Development of a hydrophobic TFME combined with DLLME in the extraction of PAHs from personal care products before GC-FID determination

doi:10.21203/rs.3.rs-3111038/v1

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Development of a hydrophobic TFME combined with DLLME in the extraction of PAHs from personal care products before GC-FID determination

https://doi.org/10.21203/rs.3.rs-3111038/v1

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In this research, a thin film microextraction method was developed for the extraction of polycyclic aromatic hydrocarbons from personal care products prior to their quantification by gas chromatography equipped with a flame ionization detector. Firstly, a thin mesh was immersed in a mixture of stearic acid solution in ethanol and hydrochloric acid to obtain a hydrophobic surface and then it was used in the microextraction of the target analytes. The stair-like hierarchical and hydrophobic structure of the mesh provided large contact area and high tendency towards the analytes. After desorption of the analytes from the surface of the mesh, the obtained eluent was used in the following preconcentration step e.g., dispersive liquid-liquid microextraction. The effective factors were studied and the method was validated under optimal conditions. Calibration curves were linear in the ranges of 0.3–1000, 0.1–1000, 0.1–1000, 0.1–1000, and 0.5–1000 µg/L and detection limits were 0.10, 0.04, 0.04, 0.04, and 0.20 µg/L for acenaphthene, phenanthrene, anthracene, pyrene and benzo[a] pyrene, respectively. The repeatability of the method (for 5 thin mesh made under the same conditions) was obtained in a range of 3.2–6.5%. This method was successfully used in the extraction and analysis of the personal care products as real samples and anthracene was found in one sample.

Earth and environmental sciences/Natural hazards

Physical sciences/Chemistry

Polycyclic aromatic hydrocarbon

Thin film microextraction

Gas chromatography

Personal care products

Polycyclic aromatic hydrocarbons (PAHs) are a group of hydrocarbons that are composed of two or more benzene rings in which at least two carbon atoms are shared between the benzene rings ¹. In some PAHs, besides carbon and hydrogen; nitrogen and sulfur participate in their structure. Up to now, different PAHs were found and identified but among them the compounds composed of four to seven benzene rings are more important than the other ones. Usually, PAHs enter to the environment from incomplete combustion of organic materials such as fossil fuels, wood, and forest, burning and ashing of fins, and industrial activities ². Benzo[a] pyrene, a high molecular weight PAH, is one of the most discussed and studied member of this class of compounds, because of its cytotoxic, mutagenic, and carcinogenic properties. However carcinogenicity and toxicity of other PAHs consisting of dibenzo (H,A) anthracene, dibenzo (H,A) pyrene, dibenzo(I,A) pyrene, and dibenzo(L,A) pyrene were also confirmed by World Health Organization and the Food Control Committee ³. A maximum residue limit (MRL) of 1 mg/kg of the eight PAHs classified as carcinogenic is recommended for all consumer products in Europe guideline ⁴.Considering the recommended MRL for PAHs, establishment of a sensitive and accurate analytical method for monitoring PAHs in different matrices is a great interest in different countries. In recent years, different analytical instruments like gas chromatography (GC) ^5–10 and liquid chromatography ^11–17 were used to determine PAHs in different samples. A main step of these methods is the use of an extraction method before analysis of PAHs to remove interfering compounds and preconcentration of the analytes. Performing microextraction procedures is advised to use in determination of PAHs due to providing high enrichment factors (EFs). Solid phase microextraction (SPME) was used in the extraction of PAHs ^18–20. The main shortage of SPME is its low adsorption capacity due to its low sorbent amount. While increasing the thickness of the coating sharpens the sensitivity of the method, but the equilibrium time is also increased. So, thin-film microextraction (TFME) was developed to overcome the limited adsorption capacity of SPME. In TFME, a thin sheet of a sorbent is applied as the extracting phase which enhanced sensitivity without increasing the equilibrium time. TFME method is a known microextraction method which is based on adsorption of the target analytes onto a proper thin film and the desorption of them to use in the following determination system. An extra support such as stainless-steel rod, mesh or blade-shaped substrate is needed to reinforce of the polymeric phase during the extraction step. TFME is considered as an analogue method of SPME in which large amount of an extractive phase with high large surface area can be provided by this method. This can provide high sensitivity and efficiency of the method. Furthermore, TFME can be done on high volumes of sample solution to reach high EF. It is crucial to note that, the great performances of TFME is strongly related to the nature of sorbent and subsequently, exploring and preparation on new sorbents is increasing. This method as a sample-preparation tool was used in many fields ^21,22. In most of these applications, it was used for the cleanup goal. TFME has clear advantages in terms of high sensitivity, short sampling times, non-invasive diagnostic tool for using in medicine application, high efficiency extraction for trace analytes, and fast extraction rate compared to other sample preparation techniques. This method can be used in situ or laboratory pretreatment method ²³. The important direction for TFME development is the exploration of new coatings and new thin-film formats for a range of applications. Hydrophobic coating is a good choice for TFME in the extraction of nonpolar analytes. Recently, materials with superhydrophobicity and superoleophilicity were investigated for highly effective separation ²⁴. In spite of significant advantages of TFME, the use of relatively high volumes of elution solvents to desorb the analytes from the film surface is the major drawback of this method. To solve this drawback, combining TFME with other approaches like dispersive liquid-liquid microextraction (DLLME) to achieve high EF was proposed.

