1. Introduction
Edible oil is a crucial basic substance for maintaining normal physiological functions in the human body, and its quality and safety are directly linked to consumers’ health [
1,
2]. When used for frying, edible oil undergoes a series of complex chemical reactions at high temperatures, including oxidation, polymerization, and hydrolysis, with oxygen in the air, moisture in the food, and the food itself. These reactions lead to significant changes in the chemical composition and physical properties of the oil, generating substances like polar compounds, free fatty acids, and peroxides that are harmful to human health. As a result, the originally high-quality edible oil gradually deteriorates into low-quality frying oil [
3]. This deteriorated frying oil not only severely destroys the original nutrients in the oil but has also been proven to be closely associated with cardiovascular diseases, diabetes, obesity, and even some cancers [
4]. Traditional methods for detecting frying oil, such as physical and chemical index determination and gas chromatography-mass spectrometry, are highly accurate. However, they involve complex operations and require high-level professionalism, expensive equipment, and long detection cycles, making them difficult to meet the needs of rapid on-site screening [
5]. Therefore, the development of fast, non-destructive, and sensitive detection technology for adulterated edible oil has become a research focus and an urgent requirement in the field of food safety.
Gas chromatography (GC), high-performance liquid chromatography (HPLC), and gas chromatography-mass spectrometry (GC-MS) are commonly used methods for detecting adulteration in edible oils [
6,
7,
8]. These chromatographic techniques can analyze and compare the types and contents of major components like fatty acids and triglycerides, as well as characteristic components such as sterols and cholesterol, in adulterated and pure edible oils, enabling qualitative and quantitative analysis of adulteration. Although these methods offer high accuracy, their complex and time-consuming preprocessing makes them unsuitable for rapid large-scale sample analysis. In recent years, with the rapid development of spectroscopic technology, it has become a research hotspot due to its advantages of being fast, non-destructive, highly sensitive, and requiring no complex sample pretreatment [
9,
10]. Zhang Fengjuan conducted a quantitative study on hazelnut oil adulteration using laser Raman spectroscopy, employed principal component analysis for qualitative analysis, and established a partial least squares regression calibration model to quantitatively detect adulterated samples [
11]. Among spectroscopic techniques, the three-dimensional excitation-emission matrix (EEM) can effectively distinguish the fluorescence characteristics of different substances or the same substance in different states by simultaneously recording the emission spectra of the sample at different excitation wavelengths. Compared with one-dimensional or two-dimensional spectra, it provides richer information for complex system analysis [
12]. This technology has shown great potential in detecting edible oil adulteration and achieved a series of key results. For instance, Hu used three-dimensional fluorescence combined with partial least squares discriminant analysis (PLS-DAs), k-nearest neighbor (KNN), support vector machine (SVM), and random forest (RF) to classify pure vegetable oil with an accuracy of 100% [
13]. Jiang used FLS920 steady-state fluorescence spectrometer to collect 3D fluorescence spectrum data, combined with 2D-LDA feature extraction method to identify adulterated sesame oil, with a recognition accuracy of 100%, which is superior to PARAFAC-QDA (85%) and NPLS-DA (95%) methods [
14]. Currently, portable fluorescence spectrometers are employed for the detection of algal phyla [
15]. This paper utilizes three-dimensional fluorescence spectroscopy to analyze edible oil. In the future, it may be feasible to realize rapid and real-time detection, with the potential for mobile phone-based detection also being implemented.
Feature extraction is a crucial step in chemometric algorithms. Independent component analysis, wavelet transform, and convolutional neural networks have demonstrated excellent performance in eliminating background interference and extracting features [
16,
17,
18]. However, these algorithms can only handle spectra presented as two-dimensional data and fail to accurately represent the multi-channel characteristics of three-dimensional fluorescence spectra. Quaternions, an extended complex system, can inherently represent and process data with multi-channel and structured features, like color images (RGB three-channel) [
19]. The quaternion theory has been applied in image processing, signal analysis, and other fields, and it has shown unique advantages in dealing with multi-channel data [
20,
21]. Therefore, exploring the application of quaternion principal component analysis in the feature extraction of three-dimensional fluorescence spectra and the detection of frying oil content of edible oil holds significant theoretical and practical value.
