Next Article in Journal
Effects of Veneering Ceramic and Methods on Failure Load of Veneered Zirconia
Next Article in Special Issue
Oxidative Stability of Long-Chain Fatty Acids with Different Unsaturation Degrees into Layered Double Hydroxides
Previous Article in Journal
Assessment of Galvanostatic Anodic Polarization to Accelerate the Corrosion of the Bioresorbable Magnesium Alloy WE43
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Applied Sciences
Volume 11
Issue 5
10.3390/app11052130
applsci-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Evaluation of the Occurrence of Phthalates in Plastic Materials Used in Food Packaging

by
Rosa Perestrelo
1,
Catarina L. Silva
1,
Manuel Algarra
2,* and
José S. Câmara
1,3,*
1
CQM-Centro de Química da Madeira, Campus da Penteada, Universidade da Madeira, 9020-105 Funchal, Portugal
2
Department of Inorganic Chemistry, Faculty of Science, Campus de Teatinos s/n, University of Málaga, 29071 Malaga, Spain
3
Departamento de Química, Faculdade de Ciências e Engenharia, Campus da Penteada, Universidade da Madeira, 9020-105 Funchal, Portugal
*
Authors to whom correspondence should be addressed.
Appl. Sci. 2021, 11(5), 2130; https://doi.org/10.3390/app11052130
Submission received: 10 February 2021 / Revised: 22 February 2021 / Accepted: 23 February 2021 / Published: 27 February 2021
(This article belongs to the Special Issue Novel Research on Safety Detection and Quality Control of Food)
Browse Figures
Versions Notes

Abstract

:

Featured Application

Application of an inexpensive, easy, eco-friendly, and rapid analytical approach in the routine monitoring of phthalates in food packaging to guarantee food safety.

Abstract

Phthalates are multifunctional synthetic chemicals found in a wide array of consumer and industrial products, mainly used to improve the mechanical properties of plastics, giving them flexibility and softness. In the European Union, phthalates are prohibited at levels greater than 0.1% by weight in most food packaging. In the current study, headspace solid-phase microextraction (HS-SPME) combined with gas chromatography-mass spectrometry (GC-MS) was optimized, through the multivariate optimization process, and validated to evaluate the occurrence of four common phthalates, di-iso-butyl phthalate (DIBP), butyl-benzyl phthalate (BBP), di-n-octyl phthalate (DOP), and 2,2,4,4-tetrabromodiphenyl (BDE), in different food packaging. The best extraction efficiency was achieved using the polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber at 80 °C for 30 min. The validated method showed good linearity, precision (RSD < 13%), and recoveries (90.2 to 111%). The limit of detection (LOD) and of quantification (LOQ) ranged from 0.03 to 0.08 µg/L and from 0.10 to 0.24 µg/L, respectively. On average, the phthalates concentration varied largely among the assayed food packaging. DIBP was the most predominant phthalate in terms of occurrence (71.4% of analyzed simples) and concentration (from 3.61 to 10.7 μg/L). BBP was quantified in only one sample and BDE was detected in trace amounts (<LOQ) in only two samples.

1. Introduction

Phthalates are a chemical group of industrial compounds with a common chemical structure, dialkyl or alkyl/aryl esters of 1,2-benzenedicarboxylic acid, commonly used for a variety of purposes, including industrial plastics, personal care products, and pharmaceuticals. Humans are exposed to phthalates through different ways such as dermal contact, inhalation, and ingestion. However, due to the abundance of plastic in our society, the exposure to phthalates is ubiquitous, constituting a major problem both at the environmental and health levels. In Europe, eight million tons of plastics was used for food and drink packaging, being one area in which plastics make a major contribution.
Although its inherent and useful features including flexibility, impermeability, strength, stability, lightness, and ease of sterilization make plastic packaging an ideal material for all types of industry in both flexible and rigid formats, they also promote food safety and shelf life and facilitate the transport and use of products. This will significantly reduce food waste, energy consumption, and the resources used. They are constituted by a complex mixture of thousands of chemical compounds made essentially of polyvinyl chloride (PVC), polyvinyl acetate (PVA), polyvinylidene chloride (PVDC), and different mixes to improve their plasticizer properties such as the incorporation of bisphenol A, used as a structural constituent, and phthalic acid-derived esters (phthalates) [1,2,3].
The occurrence of phthalates has been documented in different parts of the environment including surface water, sediments, soils, and the atmosphere, in addition to plastic materials used in food packaging [4,5], which are the most important human exposure pathway for phthalates, followed by inhalation of indoor air and ingestion of dust [6]. The European Union regulates the maximum content of these compounds in plastics that are in contact with all types of food (Commission Regulation (EU) No 10/2011 of 14 January 2011) and the management of packaging and packaging waste (Directive (EU) 2018/852 is the last amendment of Directive 94/62/EC).
The presence of phthalates in both the environment and food packages is an issue of special concern, not only from a health point of view, regarding their role as endocrine disrupting chemicals (EDCs) and their action on reducing testosterone production and changing thyroid function [7], but also due their ecological effects. Cardiovascular diseases, dysplasia, and reproductive system malformations are some of the other adverse effects associated with phthalates according to reports in several toxicity studies [8,9]. Moreover, prenatal exposure to some phthalates is linked to a male genital condition, which may increase the risk of testicular and prostate cancer, and lower fertility [10]. According to Hyland et al.’s studies [11], phthalates affect brain development and are associated with learning and behavior problems in children.
The determination of these compounds in different samples is challenging and demanded urgently for environmental and health risk assessment. The extraction procedure is the main key point of previous phthalates analyses. Extraction of phthalates in samples often employs microwave [12], Soxhlet [13], and ultrasonic techniques [14] prior to GC-MS analysis. The improvement of these procedures is followed by a pre-concentrating step, increasing phthalates detection. Usually, solid-phase extraction (SPE), solid-phase microextraction (SPME), and cloud point extraction (CPE) are the most applied to solve the matrix background [15,16], in combination with liquid chromatography (LC) and gas chromatography (GC) techniques hyphenated to conventional and mass spectrometry (MS) detectors [17], although other alternative procedures such as electronic sensors have also been used with this aim [18].
In this study, three phthalates (DIBP, BBP, DOP) and biphenyl ether (BDE) were simultaneously determined in different types of plastics used in the packaging of pasta, crackers, and frozen vegetables, by solid-phase microextraction in headspace mode (HS-SPME) followed by gas chromatography-mass spectrometry methodology. To achieve the maximum extraction efficiency, several SPME extraction parameters, namely, the fiber coating, extraction time, and temperature, were optimized using a multivariate design. Furthermore, the proposed method was validated according to IUPAC guidelines and applied to determine the levels of phthalates in several plastics used in food packaging.

