Non-targeted detection of grape molasses adulteration with sugar and apple molasses by mid-infrared spectroscopy coupled to independent components analysis.

In the light of the current food security crisis, food adulteration has resurfaced on the international scene, inflicting potential safety issues and leading more and more consumers into deception. This situation led food control actors to remobilise their potential to face this problem, particularly in terms of analytical chemistry competencies. Similar to honey, grape molasses may be considered very likely to be adulterated leading to quality and authenticity issues, especially in the Eastern Mediterranean, where it is widely consumed as a traditional sweetener. This work reports the use of attenuated total reflectance-mid-infrared spectroscopy (ATR-MIR) coupled to chemometrics, as an alternative to complex, expensive and time-consuming analytical techniques, in the aim of detecting fraudulent glucose, fructose, sucrose and apple molasses additions to pure grape molasses. After collecting a widespread unadulterated grape molasses database, spiked samples with increasing concentrations (w/w) of the selected adulterants were prepared. In order to establish a qualitative model, whose potential is to detect adulteration and discriminate between the different adulterants, samples underwent ATR-MIR analyses without any prior preparation, and the collected spectral data were subjected to independent components analysis (ICA), where Random_ICA was used to retrieve the optimal number of independent components (ICs). Thereupon, the extraction of seven ICs allowed the establishment of a qualitative model with a clear discrimination between molasses adulterated with fructose, sucrose and glucose syrup, relying on MIR specific signals and incorporated ratios of the different adulterants. However, it failed in detecting apple molasses adulteration, calling for the development of a different analytical approach. The developed model underwent a verification step using a control set recorded on a different spectrometer, proving its potential to provide reproducible discrimination and classification rates.

Bioaccessibility of lead in Dittrichia viscosa plants and risk assessment of human exposure around a fertilizer industry in Lebanon.

Total and bioaccessible lead (Pb) concentrations in Dittrichia viscosa and soil samples were considered for estimating the potential health risk, related to both plant intake and accidental soil ingestion by adult and child consumers, near a Lebanese fertilizer plant. A total of 27 plant samples, from 9 uncultivated sites situated around the plant, were analyzed in order to assess the total and bioaccessible Pb content. Physiologically based extraction test (PBET) was used to estimate oral bioaccessibility of Pb in edible plant parts. Washed and unwashed leaves were compared in order to show the importance of good consumer practice on Pb intake. Extracted Pb in the intestinal medium accounted for 24 up to 87% of Pb extracted in the gastric medium. The total hazard quotient (HQtot) and the total bioaccessible hazard quotient (BHQ), related to both plants' intake and soil ingestion, for two maximalist child and adult scenarios, were calculated in order to estimate human health risk assessment. HQtot estimations considering the total concentration of Pb in soil and plant suggest that this metal is a contributor in elevating health risks problems on local plants' consumers, especially children inhabitants. However, the integration of bioaccessible concentrations of Pb in risk estimations reduces remarkably the potential risk.

Bioaccessibility and radioisotopes of lead in soils around a fertilizer industry in Lebanon.

The use of phosphate ore by fertilizer industries is considered a major source of soil contamination by trace metals and radionuclides. Despite its low mobility and bioavailability, lead (Pb) is among soil contaminants that pose a serious risk to human health. This study evaluates the potential impact of a fertilizer factory in North Lebanon on the total content of Pb and the activity concentration of its radioisotopes in residential, non-agricultural lands around the industry, as well as its mobility and bioaccessibility in soil samples collected at different depths. Chemical extractions by EDTA and in vitro physiologically based extraction test were used to estimate, respectively, the available and bioaccessible fractions of Pb in soils. Radioisotopes 214Pb, 212Pb and 210Pb have been analyzed by gamma spectrometry. Different physicochemical soil parameters, such as pH, carbonate content, electrical conductivity, cation exchange capacity, clay, total nitrogen and redox potential, were studied. The pseudo-total Pb varied between 12.8 and 68.5 mg kg-1, while the extractable fractions were more variable, between 12 and 72% of total Pb concentration for the EDTA extracted fraction and up to 28.5% for the bioaccessible fractions. The processing of the data shows the decreases with depth in most sites of the total and available Pb and of the activity concentration of 210Pb and their positive correlations with total nitrogen. These variations and relationships with the location of studied sites show the influence of emissions from the factory or the transport of ore and by-products. The correlations between available and bioaccessible Pb on one hand, between available Pb and 210Pb on another hand, raise the question of health risk assessments taking into account the bioaccessibility of Pb and its radioisotopes.