SVR, PLSR, and various other prevalent regression analysis methods are employed for 3D FS [
22,
23,
24,
25,
26]. PSO, a random search algorithm, is based on simulating the foraging behavior of birds. This algorithm is capable of identifying the optimal solution for the research parameters in a minimal timeframe [
27]. In comparison to SVR and PLSR algorithms, PSO-LSSVR can identify the ideal key parameters adaptively, avoiding the limitations of artificial parameter selection [
28]. The PSO-LSSVR approach combines the benefits of PSO with LSSVR. As a result, the quantitative analytic approach of three-dimensional fluorescence spectroscopy combined with PSO-LSSVR is used to monitor the concentration of frying oil in edible oil.
This article employs various quaternion feature extraction methods in conjunction with classifiers to develop a judgment model for detecting adulterated edible oil. Subsequently, it establishes a quantitative model for the concentration of frying oil in adulterated edible oils, utilizing partial least squares regression (PLSRs), PSO-SVR, and PSO-LSSVR. The study identifies the optimal judgment model for adulterated edible oil and the quantitative model for frying oil concentration. This research offers a green, rapid, and pollution-free approach for detecting frying oil in edible oils.
2. Material and Methods
2.1. Sample Collection and Preparation
All oil samples were procured from local supermarkets and school canteen, comprising rapeseed oil, soybean oil, peanut oil, blending oil, and corn oil. The frying oil utilized in this study is sourced from the school cafeteria. The food item examined is chicken cutlets, which are cooked at a consistent temperature of 175 degrees Celsius for a duration of 7 min. The oil undergoes approximately 150 cycles per day. Fresh edible oils were adulterated with different concentrations of frying oil, specifically at levels of 0%, 5%, 10%, 30%, 50%, 70%, and 100%. Detailed specifications of the edible oils and the frying oil utilized in this study are provided in
Table 1.
The experimental edible oil samples were systematically labeled to denote their composition. Rapeseed oil samples with varying concentrations of frying oil were labeled C0 to C6; soybean oil samples D0 to D6; peanut oil samples H0 to H6; blended oil samples T0 to T6; and corn oil samples Y0 to Y6. Each oil type included seven distinct concentration gradients (0%, 5%, 10%, 30%, 50%, 70%, and 100% frying oil). For instance, representative sample configurations for rapeseed oil are detailed in
Table 2. Eight replicate samples were prepared for every concentration gradient across all oil types. Prior to analysis, all samples underwent vortex mixing followed by a 24 h equilibration period.
This paper involves the determination of adulterated edible oil and the detection of frying oil content. A total of 360 samples were used for the determination of adulterated edible oil, including 120 samples of edible oil and 240 samples of adulterated edible oil mixed with frying oil of different concentrations. When constructing the frying oil content detection model, there were no pure edible oil samples involved in the model building. There was a total of 240 samples, including 40 samples of 5%, 10%, 30%, 50%, 70%, and 100% frying oil. Prior to analysis, all samples were homogenized using a disposable syringe (20 mL) and subsequently transferred to colorimetric dishes.