2. Materials and Methods

2.1. Chemicals

All reagents were of analytical grade and used without any further purification. Di-iso-butyl phthalate (DIBP), butyl-benzyl phthalate (BBP), di-n-octyl phthalate (DOP), and 2,2,4,4-tetrabromodiphenyl ether (BDE) were purchased from Sigma-Aldrich Química S.A. (Spain). The digital stirring plate (Cimarec™) was supplied by Thermo Scientific (Waltham, MA, USA), while the SPME holder for manual sampling together with 50/30 µm divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS), 100 µm polydimethylsiloxane (PDMS), and 65 µm polydimethylsiloxane/divinylbenzene (PDMS/DVB) fibers, with 1 cm length, was purchased from Supelco (Bellefonte, PA, USA). Each fiber was daily conditioned according to the manufacturer’s recommendations in order to avoid carryover between sets of analyses. In addition, sodium chloride (NaCl) was supplied by Panreac (Barcelona, Spain) and He (GC carrier gas) of purity 5.0 was supplied from Air Liquide, Portugal. Ultrapure water (H2O) was obtained from a Milli-Q Plus system (18 MΩ/cm, Millipore Bedford, MA, USA).
The sources of contamination can be present in any step of the analytical procedure, such as sampling, sample preparation, and chromatographic analysis, among others [19]. Prior to use, all glassware material was washed with ethanol followed by H2O and heated at 300 °C for 2 h. Then, these materials were stored in desiccators containing aluminum oxide to avoid recontamination.

2.2. Sample Preparation

Different kinds of plastic packages were used (e.g., crackers, juice, milk, meat, legumes) in a total of 14 samples. Each plastic sample was cut into small pieces and ground with an T 25 digital ULTRA-TURRAX (IKA). An aliquot of 1.5 g of sample was added into beakers containing 6.0 mL of H2O. Then, the samples were left under agitation (400 rpm, 60 min and 25 ± 1 °C) to extract the phthalates. The supernatant was collected, coded, and stored at −20 °C, in the dark, until HS-SPME extraction.

2.3. Standard Solutions

Ethanolic phthalates standard solutions (500 µg/L) were prepared, labeled, and stored at −20 °C. For validation purposes, six standard solutions containing the target analytes at different concentrations were prepared daily by dilution of the working solutions (10 mg/L) in H2O.

2.4. HS-SPME Multivariate Optimization Process

Several factors influence the SPME efficiency, the most important being the fiber coating, extraction time, and temperature. A multivariate optimization process using a mixed standard solution containing phthalates at 60 μg/L was used to achieve the optimal extraction efficiency of HS-SPME. The study of the variables that were considered significant for the experiment was conducted using a 33 factorial design, namely, fiber coating (DVB/CAR/PDMS, PDMS, PDMS/DVB), extraction (15, 30, and 45 min), and extraction temperature (60, 70, and 80 °C). The optimal HS-SPME extraction conditions were used to analyze the samples. After sample preparation, an aliquot of 2 mL of sample and 0.2 g of NaCl was placed in an 8 mL vial. The vial was capped with a Teflon (PTFE) septum, and the fiber was introduced and exposed into the headspace for 30 min at 80 °C under constant agitation (400 rpm). Then, the fiber was removed from the vial and inserted into the GC injection port, where the extracted analytes were desorbed for 6 min at 250 °C. Each sample was analyzed in triplicate and blank chromatographic injections of the SPME device were performed before each set of analysis.

2.5. Gas Chromatography Quadrupole Mass Spectrometry (GC-qMS) Conditions

The SPME fiber with the target analytes was inserted into the injection port of an Agilent Technologies 6890N Network gas chromatograph system (Palo Alto, CA, USA) where the analytes were thermally desorbed. The gas chromatographer was equipped with a 60 m × 0.25 mm I.D. × 0.25 µm film thickness HP-5 (SGE, Dortmund, Germany) fused silica capillary column and interfaced with an Agilent 5975 quadrupole inert mass selective detector. The oven temperature program was set as follows: 120 °C (hold 3 min), increased until 190 °C at a rate of 10 °C/min (hold 4 min after reach 190 °C), further increased to 240 °C at a rate of 3 °C/min, maintained for 20 min. The total GC run time was 50.67 min. The column flow was constant at 1.0 mL/min using He of purity 5.0. The injection port was operated in the splitless mode and held at 250 °C. For the 5975 MS system, the operating temperatures of the transfer line, quadrupole, and ionization source were 270, 150, and 230 °C, respectively. Data acquisition was performed in the scan mode (30–300 m/z) with electron ionization at an energy of 70 eV and the ionization current of 10 µA. Phthalates identification was accomplished through manual interpretation through comparison of spectra and matching against the Agilent MS ChemStation Software, equipped with an NIST05 mass spectral library with a similarity threshold higher than 90%, and by the standards. The analysis was performed in triplicate, and the results were expressed as mean ± standard deviation. In addition, to evaluate the occurrence of phthalates in the GC system, blank runs of the chromatograph and direct injections of ethanol were carried out. None of phthalate targets were detected.

