive magnetic solid phase extraction-gas chromatography-mass spectrometry TE i) Magnetic dispersive solid phase extraction–dispersive liquid–liquid microextraction-gas chromatography-flame ionization detector j) Solid phase microextraction- gas chromatography-flame ionization detector k) Hollow fiber-solid phase microextraction-deep eutectic solvent-high performance liquid chromatography-ultraviolet detector l) Solvent-vapor assisted-liquid-liquid microextraction-gas chromatography-mass spectrometry m) Deep eutectic solvent based-dispersive liquid-liquid microextraction-gas chromatography-flame ionization detector n) Dispersive solid phase extraction- gas chromatography-flame ionization detector EC analytes and synthesized sorbent was vortexed for 0.5, 1.0, 2.0, 3.0, 3.6. Ionic strength effect 4.0, and 5.0 min. Between 0.5 and 3 min, the recoveries of the PAEs in- creased with the sorption time and then decreased gradually (Fig. 3b). The efficacy of salt addition on the ERs was studied by adding vari- Therefore, a sorption time of 3 min was chosen for the next experi- ous NaCl concentrations (0–5 % w/v) to the sample solution and the ments. corresponding outcomes are shown in Fig. 4. The ER values of the ana- RR lytes were enhanced by increasing NaCl concentration up to 1.0 % w/v, 3.5. Optimization of desorption agitation mode and time while any further increase resulted in a negative effect. This outcome can be related to the salting out effect, where the addition of salt to the Utilizing vortex or ultrasonic irradiation can enhance the mass sample solution decreases the solubility of the analytes, thereby in- transfer of PAEs between the elution solvent and sorbent, reducing the creasing the extraction recovery (Farajzadeh et al. 2018). However, at equilibrium time. To evaluate the effect of different agitation modes, higher amounts (>1.0 % w/v), the solution viscosity may increase, dis- specifically vortexing and sonication, all tests were performed for rupting the mass transfer rate. Therefore, subsequent investigations CO 3 min. The results (Fig. 3c) show that vortexing has a more favorable ef- were done using 1.0 % w/v NaCl. fect on the recovery of the proposed method compared to sonication. Thus, vortexing was chosen for use utilize in the subsequent steps. 3.7. Method validation Desorption time is a crucial in the extraction process as it directly af- fects the amount of analyte desorbed from the sorbent surface. To assess The analytical performance of the desired DSPE procedure such as the impact of desorption time on the ERs of the analytes, the desorption limits of detection (LODs), linear ranges (LRs), limits of quantification process was carried out within the range of 1–4 min, with the results (LOQs), relative standard deviations (RSDs), enrichment factors (EFs), displayed in Fig. 3d. Recoveries increased from 1 to 2 min, but longer and extraction recoveries (ERs%), were summarized in Table 1. Wide desorption times resulted in a decreased recovery. Therefore, 2 min, linearity for all PAEs were obtained in the range of 0.96–250 ng mL−1 which provided the highest recovery in the shortest time, was opted for with low LODs (S/N = 3) ranging from 0.11 to 0.29 ng mL−1 and LOQs further steps. (S/N = 10) in the range of 0.36–0.96 ng mL−1. To assess the precision of the proposed method, the inter-day RSDs (n = 6) of the analytes were calculated at three concentration levels (2, 25, and 100 ng mL−1), resulting in RSD values in the range of 3.1–6.1 %. Moreover, the EFs were 325 for DEP, 345 for DBP, 355 for DIB and 375 for DEHP. High ex- 7 M. Hosseini et al. Journal of Food Composition and Analysis xxx (xxxx) 107227 traction recoveries (65–75 %) indicated that the introduced method has cost-effective, and environmentally friendly. The key findings of the significant potential for the determination of PAEs in trace amounts. study include achieving high ERs (65–75 %), a great enrichment factor (325−375), low LOQs and LODs (0.36–0.96 and 0.11–0.29 ng mL−1, re- 3.8. Analysis of real samples and matrix effect and accuracy evaluation spectively), wide LRs (1–250 ng mL−1), excellent repeatability (RSDs ≤ 6.1 %), desirable RR (82–106 %). Thus, the proposed method serves as To investigate the accuracy of the method for analyzing fruit juices a favorable and efficient alternative for the analysis of PAEs in complex using added-found method, five random fruit juices samples, along with sample matrices such as fruit juice samples. deionized water after spiked with PAEs at two concentration levels (5 and 50 ng mL−1) were extracted and analyzed using the developed CRediT authorship contribution statement method. The mean relative recoveries (RR%), as summarized in Table F 2, ranged from 82 % to 106 % indicating the method have acceptable Maryam Hosseini: Writing – original draft, Methodology, Formal accuracy of the method. To investigate the matrix effect, was conducted analysis. Akram Pezeshki: Investigation, Formal analysis. Babak the introduced method on the studied fruit juices and deionized water Ghanbarzadeh: Writing – original draft, Supervision, Methodology. OO spiked at various concentrations. We plotted the obtained peak areas Mohammad Reza Afshar Mogaddam: Writing – original draft, versus concentration. The equations of the calibration curves in the Methodology, Investigation, Conceptualization. samples and deionized water can be found in Table S2. The slopes of the calibration curves obtained for the spiked samples were compared with Uncited reference those obtained for deionized water spiked at the same concentrations. The slopes of calibration curves obtained in the samples and deionized Aghaziarati et al., 2020; Khodadadeian et al., 2025; Longbottom water were statistically analyzed for accuracy using a t-test. The results and Lichtenberg 2015; Longbottom and Lichtenberg 2015; Mohebbi et PR showed that there was no significant difference between both cases. al., 2017; Pezhhanfar et al., 2023; Wu et al., 2020. This verifies that the proposed procedure was not affected by matrix ef- fects and is considered an efficient method for quantifying PAEs in Declaration of Competing Interest packed fruit juice samples. The proposed method was employed to de- termine residual PAEs in thirteen fruit juices of different brands (or- The authors declare that they have no known competing financial ange, pomegranate, and apricot juices packed in polyethylene tereph- interests or personal relationships that could have appeared to influ- thalate based plastic bottles). The pretreatment of all samples was car- ence the work reported in this paper. ried out following the procedure outlined in Section 2.5 under the opti- D mal conditions. Experimental results demonstrated that all of the fruit Data availability juice samples investigated were contaminated with the selected PAEs (the concentration range of the mentioned PAEs are summarized in The authors do not have permission to share data. Table 3). In the next step, the effect of storage temperature and time on TE the migration of PAEs from packaging into juice was investigated. This Appendix A. Supporting information was done by using the same method on juices prepared that were pre- pared in the laboratory and filled into plastic bottles. It is obvious from Supplementary data associated with this article can be found in the Table 4, by increasing the storage time and temperature the concentra- online version at doi:10.1016/j.jfca.2025.107227. tions of the compounds of interest were enhanced in the samples. EC References 3.9. Comparing the efficiency of the proposed method for extracting PAEs with other methods Abbasalizadeh, A., Sorouraddin, S.M., Farajzadeh, M.A., Nemati, M., Afshar Mogaddam, M.R., 2022. Dispersive solid phase extraction of several pesticides from fruit juices using a hydrophobic metal organic framework prior to HPLC-MS/MS determination. The efficiency of this method extracting PAEs from aqueous samples J. 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