The main goal of the present work was the development of a combined sample preparation method (TFME-DLLME) for the extraction and preconcentration of some PAHs from personal care products. Personal care products include a wide range of chemicals that can be released directly into the environment or volatilized into the air ⁴. In these groups of products, relatively limited papers were reported about their PAHs contents and their effects. In this work, TFME fiber was prepared via stainless steel mesh coated with a superhydrophobic surface prepared just by its immersing into stearic acid solution. The TFME method was followed by DLLME to more cleanup and enrichment.

2.1. Chemicals

The studied PAHs (acenaphthene, phenanthrene, anthracene, pyrene, and benzo[a]pyrene) were purchased from Merck (Darmstadt, Germany). A stock solution of the PAHs was prepared in acetone at a concentration of 1000 mg/L and utilized for the preparation of daily used working solutions. Stearic acid, sodium chloride, hydrochloric acid (37%, w/w), sodium hydroxide, chloroform, dichloromethane, carbon tetrachloride, 1,2,2 tricloroethane, 1,1,2,2 trichloromethane, 1,2,2-tricloro1,1,2-trifluoro ethane, hexane, methanol, acetone, acetonitrile, and ethanol were purchased from Merck. The steel meshes with different dimensions were bought from local store (Tabriz, Iran).

2.2. Apparatus

PAHs were analyzed by a 6890 Agilent GC (USA) equipped with a flame ionization detector (FID). Temperature programming of the GC column oven was set as follows: the initial temperature was 100°C and held for 2 min, was increased to 290°C with a ramp of 17°C/min and held for 10 min.

The analysis involved adjusting both the GC injection port and detector temperatures to 300 ˚C. Manual injection of both the extractant and standard solutions occurred through the injection port, followed by analyte separation using an HP-1 capillary column with a length of 30 m. The stationary phase had a film thickness of 0.25 µm and a column inner diameter of 0.25 mm. Various equipment including a Sartorius analytical balance with a precision of ± 0.0001 g (Göttingen, Germany), a 691-pH meter from Metrohm (Herisau, Switzerland), a BHG Hermile centrifuge, and a FESEM MIRA3 TESCAN Scanning Electron Microscope (SEM) from Welwyn Garden in the UK were utilized at different stages of the study.

2.3. Real samples

Different personal care products including face wash, vitamin C serum, and mouthwash produced by different companies, were used as real samples. All samples were packed in bottles and kept in refrigerator before analysis. The samples were centrifuged and in the case of face wash, it was diluted with the ultrapure ware at a ratio of 1:2, before performing the extraction procedure.