2.6. Method Validation

The analytical performance was evaluated in terms of selectivity, linearity, sensitivity, precision (inter-/intra-day), and recovery (as a measure of trueness). The method selectivity was evaluated by the absence of interfering peaks at the retention time (RT) of the phthalates, through the direct injection of an aliquot of the blank extract, and the solvent was injected directly. Six-point calibration curves of investigated phthalates were built in the concentration range reported in Table 1, in triplicate, to evaluate the method linearity. The evaluation was performed based on the average GC peak areas, percentage of relative standard deviation (% RSD), regression coefficients (R2), and linear ranges established for each target analyte analyzed. Sensitivity of the method was assessed through limit of detection (LOD, the lowest analyte concentration that produces a response detectable above the noise level of the system) and limit of quantification (LOQ, the lowest analyte concentration that can be accurately and precisely measured). The LOD and LOQ were determined using the residual standard deviation (Sy/x) of corresponding curves, LOD and LOQ being calculated by 3.3 Sy/x/b (b = slope) and 10 Sy/x /b, respectively, obtained in the calibration curve. Three different concentrations of target phthalates, added to the mixture of grounded packaging materials with water (1.5 g/6 mL of water), were used to evaluate the recovery of the proposed analytical method, within the linear range of the calibration curve. Seven replicates (n = 7) were carried out on the same day to determine intra-day precision (repeatability), whereas for the inter-day precision (reproducibility), five replicates (n = 5) were analyzed over six consecutive days (a total of n = 30). The recovery (accuracy) was determined as precision through the spiking of food packaging at three concentration levels. Both parameters were expressed as % RSD.

3. Results and Discussion

The phthalates chosen for the current study are the most relevant contaminants detected in environmental and food-related products [20].

3.1. Optimization of HS-SPME Procedure

To obtain the feasibility of the proposed analytical method, using the HS-SPME/GC-MS technique, a factorial design based on fiber coating, extraction time, and extraction temperature was optimized. The optimal conditions were chosen based on extraction efficiency measured by the GC-MS response (GC peak area) and reproducibility (the lowest % RSD). Figure 1 shows that the best extraction efficiency for DIBP, BBP, and DOP was achieved using the PDMS/DVB fiber at 80 °C, whereas for BDE, this was obtained using PDMS at 80 °C. Moreover, for DIBP, no significant difference was observed in terms of extraction efficiency between PDMS and the PDMS/DVB fiber at 80 °C. Therefore, the PDMS/DVB fiber was chosen for the HS-SPME extraction procedure since it provided a better extraction efficiency, with the exception of the BDE target, and better reproducibility than PDMS. Moreover, the PDMS/DVB fiber was reported to be the most suitable fiber for phthalates analysis in several environmental waters and food-related products [12,20].
It is well known that SPME is an equilibrium-based extraction procedure and therefore a time-dependent process. Nonetheless, the extraction time can be shortened with the increase in the extraction temperature, since high temperatures improve the diffusion kinetics of the target analytes [21]. In the current study, temperatures higher than 80 °C were not considered to avoid the reduction in fiber sensitivity for phthalates due to overloading the fiber with H2O molecules as well as to avoid possible degradations [20]. In addition, as microextraction is an endothermic process, high temperatures hamper the process. The extraction efficiency of HS-SPME increased for all phthalates with the increasing temperature. DOP is the only phthalate that does not show this remarkable increase, since a slight increase was observed between 70 and 80 °C; thus, 80 °C was selected as the extraction temperature. It has been reported that 80 °C is an optimal temperature to extract phthalates from environmental waters [22]. Regarding the extraction time, BBP, DOP, and BDE reached their equilibrium after 30 min, independently of the extraction temperature. For DIBP, the equilibrium was reached at 45 min. Thus, the optimal extraction conditions selected to determine phthalates in food packages were 30 min at 80 °C using a PDMS/DVB fiber coating.

3.2. Method Validation

The performance of the analytical method was assessed based on linearity, sensitivity, selectivity, precision (intra- and inter-days), and recovery (accuracy). The chromatogram profile of the optimized analytical method is depicted Figure 2, and phthalates (60 µg/L) were totally separated in less than 28 min.
Table 1 summarizes the phthalates involved in the current study, RT, linear range, R2, LOD, and LOQ, whereas Table 2 reports the recovery and precision data.
To build the calibration curves for the phthalates, mixed working solutions were prepared in the concentration range 0.5 to 60 µg/L and plotted using their GC peak area. For all targets under study, a good linearity (R2 ≥ 0.995) with residuals not exceeding ±10% was achieved over the whole range of concentrations tested. The LODs ranged from 0.03 (BBP) to 0.08 (BDE) µg/L, while LOQs ranged from 0.10 (BBP) to 0.24 (BDE) µg/L. Regarding DIBP, the LOD and LOQ obtained were lower than the default maximum residue limit (MRL, 300 µg/L) established by many government agencies worldwide, including the European Environment Agency, the USEPA, and the Chinese Ministry of Health [23].
The precision of the method was assessed by intra- (repeatability) and inter-day (reproducibility) precisions. The intra-day precision varied from 0.65 to 7.93%, whereas the inter-day precision ranged from 1.65 to 12.68%. The recovery was performed by spiking the phthalates in the food package solution at three levels of concentration (low, medium, and high), which ranged from 90.2 to 111% (Table 2). The literature has reported that a quantitative method should be demonstrated as being able to provide mean recoveries within the range of 70–120% and precision with % RSD values lower than 20%. Similar precisions and recoveries for phthalates were obtained in different matrices using HS-SPME/GC-MS [20,24,25].
In addition, the LODs and LOQs obtained in this work (Table 1) are slightly betterthan those obtained by other authors employing HS-SPME/GC-MS to determine phthalates in plastic containers [24], milk [25], and beers [20].
However, a higher LOD (from 0.12 to 0.50 µg/L) was achieved previously to quantify six phthalates in environmental waters using liquid–liquid extraction (LLE) followed by GC-MS [26]. A summary of the different analytical methods, used for phthalates determination in plastic packaging, is presented in Table 3 [20,21,24,27,28,29,30,31,32,33,34,35,36].