2.2. Fluorescence Spectral Acquisition
Fluorescence spectra were acquired using an F-7000 spectrometer (Hitachi High-Technologies, Tokyo, Japan). Measurements employed a 10 mm path length non-fluorescent quartz cuvette. Instrumental parameters were configured as follows: excitation range 200–890 nm (20 nm increment, 5 nm slit), emission range 220–900 nm (10 nm increment, 5 nm slit), scan rate 30,000 nm/min, photomultiplier tube voltage 520 V, and 150 W xenon excitation source. In order to reduce the difference in fluorescence intensity caused by the time change in instrument and light source and ensure the accuracy of measurement, the spectrometer needs to be preheated for 20 min before each collection and the average of three measurements for each sample is taken as the final measurement result. All data analyses were performed in MATLAB (v. 2018a, MathWorks, Torrance, CA, USA), with visualizations generated using Origin2017 and Visio 2003 (Microsoft, Redmond, WA, USA).
2.3. Technical Roadmap
The overall technical workflow of this study is illustrated in
Figure 1.
Initially, three-dimensional fluorescence spectral data were acquired for pure edible oils and for edible oils adulterated with frying oil at varying concentrations. Subsequent to data collection, Rayleigh scattering regions were removed to eliminate artifacts that may interfere with spectral analysis. An automated peak-detection algorithm was then applied to extract key spectral features, including peak positions and fluorescence intensities. The preprocessed spectral data were subjected to qualitative analysis to determine the presence of frying oil adulteration. For this purpose, the following three feature extraction methods were employed: summation quaternion principal component analysis (QsPCA), modular quaternion principal component analysis (QqPCA), and multiplication quaternion principal component analysis (QmPCA). Classification was performed using the following three machine learning algorithms: KNN, PSO-SVM, and GA-SVM. For samples confirmed to contain frying oil, quantitative analysis was conducted to predict the adulteration level. This was achieved using regression models, including PLSR, PSO-SVR, and PSO-LSSVR.
4. Conclusions
4.1. Identification of Adulterated Edible Oil
In the establishment of the adulterated edible oil judgment model, 120 pure edible oil samples and 120 adulterated edible oil samples measured experimentally were used, totaling 240 samples. The 3D FS of 240 samples were measured. Perform QsPCA, QqPCA, and QmPCA on 240 samples to obtain a QPCA graph. The results show that QsPCA and QqPCA can effectively distinguish between edible oil and frying oil. The QmPCA can basically distinguish between edible oil and frying oil. The extraction of quaternion features through summation can be achieved by using fewer quaternion principal components for differentiation.
When selecting fluorescence spectrum data at excitation wavelengths of 360 nm, 380 nm, and 400 nm, the data obtained by summation quaternion feature extraction can be used as inputs for KNN, PSO-SVM, and GA-SVM, all of which can achieve 100% accuracy. The algorithm that uses the least quaternion principal component is the PSO-SVM algorithm. Only the first three quaternion principal component features need to be selected as inputs for PSO-SVM to establish a detection model for adulterated edible oil. The classification accuracy of the model can reach 100%.
4.2. Quantitative Model for Frying Oil
The experiment obtained 40 edible oil samples doped with 5%, 10%, 30%, 50%, 70%, and 100% frying oil, for a total of 240 samples. Select fluorescence spectral data at excitation wavelengths of 360 nm, 380 nm, and 400 nm as inputs for PLSR, PSO-SVR, and PSO-LSSVR, respectively, to establish a quantitative model for the proportion of frying oil in adulterated edible oil. The results show that the detection effect of frying oil concentration in adulterated edible oil based on PSO-LSSVR was the best, and the correlation coefficient of the test set reached 0.9663, proving that the correlation coefficient between the predicted value and the true value of the model reached 0.9663, and the root mean square error is 0.3685.
4.3. Prospect
This article presents a novel identification and quantitative detection framework for detecting adulterated edible oils and frying oils efficiently. Nonetheless, the efficacy of the quantitative detection model for frying oil is suboptimal. Future efforts should explore alternative quantitative analysis approaches or data selection from diverse spectral ranges to develop a more robust quantitative detection model for frying oil, aiming to attain a correlation coefficient of 0.99 or above in the test set, alongside minimizing the root mean square error. Subsequent research should focus on mitigating the risk of model overfitting and bolstering model stability.