Chemical Variability of the Essential Oil of Origanum ehrenbergii Boiss. from Lebanon, Assessed by Independent Component Analysis (ICA) and Common Component and Specific Weight Analysis (CCSWA).

Origanum ehrenbergii Boiss., an endemic plant to Lebanon, is widely acknowledged in Lebanese traditional medicine. The aim of the present study was to evaluate the influence of the drying method, region, and time of harvest on yield and chemical composition of O. ehrenbergii essential oils (EOs). Plants were harvested monthly throughout 2013 and 2014, from two different regions, Aabadiye and Qartaba, then dried using two drying methods: lyophilization and shade-drying at 4 °C. EO was extracted by hydrodistillation and analyzed by GC/MS. GC-MS data, combined with independent component analysis (ICA) and common component and specific weight analysis (CCSWA), showed that drying techniques, region of harvest, and soil composition have no effect on the chemical composition of O. ehrenbergii EOs. Of the factors analyzed, only harvesting time affected the EO composition of this species. High and stable amounts of carvacrol, associated with reliable antimicrobial activities, were detected in material harvested between March and October. EOs obtained from plants harvested in Aabadiye in January and February showed high amounts of thymoquinone, related to anti-inflammatory and cytotoxic effects. The use of ICA and CCSWA was proven to be efficient, and allowed the development of a discriminant model for the classification of O. ehrenbergii chemotype and the determination of the best harvesting time.

Characterization of spatial and temporal patterns in surface water quality: a case study of four major Lebanese rivers.

In this work, four major Lebanese rivers were investigated, the Damour, Ibrahim, Kadisha, and Orontes, which are located in South, Central, and North Lebanon and Bekaa Valley, respectively. Five sampling sites were considered from upstream to downstream, and 12 sampling campaigns over four seasons were conducted during 2010-2011. Thirty-seven physicochemical parameters and five microbial tests were evaluated. A principal component analysis (PCA) was used for data evaluation. The first PCA, applied to the matrix-containing data that was acquired on all four rivers, showed that each river was distinct in terms of trophic state and pollution sources. The Ibrahim River was more likely to be polluted with industrial and human discharges, while the Kadisha River was severely polluted with anthropogenic human wastes. The Orontes and Damour rivers seemed to have the lowest rates of water pollution, especially the Orontes, which had the best water quality. PCA was also performed on individual data matrices for each river. In all cases, the results showed that the springs of each river have good water quality and are free from severe contamination. The other monitoring sites on each river were likely exposed to human activities and showed important spatial evolution. Through this work, a spatiotemporal fingerprint was obtained for each studied river, defining a "water mass reference" for each one. This model could be used as a monitoring tool for subsequent water quality surveys to highlight any temporal evolution of water quality. Graphical abstract ᅟ.

An untargeted evaluation of food contact materials by flow injection analysis-mass spectrometry (FIA-MS) combined with independent components analysis (ICA).