3.3. Quantification of Phthalates in Plastic-Based Food Packaging

The HS-SPME/GC-qMS method was applied to investigate the occurrence of phthalates in 14 types of plastic-based food packaging acquired in a local market. The RT and mass spectra comparison confirmed the occurrence of individual phthalates. Table 4 shows the phthalates concentration found in 14 plastic packages used in the food industry and determined by HS-SPME/GC-MS after method validation. DIBP was the most prominent phthalate found in all samples, with a frequency of occurrence (FO) of 100%, and its concentration ranged from 3.61 to 10.6 µg/L. DOP was the second most dominant phthalate detected in food packages (FO = 64%) at concentrations ranging from 1.03 to 2.83 µg/L. BDE was detected in two samples, but its concentration was lower than the LOQ. BBP was detected only in one sample, and its concentration did not exceed 1.42 µg/L. Therefore, the results indicate that the proposed green extraction technique was effective and feasible for the determination of phthalates in plastic-based food packaging.
Several studies (Table 5) revealed that phthalates and the ester derivative are passively ingested from the general environment, foods, drinks, breathing air, and dairy life products, causing various dysfunctions [3,20,30,31,34,37,38,39,40,41,42,43,44,45,46]. Exposures to DEHP, BBP, DBP, and DEP are associated with dermatitis, conjunctivitis, and allergic symptoms [47]. Other studies have found a relationship of asthma and worsening of pulmonary functions with these phthalates [48].

4. Conclusions

The detection of phthalates in plastics used in food packaging is of utmost importance in order to ensure the high quality and safety of packed food and food-derived products. In this context, a sensitive method based on the HS-SPME approach combined with GC-MS was developed using multivariate optimization. The optimal HS-SPME conditions were achieved using the PDMS/DVB fiber at 80 °C for 30 min. The performance of the HS-SPME/GC-MS methodology was evaluated in terms of linearity, LODs, LOQs, precision, and recovery. A good linearity (R2 ≥ 0.995), intra-day/inter-day precision (RSD < 13%), and recovery (90.2 to 111%) were obtained for the quantification of phthalates. The LODs ranged from 0.03 to 0.08 µg/L, while the LOQs ranged from 0.10 to 0.24 µg/L. The method was applied to 14 foodstuff plastic packages, and DIBP was the most prominent phthalate found in all samples (FO of 100%), with a concentration ranging from 3.61 to 10.6 µg/L. The results obtained show the applicability and feasibility of HS-SPME/GC-MS for the quantification of phthalates in foodstuff plastic packages. In addition, this inexpensive, easy, eco-friendly, and rapid analytical approach can be used in routine monitoring studies, as well as for food safety analysis.