2.4. Preparation of hydrophobic thin film

A piece of stainless-steel mesh (0.5 × 2 cm × cm) was cleaned by water and then successively sonicated in 2 mol L^− 1 hydrochloric acid solution (10 min), acetone (5 min), ethanol (5 min), and deionized water (5 min) to remove oxidizing materials, organic compounds, oil, etc. Then, the mesh was dried and immersed into a mixture of 0.06 mol L^− 1 stearic acid solution prepared in ethanol and HCl solution (6 mol L^− 1) mixture adjusted at 60°C. After 30 min, the prepared coated mesh was taken by a forceps, washed with water, dried at room temperature, and used in the sample preparation method. The method was similar to literature [24] with a brief modification.

2.5. Sample preparation by TFME-DLLME

The TFME procedure was started by immersion of the prepared thin film mesh into 10 mL deionized water spiked with the analytes at a concentration of 50 ng/mL (each PAH) or real sample placed into a glass vial. The vial was placed into a water bath and it was sonicated for 15 min at 30 ˚C. After that, the mesh was withdrawn and immersed into 1.5 mL acetone as the desorption solvent. The desorption procedure was accelerated by sonication for 15 min. After that the mesh was removed by a forceps and the eluent was mixed with 20 µL CCl₄ and immediately injected in 5 mL distillated water. The cloudy solution was centrifuged and 1 µL of the organic phase was injected into GC-FID (Fig. 1).

3.1. Microscopic images of thin film

Figure 2 shows the SEM images of the structure of original stainless-steel mesh, preconditioned stainless steel, and the mesh coated by stearic acid. Figures 2A and 2B show the stainless-steel mesh before and after conditioning. A relatively smooth, clear, grid, and homogenous surface is obvious. Figures 2C and 2D show different magnifications of the coated mesh. It can be seen that the stainless-steel mesh surface has an uniform nanostructure and it was covered by a thin film which indicates its successful chemically modification with stearic acid.

3.2. Optimization of TFME effective parameters

3.2.1. Selection of stainless-steel mesh thickness

Thickness of the used mesh for extraction of the analytes can play a significant role in the method efficiency due to providing different surfaces of the sorbent. In order to investigate the effect of mesh thickness, a series of experiments was done with the meshes constructed by the wires with different diameters (0.2, 0.3, and 0.4 mm) having a constant dimension (0.5 × 2 cm × cm). After performing the TFME procedure, the obtained data (Fig. 3), confirm that the mesh constructed with the wire having diameter of 0.4 mm has better efficiency in the extraction of the analytes. Thus, it was selected for the next tests.

3.2.2. Optimization of mesh dimensions

It is obvious that mesh dimensions has a significant role in the method efficacy by providing different surface areas to adsorb the analytes and it should be optimized. In this study, two pieces of the mesh were cut with the dimensions of 0.5×2 cm × cm and 0.5×1 cm × cm and used in the extraction of PAHs. It must be noted that at dimensions, higher than 0.5×2 cm × cm elution of the analytes from the film surface was difficult with 1.5 mL elution solvent. The data in Fig. 4 show that higher analytical signals are obtained with the larger mesh. Therefore, the mesh the dimensions of 0.5×2 cm × cm was used in the next experiments.

3.2.3. Adsorption time

In TFME approaches, adsorption time is an important factor that affects distribution of the analytes between solution and the thin film. In this study, to investigate the effect of adsorption time on the efficacy of the method, several experiments were done at the times between 5 and 30 min. The results (Fig. S1) showed that increasing the adsorption time has a positive effect on the method efficiency till 15 min while at higher times analytical signals decrease. Increasing the analytical signals can be related to the contact time of the analytes with the adsorbent. However, at higher adsorption times (> 15 min) decreasing the analytical data can be attributed to back-extraction of the analytes into solution. Therefore, 15 min was chosen as the optimal adsorption time.

3.2.4. Study of temperature

The effect of sample solution temperature on the efficiency of the method should be studied due to the its effects on migration rates of the analytes and the sample solution viscosity. For this purpose, the sample solution temperature effect on the method efficiency was studied in the range of 20–60 ˚C. As can be seen from Fig. 5, the extraction efficiency increases up to 30 ˚C and then decreases continuously. Increasing the analytical signals up to 30 ⁰C can be related to increasing distribution coefficients and migration rates of the analytes between the solution and thin film. However, instability of stearic acid thin film on the surface of the mesh was occurred at higher solution temperatures and the analytical signals were reduced at those temperatures. Therefore, the experiments were done by adjusting the temperature at 30 ˚C in the following tests.