Food contact materials (FCMs), especially plastics, are known to be a potential source of contaminants in food. In fact, various groups of additives are used to protect the integrity of the material during processing and life time. However, these intentionally added substances (IAS) could also lead to degradation products called non-intentionally added substances (NIAS), due to reactions occurring in the polymeric material. Complex mixtures of components may therefore be generated within the material, creating a source of potential migrating substances towards food in contact. In this context, an innovative analytical approach is proposed in order to assess IAS and NIAS in plastic FCMs for a fast screening of their composition. For this purpose, solvent extracts of polyethylene (PE) pellets, containers and films were analyzed by flow injection analysis-mass spectrometry (FIA-MS). This direct approach offers the ability to perform a large number of analyses in a short time. Mass spectral fingerprints were then treated by a multivariate data analysis technique called independent components analysis (ICA) in order to overcome the complexity of such data and to highlight hidden information related to IAS and NIAS molecules. ICA applied on mass spectral fingerprints of PE extracts highlighted group discriminations related to different m/z values which were putatively assigned to IAS and also to NIAS. In order to confirm these putative annotations, a hybrid LTQ-Orbitrap was used for high resolution mass spectrometry analysis. Moreover, MS/MS experiments were performed on some discriminant ions to improve their putative identification. The proposed methodology combining FIA-MS fingerprints and ICA proved its efficiency in identifying IAS and NIAS in plastic FCMs and its capability to discriminate different PE samples, in a relatively fast approach compared to classical analytical techniques. This approach may help the FCMs classification for compounders in the selection of the starting substances in plastic formulation and for plastic converters in the control of manufacturing processes as well as for the monitoring of final products.

Determination of the optimal number of components in independent components analysis.

Independent components analysis (ICA) may be considered as one of the most established blind source separation techniques for the treatment of complex data sets in analytical chemistry. Like other similar methods, the determination of the optimal number of latent variables, in this case, independent components (ICs), is a crucial step before any modeling. Therefore, validation methods are required in order to decide about the optimal number of ICs to be used in the computation of the final model. In this paper, three new validation methods are formally presented. The first one, called Random_ICA, is a generalization of the ICA_by_blocks method. Its specificity resides in the random way of splitting the initial data matrix into two blocks, and then repeating this procedure several times, giving a broader perspective for the selection of the optimal number of ICs. The second method, called KMO_ICA_Residuals is based on the computation of the Kaiser-Meyer-Olkin (KMO) index of the transposed residual matrices obtained after progressive extraction of ICs. The third method, called ICA_corr_y, helps to select the optimal number of ICs by computing the correlations between calculated proportions and known physico-chemical information about samples, generally concentrations, or between a source signal known to be present in the mixture and the signals extracted by ICA. These three methods were tested using varied simulated and experimental data sets and compared, when necessary, to ICA_by_blocks. Results were relevant and in line with expected ones, proving the reliability of the three proposed methods.

Spatial and temporal assessment of surface water quality in the Arka River, Akkar, Lebanon.

Surface water quality monitoring constitutes a crucial and important step in any water quality management system. Twenty-three physicochemical and microbiological parameters were assessed in surface water samples collected from the Arka River located in the Akkar District, north of Lebanon. Eight sampling locations were considered along the river and seven sampling campaigns were performed in order to evaluate spatial and temporal influences. The extraction of relevant information from this relatively large data set was done using principal component analysis (PCA), being a very well established chemometric tool in this field. In a first step, extracted PCA loadings revealed the implication of several physicochemical parameters in the discriminations and trends highlighted by PCA scores, mainly due to soil leaching and seawater intrusion. However, further investigations showed the implication of organic and bacterial parameters in the discrimination of stations in the Akkar flatland. These discriminations probably refer to anthropogenic pollution coming from the agricultural area and the surrounding villages. Specific ultraviolet absorption (SUVA) indices confirmed these findings since values decreased for samples collected across the villages and the flatland, indicating an increase in anthropogenic dissolved organic matter. This study will hopefully help the national and local authorities to ameliorate the surface water quality management, enabling its proper use for irrigation purposes.

Chemometric Tools to Highlight the Variability of the Chemical Composition and Yield of Lebanese Origanum syriacum L. Essential Oil.