Author Contributions

R.P.: investigation, methodology, data curation, writing—original draft. C.L.S.: investigation, methodology, visualization, data curation. M.A.: conceptualization, data curation, review and editing. J.S.C.: conceptualization, resources, project administration, funding acquisition, supervision, review and editing. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by FCT-Fundação para a Ciência e a Tecnologia through the CQM Base Fund (UIDB/00674/2020, and Programmatic Fund—UIDP/00674/2020) and through the Madeira 14-20 Program, project PROEQUIPRAM—Reforço do Investimento em Equipamentos e Infraestruturas Científicas na RAM (M1420-01-0145-FEDER-000008), and by ARDITI-Agência Regional para o Desenvolvimento da Investigação Tecnologia e Inovação, through the project M1420-01-0145-FEDER-000005—Centro de Química da Madeira—CQM+ (Madeira 14-20 Program). MA would like to thank to project RTI2018-099668-BC22 of Ministerio de Ciencia, Innovación y Universidades.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Bošnir, J.; Puntarić, D.; Galić, A.; Škes, I.; Dijanić, T.; Klarić, M.; Grgić, M.; Čurković, M.; Šmit, Z. Migration of Phthalates from Plastic Containers into Soft Drinks and Mineral Water. Food Technol. Biotechnol. 2007, 45, 91–95. [Google Scholar]
  2. Wang, Y.; Zhu, H.; Kannan, K. A review of biomonitoring of phthalate exposures. Toxics 2019, 7, 21. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  3. Fierens, T.; Vanermen, G.; Van Holderbeke, M.; De Henauw, S.; Sioen, I. Effect of cooking at home on the levels of eight phthalates in foods. Food Chem. Toxicol. 2012, 50, 4428–4435. [Google Scholar] [CrossRef] [PubMed]
  4. Cheng, Z.; Nie, X.P.; Wang, H.S.; Wong, M.H. Risk assessments of human exposure to bioaccessible phthalate esters through market fish consumption. Environ. Int. 2013, 57–58, 75–80. [Google Scholar] [CrossRef]
  5. Kickham, P.; Otton, S.V.; Moore, M.M.; Ikonomou, M.G.; Gobas, F.A.P.C. Relationship between biodegradation and sorption of phthalate esters and their metabolites in natural sediments. Environ. Toxicol. Chem. 2012, 31, 1730–1737. [Google Scholar] [CrossRef] [PubMed]
  6. GIbarra, V.G.; De Quirós, A.R.B.; Losada, P.P.; Sendón, R. Non-target analysis of intentionally and non intentionally added substances from plastic packaging materials and their migration into food simulants. Food Packag. Shelf Life 2019, 21, 100325. [Google Scholar] [CrossRef]
  7. Meeker, J.D.; Ferguson, K.K. Relationship between urinary phthalate and bisphenol a concentrations and serum thyroid measures in u.s. adults and adolescents from the national health and nutrition examination survey (NHANES) 2007–2008. Environ. Health Perspect. 2011, 119, 1396–1402. [Google Scholar] [CrossRef] [PubMed]
  8. Li, N.; Zhou, L.; Zhu, J.; Liu, T.; Ye, L. Role of the 17β-hydroxysteroid dehydrogenase signalling pathway in di-(2-ethylhexyl) phthalate-induced ovarian dysfunction: An in vivo study. Sci. Total Environ. 2020, 712, 134406. [Google Scholar] [CrossRef]
  9. Van’T Erve, T.J.; Rosen, E.M.; Barrett, E.S.; Nguyen, R.H.N.; Sathyanarayana, S.; Milne, G.L.; Calafat, A.M.; Swan, S.H.; Ferguson, K.K. Phthalates and Phthalate Alternatives Have Diverse Associations with Oxidative Stress and Inflammation in Pregnant Women. Environ. Sci. Technol. 2019, 53, 3258–3267. [Google Scholar] [CrossRef]
  10. Benjamin, S.; Masai, E.; Kamimura, N.; Takahashi, K.; Anderson, R.C.; Faisal, P.A. Phthalates impact human health: Epidemiological evidences and plausible mechanism of action. J. Hazard. Mater. 2017, 340, 360–383. [Google Scholar] [CrossRef]
  11. Hyland, C.; Mora, A.M.; Kogut, K.; Calafat, A.M.; Harley, K.; Deardorff, J.; Holland, N.; Eskenazi, B.; Sagiv, S.K. Prenatal Exposure to Phthalates and Neurodevelopment in the CHAMACOS Cohort. Environ. Health Perspect. 2019, 127, 107010. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  12. Celeiro, M.; Lamas, J.P.; Vila, M.; Garcia-Jares, C.; Homem, V.; Ratola, N.; Dagnac, T.; Llompart, M. Determination of multiclass personal care products in continental waters by solid-phase microextraction followed by gas chromatography-tandem mass spectrometry. J. Chromatogr. A 2019, 1607, 460398. [Google Scholar] [CrossRef]
  13. Tran-Lam, T.-T.; Dao, Y.; Nguyen, D.; Ma, H.; Pham, T.; Le, G. Optimization of Sample Preparation for Detection of 10 Phthalates in Non-Alcoholic Beverages in Northern Vietnam. Toxics 2018, 6, 69. [Google Scholar] [CrossRef] [Green Version]
  14. Fernández-González, V.; Moscoso-Pérez, C.; Muniategui-Lorenzo, S.; López-Mahía, P.; Prada-Rodríguez, D. Reliable, rapid and simple method for the analysis of phthalates in sediments by ultrasonic solvent extraction followed by head space-solid phase microextraction gas chromatography mass spectrometry determination. Talanta 2017, 162, 648–653. [Google Scholar] [CrossRef] [PubMed]
  15. Viñas, P.; Campillo, N.; Pastor-Belda, M.; Oller, A.; Hernández-Córdoba, M. Determination of phthalate esters in cleaning and personal care products by dispersive liquid-liquid microextraction and liquid chromatography-tandem mass spectrometry. J. Chromatogr. A 2015, 1376, 18–25. [Google Scholar] [CrossRef]