3.2.5. Selection of desorption solvent type and volume

In order to select the best solvent for the elution of the studied PAHs from the thin film surface, various organic solvents including acetone, acetonitrile, methanol, and ethanol were tested. The miscibility of the elution solvent with the aqueous phase used in the following DLLME step as a dispersive solvent was considered as a factor in the selection of the elution solvent. The obtained data (Fig. S2a), show that acetone acts better than the other tested solvents in the elution of the analytes from the thin film surface and enrichment of the analytes by the DLLME approach. So, acetone was used in the following experiments.

According to the significant role of the elution solvent volume in desorption of the analytes from the thin film surface and their enrichment in the DLLME step, acetone volume was investigated in the range of 1.25-2.00 mL and the obtained data (Fig. S2b) depict that 1.50 mL is more effective than the other volumes compared to other tested volumes. Therefore, 1.50 mL acetone was selected as the elution solvent for the further experiments. Notably, the volumes lower than < 1.25 mL was not enough for complete immersion of the mesh and the method failed to work.

3.2.6. Optimization of desorption time

Complete desorption of the adsorbed analytes onto by the prepared thin film has a great effect on the method efficiency. In this method, the effect of desorption time was studied by sonication of the thin film into the elution solvent and at different times (5–25 min). The obtained results (Fig. 6) show that desorption of the analytes improvs by increasing sonication time until 15 min and after that, it reaches nearly constant values. As a result, 15 min was selected as the optimum sonication time in the following experiments.

3.2.7. Salt addition

Adding an inorganic salt increases the ionic strength of the solution and reduces the analytes solubility in the solution, which may improve the efficiency of lipophilic analytes in extraction methods. Therefore, the effect of NaCl addition on the extraction efficiency of the TFME step was investigated by performing the method on spiked NaCl solutions in the range of 0 to 6% (w/v). The obtained data confirmed that salt addition was not effective and the experiments were done without salt addition.

3.2.8. pH effect

Figure 7 shows the effect of solution pH on the extraction efficiency of the method. As can be seen, acidic solutions with the pHs of 4 to 6 show better results. Considering the inertness of the compounds of interest to the pH changes, it seems that pH affects the structure of TFME and stearic acid According to the data, it can be seen that in alkaline and highly acidic pHs, the amounts of extracted analytes decrease, which is probably due to charging the fiber surface at highly acidic solution (pH = 2). On the other hand, at alkaline pHs ionization of stearic acid is occurred. Therefore, pH equal to 6 was chosen as the optimal solution pH.

3.3. Optimization of DLLME parameters

3.3.1. Optimization of extraction solvent type and volume

The analytes extracted through the TFME step were further concentrated using a DLLME procedure. This involved mixing the eluent containing the analytes with an appropriate water-immiscible organic solvent, and injecting the resulting mixture into 5 mL of deionized water. The dissolved analytes in the eluent were then concentrated into a small volume of the water-immiscible organic solvent. The efficiency of this process was found to be dependent on the nature of the organic solvent used. Several experiments were conducted using different solvents including chloroform, carbon tetrachloride, dichloromethane, 1,2,2-trichloroethane, and 1,1,2-trichloro 1,2,2-trifluoroethane (Fig. 3SA). Based on the results, carbon tetrachloride was found to be the most effective solvent for the subsequent experiments.

To determine the optimal extraction solvent volume, tests were carried out using carbon tetrachloride at volumes ranging from 15 to 35 µL (Fig. 3SB). It was observed that as the volume of the extraction solvent increased, the volume of the sedimented phase also increased from 10 to 28 µL. However, the analytical signals decreased with increasing extraction solvent volume. Therefore, subsequent experiments were conducted using a fixed volume of 15 µL carbon tetrachloride to obtain high analytical signals and extraction factors (EFs). It is notable that in the experiments with different concentrations of salt or pHs, significant changes in the analytical signals were not observed.

3.4. Method validation

The introduced method was validated by calculating LOD (signal (S)/noise (N) = 3), LOQ (S/N = 10), coefficient of determination (r²), linear range (LR), repeatability (relative standard deviation, RSD), EF, and extraction recovery (ER). According to the calibration curves plotted by performing the method on eight aqueous standard solutions versus concentration, r² values were ≥ 0.9948 for all analytes. The repeatability of thin film fabrication (for 5 thin film made under the same conditions) was obtained in a range of 2.5–5.3%. EF is defined as the ratio of the analyte concentration in the final organic phase (C_org) to the initial analyte concentration in the aqueous phase (C_aq) according to the following equation.

EF = C_org/C_aq (1)

The EF can also be calculated from the ratio of the slopes of the calibration curves obtained with and without the pre-concentration. ER% was calculated from below equation:

ER% = (V_org/ V_aq) × EF × 100 (2)

where V_org is the final volume of the organic phase and V_aq is the volume of the aqueous phase. EF and ER for the analytes were in the ranges of 590–650 and 59–65%, respectively. The results are tabulated in Table 1.

Table 1

Quantitative features of the developed method.
Analytes	LOD ^a)	LOQ ^b)	LR ^c)	r^{2 d)}	RSD ^e) % (n = 5) at the concentration of			ER ± SD ^f)	EF ± SD ^g)
Analytes	LOD ^a)	LOQ ^b)	LR ^c)	r^{2 d)}	10 ng/mL	100 ng/mL	1000 ng/mL	ER ± SD ^f)	EF ± SD ^g)
Acenaphthene	0.10	0.30	0.3–100	0.9951	6.5	3.7	3.7	59 ± 5	590 ± 30
Phenanthrene	0.04	0.10	0.1–100	0.9964	5.2	3.7	3.6	60 ± 4	600 ± 40
Anthracene	0.04	0.10	0.1–100	0.9957	5.3	3.2	3.9	65 ± 3	650 ± 35
Pyrene	0.04	0.10	0.1–100	0.9960	4.8	4.0	3.5	61 ± 5	610 ± 55
Benzo[a] pyrene	0.20	0.50	0.5–100	0.9948	4.4	3.7	3.4	59 ± 6	590 ± 60
a) Limit of detection (S/N = 3) (ng/mL) b) Limit of quantification (S/N = 10) (ng/mL) c) Linear range (ng/mL) (n = 8) d) Coefficient of determination e) Relative standard deviation. f) Enrichment factor ± standard deviation (n = 3) g) Extraction recovery ± standard deviation (n = 3)

3.5. Real sample analysis

To evaluate the method's utility in real samples, the optimized TFME-DLLME-GC-FID approach was done on three cosmetic samples including vitamin C serum, face wash, and mouse wash samples. The results of analyses using standard addition method showed that the samples were free of the analytes except, face wash sample anthracene was found at the concentration of 3.2 ± 0.8 ng/mL (n = 3). To check the matrix effect, all samples were spiked with the analytes at two concentrations of 10 and 100 ng mL^− 1 (each analyte) and the method was done on them. The obtained results were compared with the spiked deionized solutions at similar concentrations and the data were calculated as mean relative recovery. The obtained results (Table 2) confirm that the samples matrices are not effective on the method efficiency.

Table 2

Study of matrix effect.
Sample	Mean relative recovery (%) ± standard deviation (n = 4)
Sample	Acenaphthene	Phenanthrene	Anthracene	Pyrene	Benzo [a]pyrene
All samples were spiked with each analyte at a concentration of 10 ng mL^− 1.
Vitamin C serum	80 ± 5	83 ± 3	86 ± 4	90 ± 5	93 ± 3
Mouth wash	81 ± 4	89 ± 5	88 ± 5	86 ± 4	85 ± 5
Face wash	80 ± 6	81 ± 5	80 ± 3	80 ± 4	82 ± 6
All samples were spiked with each analyte at a concentration of 100 ng mL^− 1.
Vitamin C serum	92 ± 2	96 ± 3	98 ± 5	92 ± 4	93 ± 3
Mouth wash	93 ± 3	99 ± 5	101 ± 3	91 ± 3	95 ± 4
Face wash	89 ± 5	91 ± 4	95 ± 4	96 ± 5	99 ± 5

3.6. Comparison of the method with other approaches

The established TFME-DLLME-GC-FID was compared with the other developed approaches for PAHs determination considering several parameters. The analytical features of the methods are listed in Table 3. The data regarding these values obtained by this method are better than or comparable with the other methods. All listed methods in Table 3 are TFME- and SPME-based approaches. The introduced method has the LRs wider than all the compared cases. The repeatability of the method is comparable or better than to other methods. The LODs of the method is low due to mesh-like structure of the sorbent with high surface area and also combining with DLLME. It should be noted that in all compared methods, mass spectrometer was used as the detector which is more sensitive than FID.

Table 3

Comparison of the method with other methods.
Method	Sorbent	LOD ^a)	LOQ ^b)	LR ^c)	RSD ^d)(%)	Ref.
HS-SPME/GC-MS ^e)	Ethoxylated noxylphenol	0.01–0.5	0.5	0.5–200	4.9–8.4	[26]
HS-TFME-GC-MS ^f)	Acrylonitrile butadiene styrene	0.08–0.2	0.26–0.66	0.5–300	4.1–8.9	[27]
TFME/GC-MS ^g)	Molecularly imprinted polymer	0.029–0.166	-	0.5–40	< 6	[28]
SPME/GC-MS ^h)	Covalent organic framework	0.006–0.024	-	0.1–50	5.79–9.98	[29]
TFME-DLLME/GC-FID ⁱ⁾	Stearic acid	0.04–0.20	0.10–0.5	0.1–100	3.2–6.5	This work
^a) Limit of detection (ng mL^− 1). ^b) Limit of quantification (ng mL^− 1). ^c) Linear range (ng mL^− 1). ^d) Relative standard deviation. ^e) Headspace solid phase microextraction- gas chromatography-mass spectrometry. ^f) Headspace thin film microextraction- gas chromatography-mass spectrometry. ^g) Thin film microextraction- gas chromatography-mass spectrometry. h) Solid phase microextraction-gas chromatography-mass spectrometry. i) Thin film microextraction-dispersive liquid-liquid microextraction-gas chromatography-flame ionization detector.

In this research, a combined TFME-DLLME method along with GC-FID was utilized to extract and measure some PAHs in personal care products. In TFME, a thin film was made using the stainless-steel mesh coated with stearic acid. TFME can be considered an analog of SPME in which a large amount of an extractive phase with high large surface area can be achieved. These properties in the present method provide the method's sensitivity and efficiency. This method was used to extract and determine some PAHs in personal care products. High sensitivity, no use of dangerous solvents, low LODs, and high efficiency low amount of adsorbent were advantages of the proposed method. The mesh form provides more surface area for modification and as a result effective extraction was occurred.

PAH: Polycyclic aromatic hydrocarbon; GC, Gas chromatography, TFME, Thin film microextraction; EF, Enrichment factor

Acknowledgments

The authors would like to thank the Tabriz University of Medical Sciences (Food and Drug Safety Research Center) for financial support.

Data Availability

The datasets used and/or analysed during the current study available from the corresponding author on reasonable request.

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No competing interests reported.

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Development of a hydrophobic TFME combined with DLLME in the extraction of PAHs from personal care products before GC-FID determination

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Abstract

Figures

1. Introduction

2. Experimental

2.1. Chemicals

2.2. Apparatus

2.3. Real samples

2.4. Preparation of hydrophobic thin film

2.5. Sample preparation by TFME-DLLME

3. Results and discussion

3.1. Microscopic images of thin film

3.2. Optimization of TFME effective parameters

3.2.1. Selection of stainless-steel mesh thickness

3.2.2. Optimization of mesh dimensions

3.2.3. Adsorption time

3.2.4. Study of temperature

3.2.5. Selection of desorption solvent type and volume

3.2.6. Optimization of desorption time

3.2.7. Salt addition

3.2.8. pH effect

3.3. Optimization of DLLME parameters

3.3.1. Optimization of extraction solvent type and volume

3.4. Method validation

3.5. Real sample analysis

3.6. Comparison of the method with other approaches

4. Conclusions

Abbreviations

Declarations

References

Additional Declarations

Supplementary Files

Status:

Version 1