This study deals with the variation in the yield and composition of Lebanese Origanum syriacum L. essential oil (EO) according to harvesting time, drying methods used, and geographical location. Plant material was harvested twice a month all over 2013 and 2014 from Qartaba and Achkout located at high altitude and from Byblos at low altitude. EOs of the aerial parts were obtained by hydrodistillation. The highest yields were obtained at full flowering stage and slightly reduced after flowering. The GC/MS analysis revealed the presence of 50 components representing 90.49 - 99.82%, 88.79 - 100%, and 95.28 - 100% of the total oil extracted from plants harvested from Qartaba, Achkout, and Byblos, respectively. The major components in the oils were: carvacrol (2.1 - 79.8%), thymol (0.3 - 83.7%), p-cymene (2.8 - 43.8%), thymoquinone (0.4 - 27.7%), γ-terpinene (0.4 - 10.0%), octan-3-ol (0.3 - 4.9%), caryophyllene oxide (0.2 - 4.7%), oct-1-en-3-ol (0.3 - 3.7%), ß-caryophyllene (0.7 - 3.2%), cis-sabinene hydrate (0.1 - 2.8%), terpinen-4-ol (0.1 - 2.8%), and α-terpinene (0.2 - 2.2%). Independent components analysis (ICA) revealed that two groups were discriminated, reflecting compositional differences in the EOs profiles of the Lebanese oregano samples: O. syriacum grown in Qartaba and Achkout belongs to carvacrol chemotype, while O. syriacum grown in Byblos belongs to thymol chemotype. The flowering phase was the most productive period in terms of yield, bringing marked changes in the EO composition by increasing the amounts of carvacrol or thymol, and decreasing those of thymoquinone and p-cymene.

Attenuated total reflectance-mid infrared spectroscopy (ATR-MIR) coupled with independent components analysis (ICA): A fast method to determine plasticizers in polylactide (PLA).

Compliance of plastic food contact materials (FCMs) with regulatory specifications in force, requires a better knowledge of their interaction phenomena with food or food simulants in contact. However these migration tests could be very complex, expensive and time-consuming. Therefore, alternative procedures were introduced based on the determination of potential migrants in the initial material, allowing the use of mathematical modeling, worst case scenarios and other alternative approaches, for simple and fast compliance testing. In this work, polylactide (PLA), plasticized with four different plasticizers, was considered as a model plastic formulation. An innovative analytical approach was developed, based on the extraction of qualitative and quantitative information from attenuated total reflectance (ATR) mid-infrared (MIR) spectral fingerprints, using independent components analysis (ICA). Two novel chemometric methods, Random_ICA and ICA_corr_y, were used to determine the optimal number of independent components (ICs). Both qualitative and quantitative information, related to the identity and the quantity of plasticizers in PLA, were retrieved through a direct and fast analytical method, without any prior sample preparations. Through a single qualitative model with 11 ICs, a clear and clean classification of PLA samples was obtained, according to the identity of plasticizers incorporated in their formulations. Moreover, a quantitative model was established for each formulation, correlating proportions estimated by ICA and known concentrations of plasticizers in PLA. High coefficients of determination (higher than 0.96) and recoveries (higher than 95%) proved the good predictability of the proposed models.

Independent components analysis coupled with 3D-front-face fluorescence spectroscopy to study the interaction between plastic food packaging and olive oil.

Olive oil is one of the most valued sources of fats in the Mediterranean diet. Its storage was generally done using glass or metallic packaging materials. Nowadays, plastic packaging has gained worldwide spread for the storage of olive oil. However, plastics are not inert and interaction phenomena may occur between packaging materials and olive oil. In this study, extra virgin olive oil samples were submitted to accelerated interaction conditions, in contact with polypropylene (PP) and polylactide (PLA) plastic packaging materials. 3D-front-face fluorescence spectroscopy, being a simple, fast and non destructive analytical technique, was used to study this interaction. Independent components analysis (ICA) was used to analyze raw 3D-front-face fluorescence spectra of olive oil. ICA was able to highlight a probable effect of a migration of substances with antioxidant activity. The signals extracted by ICA corresponded to natural olive oil fluorophores (tocopherols and polyphenols) as well as newly formed ones which were tentatively identified as fluorescent oxidation products. Based on the extracted fluorescent signals, olive oil in contact with plastics had slower aging rates in comparison with reference oils. Peroxide and free acidity values validated the results obtained by ICA, related to olive oil oxidation rates. Sorbed olive oil in plastic was also quantified given that this sorption could induce a swelling of the polymer thus promoting migration.

Rapid discrimination of plastic packaging materials using MIR spectroscopy coupled with independent components analysis (ICA).

Plastic packaging wastes increased considerably in recent decades, raising a major and serious public concern on political, economical and environmental levels. Dealing with this kind of problems is generally done by landfilling and energy recovery. However, these two methods are becoming more and more expensive, hazardous to the public health and the environment. Therefore, recycling is gaining worldwide consideration as a solution to decrease the growing volume of plastic packaging wastes and simultaneously reduce the consumption of oil required to produce virgin resin. Nevertheless, a major shortage is encountered in recycling which is related to the sorting of plastic wastes. In this paper, a feasibility study was performed in order to test the potential of an innovative approach combining mid infrared (MIR) spectroscopy with independent components analysis (ICA), as a simple and fast approach which could achieve high separation rates. This approach (MIR-ICA) gave 100% discrimination rates in the separation of all studied plastics: polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polystyrene (PS) and polylactide (PLA). In addition, some more specific discriminations were obtained separating plastic materials belonging to the same polymer family e.g. high density polyethylene (HDPE) from low density polyethylene (LDPE). High discrimination rates were obtained despite the heterogeneity among samples especially differences in colors, thicknesses and surface textures. The reproducibility of the proposed approach was also tested using two spectrometers with considerable differences in their sensitivities. Discrimination rates were not affected proving that the developed approach could be extrapolated to different spectrometers. MIR combined with ICA is a promising tool for plastic waste separation that can help improve performance in this field; however further technological improvements and developments are required before it can be applied at an industrial level given that all tests presented here were performed under laboratory conditions.

Chemometric tools to highlight possible migration of compounds from packaging to sunflower oils.

Polyethylene terephthalate (PET) could be considered for the packaging of vegetable oils taking into account the impact of its oxygen permeability on the oxidation of the oil and the migration of volatile organic compounds (VOC) from the polymer matrix. After accelerated aging tests at 40 °C for 10, 20, and 30 days, the headspace of three sunflower oils packed in PET with high density polyethylene caps was carried out using solid phase microextraction. VOCs such as benzene hydrocarbons, ethylbenzene, xylene isomers and diethyl phthalate were identified in vegetable oils by gas chromatography coupled to mass spectrometry. Chemometric tools such as principal components analysis (PCA), independent components analysis (ICA), and a multiblocks analysis, common components and specific weight analysis (CCSWA) applied to analytical data were revealed to be very efficient to discriminate between samples according to oil oxidation products (hexanal, heptanal, 2-pentenal) and to the migration of packaging contaminants (xylene).

Chemometric tools to highlight non-intentionally added substances (NIAS) in polyethylene terephthalate (PET).

In an effort to identify non-intentionally added substances (NIAS), which is still a challenging task for analytical chemists, PET pellets, preforms and bottles were analyzed by an optimized headspace solid phase microextraction coupled to gas chromatography-mass spectrometry (HS-SPME/GC-MS). Fingerprints obtained by the proposed method were analyzed by three chemometric tools: Principal Components Analysis (PCA), Independent Components Analysis (ICA) and a multi-block method (Common Components and Specific Weights Analysis CCSWA) in order to extract pertinent variations in NIAS concentrations. Total ion current (TIC) chromatograms were used for PCA and ICA while extracted ion chromatograms (EIC) were used for CCSWA, each ion corresponding to a block. PCA managed to discriminate pellets and preforms from bottles due to several NIAS. Volatiles like 2-methyl-1,3-dioxolane, ethylene glycol, ethylbenzene and xylene were responsible for the discrimination of pellets and preforms. Less volatile compounds like linear aldehydes and phthalates were responsible for the discrimination of bottles. ICA showed more specific discriminations especially for bottles and pellets while CCSWA managed to discriminate preforms. The proposed methodology, combining HS-SPME/GC-MS with chemometric tools proved its efficiency in highlighting NIAS in PET samples in a relatively simple and fast approach compared to classical techniques.