  16. Amanzadeh, H.; Yamini, Y.; Moradi, M.; Asl, Y.A. Determination of phthalate esters in drinking water and edible vegetable oil samples by headspace solid phase microextraction using graphene/polyvinylchloride nanocomposite coated fiber coupled to gas chromatography-flame ionization detector. J. Chromatogr. A 2016, 1465, 38–46. [Google Scholar] [CrossRef]
  17. Scognamiglio, V.; Antonaccia, A.; Patrolecco, L.; Lambreva, M.D.; Litescuc, S.C.; Ghugea, S.A.; Rea, G. Analytical tools monitoring endocrine disrupting chemicals. TrAC Trends Anal. Chem. 2016, 80, 555–567. [Google Scholar] [CrossRef]
  18. Net, S.; Delmont, A.; Sempéré, R.; Paluselli, A.; Ouddane, B. Reliable quantification of phthalates in environmental matrices (air, water, sludge, sediment and soil): A review. Sci. Total Environ. 2015, 515–516, 162–180. [Google Scholar] [CrossRef] [PubMed]
  19. Fan, X.-J.; Liu, S.-Z.; Li, H.-H.; He, J.; Feng, J.-T.; Zhang, X.; Yan, H. Effects of Portulaca oleracea L. extract on lipid oxidation and color of pork meat during refrigerated storage. Meat Sci. 2019, 147, 82–90. [Google Scholar] [CrossRef]
  20. Carnol, L.; Schummer, C.; Moris, G. Quantification of six phthalates and one adipate in Luxembourgish beer using HS-SPME-GC/MS. Food Anal. Methods 2017, 10, 298–309. [Google Scholar] [CrossRef]
  21. Zhang, N.; Lei, X.; Huang, T.; Su, L.; Zhang, L.; Xie, Z.; Wu, X. Guanidyl-functionalized polyhedral oligomeric silsesquioxane porous hybrid polymer coating for specific solid phase microextraction of phthalate esters in foodstuff. Chem. Eng. J. 2020, 386, 124003. [Google Scholar] [CrossRef]
  22. Sánchez-Avila, J.I.; Kretzschmar, T. Simultaneous Determination of Polycyclic Aromatic Hydrocarbons, Alkylphenols, Phthalate Esters and Polychlorinated Biphenyls in Environmental Waters Based on Headspace-Solid Phase Microextraction Followed by Gas Chromatography-Tandem Mass Spectrometry. J. Environ. Anal. Chem. 2017, 4, 1–11. [Google Scholar] [CrossRef]
  23. Wang, W.; Leung, A.O.W.; Chu, L.H.; Wong, M.H. Phthalates contamination in China: Status, trends and human exposure-with an emphasis on oral intake. Environ. Pollut. 2018, 238, 771–782. [Google Scholar] [CrossRef]
  24. Moreira, M.; André, L.; Cardeal, Z. Analysis of Phthalate Migration to Food Simulants in Plastic Containers during Microwave Operations. Int. J. Environ. Res. Public Health 2013, 11, 507–526. [Google Scholar] [CrossRef]
  25. Razavi, N.; Yazdi, A.S. New application of chitosan-grafted polyaniline in dispersive solid-phase extraction for the separation and determination of phthalate esters in milk using high-performance liquid chromatography. J. Sep. Sci. 2017, 40, 1739–1746. [Google Scholar] [CrossRef]
  26. Zaater, M.F.; Tahboub, Y.R.; Al Sayyed, A.N. Determination of phthalates in Jordanian bottled water using GC-MS and HPLC-UV: Environmental study. J. Chromatogr. Sci. 2014, 52, 447–452. [Google Scholar] [CrossRef] [PubMed]
  27. Pang, Y.H.; Yue, Q.; Huang, Y.Y.; Yang, C.; Shen, X.F. Facile magnetization of covalent organic framework for solid-phase extraction of 15 phthalate esters in beverage samples. Talanta 2020, 206, 120194–120204. [Google Scholar] [CrossRef]
  28. Yue, Q.; Huang, Y.Y.; Shen, X.F.; Yang, C.; Pang, Y.H. In situ growth of covalent organic framework on titanium fiber for headspace solid-phase microextraction of 11 phthalate esters in vegetables. Food Chem. 2020, 318, 126507. [Google Scholar] [CrossRef] [PubMed]
  29. Mirzajani, R.; Kardani, F.; Ramezani, Z. Fabrication of UMCM-1 based monolithic and hollow fiber—Metal-organic framework deep eutectic solvents/molecularly imprinted polymers and their use in solid phase microextraction of phthalate esters in yogurt, water and edible oil by GC-FID. Food Chem. 2020, 314, 126179. [Google Scholar] [CrossRef] [PubMed]
  30. Korkmaz, S.D.; Küplülü, Ö. Determination of phthalates in some milk products by liquid chromatography/tandem mass spectrometry. Ank. Univ. Vet. Fak. Derg. 2019, 66, 231–236. [Google Scholar] [CrossRef]
  31. Tsai, M.-Y.; Ho, C.-H.; Chang, H.-Y.; Yang, W.-C.; Lin, C.-F.; Lin, C.-T.; Xue, Y.-J.; Lai, J.-M.; Wang, J.-H.; Chang, G.-R. Analysis of Pollution of Phthalates in Pork and Chicken in Taiwan Using Liquid Chromatography–Tandem Mass Spectrometry and Assessment of Health Risk. Molecules 2019, 24, 3817. [Google Scholar] [CrossRef] [Green Version]
  32. Santana-Mayor, Á.; Socas-Rodríguez, B.; Rodríguez-Ramos, R.; Rodríguez-Delgado, M.Á. A green and simple procedure based on deep eutectic solvents for the extraction of phthalates from beverages. Food Chem. 2020, 312, 125798. [Google Scholar] [CrossRef]
  33. Notardonato, I.; Protano, C.; Vitali, M.; Bhattacharya, B.; Avino, P. A Method Validation for Simultaneous Determination of Phthalates and Bisphenol A Released from Plastic Water Containers. Appl. Sci. 2019, 9, 2945. [Google Scholar] [CrossRef] [Green Version]
  34. Nlu, Y.; Gao, W.; Li, H.; Zhang, J.; Llan, Y. Rapid determination of 17 phthalate esters in capsanthin by QuEChERS coupled with gas chromatography-mass spectrometry. Anal. Sci. 2020, 36, 485–490. [Google Scholar] [CrossRef] [Green Version]
  35. Fan, J.C.; Ren, R.; Jin, Q.; He, H.L.; Wang, S.T. Detection of 20 phthalate esters in breast milk by GC-MS/MS using QuEChERS extraction method. Food Addit. Contam. Part A Chem. Anal. Controlexposure Risk Assess. 2019, 36, 1551–1558. [Google Scholar] [CrossRef] [PubMed]
  36. Wu, Y.; Zhou, Q.; Yuan, Y.; Wang, H.; Tong, Y.; Zhan, Y.; Sheng, X.; Sun, Y.; Zhou, X. Enrichment and sensitive determination of phthalate esters in environmental water samples: A novel approach of MSPE-HPLC based on PAMAM dendrimers-functionalized magnetic-nanoparticles. Talanta 2020, 206, 120213. [Google Scholar] [CrossRef]
  37. Zaytseva, N.V.; Ulanova, T.S.; Karnazhitskaya, T.D.; Zorina, A.S.; Permyakova, T.S. Determination of phthalates in juice product by high-performance liquid chromatography/mass spectrometry. Vopr. Pitan. 2018, 87, 117–124. [Google Scholar] [CrossRef] [PubMed]
  38. Salazar-Beltrán, D.; Hinojosa-Reyes, L.; Ruiz-Ruiz, E.; Hernández-Ramírez, A.; Guzmán-Mar, J.L. Phthalates in Beverages and Plastic Bottles: Sample Preparation and Determination. Food Anal. Methods 2018, 11, 48–61. [Google Scholar] [CrossRef]
  39. Zhou, J.; Qi, Y.; Wu, H.; Diao, Q.; Tian, F.; Li, Y. Simultaneous determination of trace migration of phthalate esters in honey and royal jelly by GC-MS. J. Sep. Sci. 2014, 37, 650–657. [Google Scholar] [CrossRef] [PubMed]
  40. Zhang, Y.; Huang, B.; Sabel, C.E.; Thomsen, M.; Gao, X.; Zhong, M.; Chen, Z.; Feng, P. Oral intake exposure to phthalates in vegetables produced in plastic greenhouses and its health burden in Shaanxi province, China. Sci. Total Environ. 2019, 696, 133921. [Google Scholar] [CrossRef] [PubMed]
  41. An, J.; Kim, Y.Y.; Cho, H.D.; Kim, J.; Lee, J.Y.; Lee, Y.; Jo, E.; Lee, J.; Cha, S.; Han, S.B. Development and investigation of a QuEChERS-based method for determination of phthalate metabolites in human milk. J. Pharm. Biomed. Anal. 2020, 181, 113092. [Google Scholar] [CrossRef] [PubMed]
  42. Schecter, A.; Lorber, M.; Guo, Y.; Wu, Q.; Yun, S.H.; Kannan, K.; Hommel, M.; Imran, N.; Hynan, L.S.; Cheng, D.; et al. Phthalate Concentrations and Dietary Exposure from Food Purchased in New York State. Environ. Health Perspect. 2013, 121, 473–479. [Google Scholar] [CrossRef] [Green Version]
  43. Du, L.; Ma, L.; Qiao, Y.; Lu, Y.; Xiao, D. Determination of phthalate esters in teas and tea infusions by gas chromatography-mass spectrometry. Food Chem. 2016, 197, 1200–1206. [Google Scholar] [CrossRef] [PubMed]
  44. Del Carlo, M.; Pepe, A.; Sacchetti, G.; Compagnone, D.; Mastrocola, D.; Cichelli, A. Determination of phthalate esters in wine using solid-phase extraction and gas chromatography-mass spectrometry. Food Chem. 2008, 111, 771–777. [Google Scholar] [CrossRef]
  45. Abtahi, M.; Dobaradaran, S.; Torabbeigi, M.; Jorfi, S.; Gholamnia, R.; Koolivand, A.; Darabi, H.; Kavousi, A.; Saeedi, R. Health risk of phthalates in water environment: Occurrence in water resources, bottled water, and tap water, and burden of disease from exposure through drinking water in Tehran, Iran. Environ. Res. 2019, 173, 469–479. [Google Scholar] [CrossRef]
  46. Luo, Q.; Liu, Z.H.; Yin, H.; Dang, Z.; Wu, P.X.; Zhu, N.W.; Lin, Z.; Liu, Y. Migration and potential risk of trace phthalates in bottled water: A global situation. Water Res. 2018, 147, 362–372. [Google Scholar] [CrossRef]
  47. Overgaard, L.E.K.; Bonefeld, C.M.; Frederiksen, H.; Main, K.M.; Thyssen, J.P. The association between phthalate exposure and atopic dermatitis with a discussion of phthalate induced secretion of interleukin-1β and thymic stromal lymphopoietin. Expert Rev. Clin. Immunol. 2016, 12, 609–616. [Google Scholar] [CrossRef]
  48. Kim, J.; Kim, J.I.; Lee, C.W. Development and validation of a modified QuEChERS method coupled with LC-MS/MS to determine arbutin in pear peels. Food Sci. Biotechnol. 2016, 25, 987–992. [Google Scholar] [CrossRef]
  49. Guo, Y.; Zhang, Z.; Liu, L.; Li, Y.; Ren, N.; Kannan, K. Occurrence and profiles of phthalates in foodstuffs from China and their implications for human exposure. J. Agric. Food Chem. 2012, 60, 6913–6919. [Google Scholar] [CrossRef] [PubMed]
Applsci 11 02130 g001 550
Figure 1. Multivariate analysis for HS-SPME optimization of phthalates target. Conditions: sample volume: 2 mL; concentration of phthalates: 60 μg/L; NaCl amount: 0.2 g; extraction time: 15, 30, and 45 min; extraction temperature: 60, 70, and 80 °C; desorption time and temperature: 6 min and 250 °C.
Figure 1. Multivariate analysis for HS-SPME optimization of phthalates target. Conditions: sample volume: 2 mL; concentration of phthalates: 60 μg/L; NaCl amount: 0.2 g; extraction time: 15, 30, and 45 min; extraction temperature: 60, 70, and 80 °C; desorption time and temperature: 6 min and 250 °C.
Applsci 11 02130 g001
Applsci 11 02130 g002 550
Figure 2. HS-SPME/GC-MS chromatograms of phthalates at 60 μg/L using PDMS/DVB fiber at 80 °C for 30 min.
Figure 2. HS-SPME/GC-MS chromatograms of phthalates at 60 μg/L using PDMS/DVB fiber at 80 °C for 30 min.
Applsci 11 02130 g002
Table
Table 1. Figures of merit of the phthalates HS-SPME/GC-qMS methodology.
Table 1. Figures of merit of the phthalates HS-SPME/GC-qMS methodology.
RT (min)PAEsLinear Range (µg/L)EquationR2LOD (µg/L)LOQ (µg/L)
13.18DIBP0.5–60y = 817,649x + 1060.9960.060.21
22.55BBP0.5–60y = 66,577x + 116,1150.9990.030.10
26.49BDE1–60y = 124,317x + 755,4680.9950.080.24
27.77DOP1–60y = 44,993x – 100,8070.9990.070.23
Table
Table 2. Recovery and precision of phthalates in food packaging, using sample 3, at three spiked levels *.
Table 2. Recovery and precision of phthalates in food packaging, using sample 3, at three spiked levels *.
RT (min)CompoundsSpiked Level (µg/L)% REC ± SDIntra-Day (%)Inter-Day (%)
13.17DIBP0.590.20 ± 1.33.57.5
3091.60 ± 0.91.95.8
60104.9 ± 1.80.93.3
22.55BBP0.5107.9 ± 2.05.98.5
30111.3 ± 1.91.36.7
60105.7 ± 3.20.91.7
26.49BDE198.30 ± 0.87.912.7
3091.30 ± 1.43.710.6
6094.00 ± 1.70.63.5
27.77DOP1109.2 ± 4.31.58.2
3099.20 ± 1.61.43.1
6095.50 ± 0.80.72.2
RT—retention time; % REC—recovery percentage; SD—standard deviation; * validation obtained for sample 3.
Table
Table 3. Comparison of the analytical performance of the developed method in this study with other studies reported in the literature.
Table 3. Comparison of the analytical performance of the developed method in this study with other studies reported in the literature.
Target AnalytesSamplesExtraction ProcedureAnalytical MethodLOD (µg/L)LOQ (µg/L)Rec (%)Ref.
6 PAEsMilk productsLLELC-MS/MS-20–30 µg/kg84–96[30]
5 PAEsMeatsLLELC-MS/MS-40 µg/kg96–103[31]
8 PAEsTea, juicesDES-VA-EDLLMEHPLC-DAD5.1–17.817.2–59.484–120[32]
6 PAEs, BPAWatersSB-DLLMEGC-MS0.001–0.0080.005–0.01495–99[33]
17 PAEsCapsanthinQuEChERSGC-MS0.2–0.5 µg/kg0.6–1.5 µg/kg83–118[34]
20 PAEsBreast milkQuEChERSGC-MS/MS0.004–1.3 µg/kg0.02–4.2 µg/kg83–123[35]
3 PAEsWatersMSPEHPLC-VWD0.025–0.160.082–0.5493–102[36]
15 PAEsBeveragesMSPEGC-MS/MS0.005–2.7480.018–9.15179–122[27]
6 PAEs, BPAHoneyUVA-DLLMEGC-MS3–13 µg/kg7–22 µg/kg71–100[20]
6 PAEs, 1 AdipateBeersHS-SPMEGC-MS0.006–0.5900.020–1.95974–101[28]
11 PAEsVegetablesHS-SPMEGC-MS/MS0.001–0.430--[21]
10 PAEsMilk and riceSPMEGC-MS0.054–2.51 ng/L0.18–8.37 ng/L89–114[24]
4 PAEsYogurts, watersHFLMP-SPMEGC-FID0.008–0.0300.028–0.12096–100[29]
4 PAEsFood packagingHS-SPMEGC-MS0.03–0.080.10–0.2490–111This study
BPA—bisphenol A; DES-VA-EDLLME—deep eutectic solvent-based dispersive liquid–liquid microextraction; GC-FID—gas chromatography-flame ionization detection; GC-MS—gas chromatography-mass spectrometry; GC-MS/MS—gas chromatography tandem mass spectrometry; HFLMP-SPME—hollow fiber liquid membrane-protected solid-phase microextraction; HPLC-DAD—high-performance liquid chromatography-diode-array detection; HPLC-VWD—high-performance liquid chromatography-variable wavelength detector; HS-SPME—headspace solid-phase microextraction; LC-MS/MS—liquid chromatography tandem mass spectrometry; LLE—liquid–liquid extraction; MSPE—magnetic solid-phase extraction; PAEs—phthalates; QuEChERS—quick, easy, cheap, effective, rugged, and safe; SB-DLLME—solvent-based dispersive liquid–liquid microextraction; SPME—solid-phase microextraction; UVA-DLLME—ultrasound vortex assisted dispersive liquid–liquid microextraction.
Table
Table 4. Occurrence of phthalates in plastic-based food packages.
Table 4. Occurrence of phthalates in plastic-based food packages.
SamplesPhthalates Concentration (µg/L) ± SD
DIBPBBPBDEDOP
Plastic 1<LOD---
Plastic 2<LOD---
Plastic 3<LOD---
Plastic 4<LOD1.4 ± 0.01<LOD2.8 ± 0.04
Plastic 54.8 ± 0.3--1.0 ± 0.01
Plastic 610.6 ± 0.2--2.2 ± 0.06
Plastic 79.0 ± 0.4--1.8 ± 0.07
Plastic 86.1 ± 0.3--1.1 ± 0.08
Plastic 98.2 ± 0.4---
Plastic 104.7 ± 0.05--2.2 ± 0.02
Plastic 113.6 ± 0.7--1.9 ± 0.2
Plastic 1210.7 ± 0.6---
Plastic 136.8 ± 0.8--1.9 ± 0.4
Plastic 144.3 ± 0.2-<LOD2.5 ± 0.2
SD: standard deviation; < LOD: lower than limit of detection; -: not detected.
Table
Table 5. Levels of different phthalates found in different types of samples reported in the literature.
Table 5. Levels of different phthalates found in different types of samples reported in the literature.
SamplesPhthalatesConcentration RangeRef.
MeatsDEHP (Pork and Chicken)0.62, 0.8 mg/kg[31]
DEHP (Fruit jam, Salted meat); DnBP170 μg/kg, 2380 μg/kg; 1580 μg/kg[42]
SpicesDEHP; DiBP, DBP; BBzP2598 μg/kg; >300 μg/kg[3,49]
TeaDMP, DEP, DIBP; DBP; DEHP1.135–3.734 mg/kg[43]
WineDMP, DEP/DBP/BBP0.024–0.029 μg/mL[44]
WatersDEHP, DBP, DEP, BOP
DEHP, BBP, DBP, DEP, DMP (Bottled water)		0.76/0.96/1.06/0.77 μg/L
3.42/2.89/13.99/5.35/1.15/2.07 μg/L		[46]
CapsanthinDBP, DEHP0.872/0.992 μg/g[34]
BeersDMP, DEP, DBP, BBP, DEHP, DOP, DEHA0.588, 0.175, 0.118, 0.079, 0.009, 0.006, 0.009 μg/L[20]
JuiceDOP, DBP, DIBP, DEHP, BBP (Juice)0.01–08 mg/dm3[37]
BeveragesDEHP, DEP0.580 /0.070 μg/L[38]
Honey/Royal JellyDIBP, BBP, BDE, DOP,0.3/1.5; 0.8/3; 0.3/1.5; 1.2; 6 ng/g[39]
VegetablesDEHP, DnBP, DiBP, DEP, BBP1881–4664/985/338/9/2 μg/kg[40]
Powdered and Human/Raw MilkMono-BP, mono-BzP,
DnBP, BzBP, DEHP		0.1–500 ng/mL
18/1.2/21 μg/kg		[3,41]
YoghurtDEHP, DBP, BBP170/112/63 μg/kg[30]
Plastic ContainersDIBP, BBP, BDE, DOP4.39/1.42/<LOD/1.03 µg/LThis study
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Perestrelo, R.; Silva, C.L.; Algarra, M.; Câmara, J.S. Evaluation of the Occurrence of Phthalates in Plastic Materials Used in Food Packaging. Appl. Sci. 2021, 11, 2130. https://doi.org/10.3390/app11052130

AMA Style

Perestrelo R, Silva CL, Algarra M, Câmara JS. Evaluation of the Occurrence of Phthalates in Plastic Materials Used in Food Packaging. Applied Sciences. 2021; 11(5):2130. https://doi.org/10.3390/app11052130

Chicago/Turabian Style

Perestrelo, Rosa, Catarina L. Silva, Manuel Algarra, and José S. Câmara. 2021. "Evaluation of the Occurrence of Phthalates in Plastic Materials Used in Food Packaging" Applied Sciences 11, no. 5: 2130. https://doi.org/10.3390/app11052130

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop