Marinades significantly influence the PAHs levels in meat products. For that, this work aimed to study the impact of Lebanese red and white dressings along with some of their constituents (apple vinegar, lemon, garlic paste, and yogurt) on the formation of polycyclic aromatic hydrocarbons (PAHs) in charcoal grilled meat products. The results showed that both white and red dressings increased the PAH4 formation in meat products with a slightly higher effect in case of white sauces (PAHs increased by 146.7 % with white sauce and by 120 % in red toppings). Furthermore, yogurt marination enhanced the PAHs levels by 137.8 % as a result of its composition that contains PAHs precursors. On the other hand, PAHs levels were significantly (p < 0.05) reduced by 46.6 % upon using apple vinegar, by 37 % upon using lemon, and by 55.6 % with garlic paste due to their acidity and antioxidant activity.
Antimicrobial residues in milk pose a significant risk to human health, prompting regulatory bodies to establish safety limits to protect consumers. While traditional screening methods have primarily targeted single analytes or classes, recent advancements in multiclass screening techniques offer more comprehensive and efficient monitoring. This review highlights these advancements and focuses on methods developed since 2010, such as microbial inhibition tests, immunoassays, biosensors and LC–MS-based approaches. It also discusses the strengths and limitations of these techniques, as well as the challenges associated with analysing milk's complex matrix, emphasising the ongoing need for innovation in food safety practices.
Antimicrobials are administered in livestock for different uses leading to milk contamination and several undesirable effects. Because there is a lack of surveillance of antimicrobial residues (AMRs) in milk and dairy products in Lebanon, this study aims to determine the occurrence of AMRs in 90 Lebanese samples of milk and labneh (concentrated yoghurt). Multi-residue screening methods with suitable sample preparations were applied to detect 71 AMRs in milk and labneh, respectively, using LC-MS/MS. Of the total number of samples, 71% was contaminated with AMRs and (fluoro)quinolones and macrolides were the most detected families. Additional confirmation tests proved that 6.7% of the milk samples were non-compliant for the macrolides tilmicosin, tulathromycin and spiramycin. Moreover, some labneh prepared from contaminated milk samples was analysed to determine the fate of AMRs during the manufacturing process. The results showed that some AMRs could be concentrated, eliminated or degraded, based on their physicochemical characteristics.
Lebanon's agricultural sector, known for its diverse crop and livestock production, faces challenges in the international market due to the presence of chemical residues and contaminants in its food exports. Recent rejections of these exports have raised global concerns about food safety, increasingly seen as vital for public health and economic prosperity. This review focuses on examining scientific studies about the levels of various chemical residues including pesticides, and veterinary drugs and contaminants like mycotoxins, and polycyclic aromatic hydrocarbons, and heavy metals in Lebanese food products. Findings indicate that these residues and contaminants often exceed both the maximum residue limits (MRLs) and maximum limits (MLs) set by the Codex Alimentarius and the European Union. The review concludes with recommendations for reducing these contaminants and residues to enhance Lebanon's food safety and quality, aligning with international standards, and mitigating the risk of export rejections.
In this paper, we investigate for the first time the contamination source and the ecological risk associated to organochlorinated compounds in the Litani system. For this purpose, the levels of 7 polychlorinated biphenyls (PCBs) and 13 organochlorinated pesticides (OCPs) were assessed, using a microwave-assisted extraction coupled to gas chromatography-electron capture detector (MAE/GC-ECD) method, in surficial sediments from 30 sites along the main course of the river, two major tributaries, and the Quaraoun Lake. ∑7PCBs exhibited total concentrations ranging from 0.11 to 8 ng g−1 of dry weight and are not able apparently to pose ecological risks since none of the samples showed concentration above the effects range low (ERL) guideline (22.7 ng g−1). The detected levels of OCPs in the river were significantly higher than those of PCBs; ∑13OCPs range from 0.5 to 46.5 ng g−1 of dry weight. Overall, the integrated eco-toxicological risk imposed by the organochlorine contamination in the Litani River, estimated as the mean effects range medium quotient (mERMq), is considered low with risk probability lower than 21
Labneh is a dairy product highly consumed in Lebanon, prepared from straining yogurt. Because there is a lack of surveillance of the antimicrobial residues (AMRs) in milk and dairy products in Lebanon, this project was launched to develop a screening method for the detection of AMRs in labneh. In this study, we optimized a multi-residue screening method to detect 71 AMRs based on liquid–liquid extraction using buffered acetonitrile with 2 M ammonium acetate followed by freezing out the supernatant for 30 min at −23 °C. The extracts were then analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS). This method was then validated against the Guidance (EU) CRLs 2010/01. The performance of the method showed a good specificity with no false negative rate and detection capabilities (CCβ) were below maximum residue levels (MRLs) for all analytes. In addition, this method demonstrated acceptable recoveries estimated in the range 70–130
Polycyclic aromatic hydrocarbons (PAHs) are environmental contaminants that continue to attract researchers' attention until these days due to their toxicity and their multisource emission. In this study, levels of 17 active molecules of PAHs were investigated in marine and continental Lebanese aquatic systems. The results showed that Lebanese seawater is more contaminated than several other sites on the Mediterranean Sea. On the marine side, the total concentration of PAHs ranges from 55.7 to 2683.8 ng L −1 in water and from 19.09 to 2025.03 ng g −1 in sediments. On the continental side, the total concentration ranges from 465.7 to 1399.9 ng L −1 in water and from 72.6 to 1074.7 ng g −1 in sediments presenting higher contamination and detection frequency than the marine sites. Pearson test was applied to determine the preference of PAHs toward one of the phases and showed that when the number of rings, the molecular mass and the log K o/ w increase, PAHs accumulate in sediments, and when the water solubility and the vapor pressure of PAHs increase, they tend to remain in the aqueous phase. Moreover, PAHs in Lebanese sediments were combustion-originated and resulted mainly from industrial sites set next to aquatic systems and heavy traffic especially along the Lebanese coastline. Regarding the toxicity effect, the use of the ERL/ERM approach revealed that few sites have individual PAHs levels that may occasionally cause biological adverse effects to benthic organisms; nevertheless, the ecosystem risk of PAHs in Lebanese sediments is low.
The use of hormones for breeding animal livestock has been banned since 1981 under the Council Directive 81/602/EC. So far, each country should monitor the use of anabolic hormones in animal production to protect the consumer's health against these unwanted residues. This paper presents the research results on steroid and non-steroid hormones residues carried out in Lebanon from 2018 to 2020. Using a newly developed and validated LC-MS/MS method, the detection and the quantification of hormones in bovine matrices were done. The targeted matrices were muscle, liver, kidney, and bile. A total of two-hundred and forty-seven samples were collected from different slaughterhouses located in six different cities in Lebanon. Interestingly, only four hormones were found: testosterone, progesterone, epitestosterone, and 6 propyl 2thiouracil. Based on the obtained data, the estimated daily intake, hazard quotient, and hazard index were calculated to evaluate an exposure assessment.
AbstractHoney is one of the most valuable sweeteners consumed by humans all over the world. Consequently, it is often a target for adulteration through the addition of different sugar syrups during or after honey production, resulting in a reduction in its nutritive value. For the first time, this study analyzes honey samples of various botanical species collected from different Lebanese regions using element analyzer (EA) and liquid chromatography (LC) coupled with isotope ratio mass spectrometry (IRMS). The δ13C of bulk honey, its protein fraction, and the main individual sugars (glucose, fructose, disaccharides, and trisaccharide) were determined, in order to characterize and evaluate the authenticity of honey consumed in Lebanon. The results showed that the δ13C values for bulk honey and its protein range from −26.5‰ to −24.5‰ and from −26.4‰ to −24.7‰, respectively, for authentic samples. δ13C values for samples adulterated with sugar syrups range from −11.2‰ to −25.1‰ for bulk honey and from −26.6‰ to −23.7‰ for its proteins, with a difference between bulk and protein values between −1 and −8.7‰. Using LC‐C‐IRMS techniques, the δ13C of individual sugars provides additional information on the presence of undeclared sugars. We found that all authentic samples had Δδ13Cf‐g and Δδ13C max values within the naturally occurring range of ±1‰ and ±2.1‰, respectively, while the adulterated samples fall outside the Δδ13C ranges. The oligosaccharide peak was detected in most adulterated samples.
Abstract This study investigates, for the first time, the PAH4 levels (benzo[a]anthracene, chrysene, benzo[b]fluoranthene, and benzo[a]pyrene) in the most traditional Lebanese meat products. The study explores the effect of the surface/mass ratio and the influence of the cooking methods; broasted frying, vertical gas grilling and charcoal gas grilling, on the PAH4 formation. A total of 176 samples from seven charcoal-grilled meat dishes, 12 broasted chicken, and 12 gas grilled chicken dishes collected from different restaurants, together with 62 house charcoal-grilled samples, were prepared and analyzed. The results show that 62 charcoal-grilled restaurant samples (35.2%) and 24 charcoal-grilled house samples (38.7%) exceeded the Maximum Residue Limits (MRLs) for PAH4 of smoked meat (12.0 µg kg−1) established by the European Commission. In restaurant samples, the PAH4 levels in all samples ranged between 1.39 and 36.94 µg kg−1, whereas in house grilling samples, the PAH4 levels in all samples ranged between 1.23 and 52.79 µg kg−1. Additionally, the results of this study illustrate that the charcoal-grilled chicken samples showed an enormous augmentation 3- to 40-fold than gas-grilled and broasted fried chicken. Besides, a high correlation was displayed between the PAH levels and the: fat content and surface/mass ratio.
The treatment of animals with antimicrobial products may lead to the contamination of edible tissues by their residues, which may represent a risk to human health. Therefore, this study aimed to determine the level of antimicrobial residues in food-producing animals (chicken, beef, and milk) in Lebanon. A total of 310 samples were collected and analysed using an LC-MS/MS for the determination of 48 compounds belonging to different families in order to map their compliance according to the European Commission decision 2002/657/EC. Results show that 60% of the analysed samples were not contaminated by any residue, while 12% presented a concentration higher than the MRLs for tetracyclines, sulphonamides, quinolones, and macrolides. Results revealed that chicken were the most contaminated by antimicrobial residues, when compared to beef and milk. The obtained results demonstrate the uncontrolled use of antimicrobials in some Lebanese farms and claim for better management of livestock.
Dechlorane Related Compounds (DRCs), including Dechlorane Plus (syn/anti-DP or syn/anti-DDC-CO) and related compounds (Dec-601 or DDC-ID, Dec-602 or DDC-DBF, Dec-603 or DDC-Ant and Chlordene Plus or DDC-PDD), are a group of polychlorinated flame retardants of concern since they were first reported in various environmental and biota matrices about one decade ago. In this work, we investigated the dietary intake of the Lebanese population to these lipophilic environmental contaminants upon the evaluation of selected foodstuff contamination. Collected food samples (n = 58) were selected to be representative of the lipid fraction of the whole diet of the Beiruti population. The samples were analysed using pressurized liquid extraction, silica multilayer column followed by gel permeation chromatography for purification and GC-EI-HRMS for separation and detection. Detection frequency of at least one compound among Dechlorane Plus (syn-DP and anti-DP), Dechlorane 602, 603 and Chlordene Plus) was 91%. The mean concentrations of Sigma 6DRCs, by food group, ranged from 4.7 to 29.5 pg g(-1) wet weight in lowerbound (LB) and from 6.7 to 76.9 pg g(-1) wet weight in upperbound (UB). Based on food habits, the dietary intake of Beiruti adults was estimated to be between 3.71 (LB) and 5.61 (UB) ng day(-1). Dechlorane Plus and Dechlorane 602 were the dominant compounds, contributing to 70 and 24% of the total intake (LB value), respectively. This study reports for the first time the occurrence of Dechioranes in Lebanese foods and proposes corresponding deterministic dietary exposure scenario. (C) 2019 Elsevier Ltd. All rights reserved.
In Lebanon, apples are among the most consumed commodities; however, pesticide residues in apples have not been evaluated so far. Therefore, this study presents the occurrence of pesticide residues in apples produced in Lebanon during 2012-2016. A total of 212 samples were analysed for the presence of pesticides using the QuEChERS multi-residue extraction method, followed by GC-MS. Pesticide residues were not observed in 23% of the samples. Whereas pesticide residues were found in 77% of the samples, among them 61% exceeded the maximum residue limits (MRL) and 16% contained residues below the MRL. The most frequently detected pesticide residues were chlorpyrifos (n=142), methidathion (n=34), cypermethrin (n=21), lambda-cyhalothrin (n=16), myclobutanil (n=13) and diazinon (n=9). A preliminary long-term exposure assessment for the detected pesticides in apples showed that Hazard Quotient (HQ) was in the range of 0.1-8% of the ADI's, indicating no risk to human health.
This work demonstrates that the fungicide thiophanate-methyl generates a sensitizing photoproduct upon irradiation in solar light and explains how the reaction proceeds. The degradation profileof aqueous thiophanatemethyl in simulated solar light showed an autoaccelerated shape indicating the formation of some photodegrading compounds. Among the detected photoproducts, I (lambda(max) = 340 nm), a quinoxaline derivative generated in the very beginning of the reaction seemed to be the molecule responsible for this autoacceleration. Further experiments were conducted to confirm this hypothesis. The laser flash photolysis (lambda(exc) = 355 nm) of I generated a transient species reminiscent to the triplet excited state of unsubstituted quinoxaline. The two triplets reacted with the phenolic probe, 2,4,6-trimethylphenol, with k = 2 x 10(9) M-1 s(-1). Steady-state irradiations showed that thiophanate-methyl drastically accelerated the photolysis of the probe in an auto-accelerated reaction confirming the production of a sensitizing photoproduct. Moreover, unsubstituted quinoxaline sensitized the degradation of thiophanate-methyl showing that this latter contains labile H atoms. All these data confirmed that I was the sensitizer responsible for the auto-accelerated light induced transformation of thiophanate-methyl. The mechanism of formation of I was studied by quantum calculations. It proceeds through photocyclisation to form a S-S bridge, followed by intra and intermolecular H abstractions and finally departure of HSS'The sensitizing properties of micropollutants photoproducts open a large array of investigations. Our study provides a reliable approach to investigate the overlooked photosensitizing effect of photoproducts during photochemical reactions in water and opens the way to a vast array of research.
In this study, we examined the photodegradation of decabromodiphenyl ether (BDE-209) on the surface of car seat covers from end-of-life vehicles (ELVs). Samples were collected at two car dismantling facilities in Sweden and cover car models from 1989 to 1998. The content of polybrominated diphenyl ethers (PBDEs) in nine real samples (fabric and polyurethane foam) was first characterized. Fabric samples that did not contain BDE-209 were then spiked with BDE-209 and irradiated in the laboratory and under sunlight. Photoproducts were identified using high performance liquid chromatography coupled to electrospray ionization mass spectrometer (HPLC-ESI-Orbitrap-MS), whereas volatile products were analyzed by gas chromatography-mass spectrometry (GC-MS). Similar photodegradation rates and oxidation products were observed in fabric samples irradiated in the laboratory and those collected from ELVs. Estimated half-life of BDE-209 on fabric inside vehicles ranged from 3 to 6 years. Thirteen major photoproducts were identified as lower brominated products, hydroxylated BDEs, brominated and hydroxylated dibenzofurans (PBDFs) and dioxins (PBDDs). Furthermore, several photoproducts were found to be transferable into water, particularly bromophenols and hydroxylated BDEs, and others into gas phase, such as bromomethanol and 1,2-dibromoethane. This should be taken into consideration for better estimating exposure to PBDEs and to develop strategies for ELV recycling.
Increasing attention is being paid to the environmental fate and impact of plastics and their additives under sunlight exposure. We evaluated the photodegradation of polystyrene (PS) films (∼100 μm) containing brominated flame retardants (BFRs): decabromodiphenylether (BDE-209), tetrabromobisphenol A (TBBPA), and tetrabromobisphenol A-bis (2.3-dibromopropylether) (TBBPA-DBPE). Irradiations were performed in a solar simulator and outdoors. Infrared (IR) analyses indicated an acceleration of the photooxidation rate of fire-retarded PS films compared to pure PS with an enhancement factor of 7 for TBBPA-DBPE and TBBPA, and 10 for BDE-209. The accelerating effect was found to be correlated with the quantum yield for BFR photodegradation and its absorbance in the PS films. The presence of BFRs also modified the PS photooxidation mechanism and resulted in the formation of 14 brominated photoproducts via bromination and oxidation of PS. Furthermore, a drastic increase in chain scissions and loss of molecular weight was revealed by size exclusion chromatography. This enhanced degradation of PS led to significant leaching (15%) of oxidation products from PS films after immersion in water, and to the gas-phase emission of several volatile brominated products. Our findings suggest that fire-retarded plastics may be a source of potentially hazardous contaminants when exposed to sunlight.
Brominated flame retardants (BFRs) are widely used as additives in plastics, textiles and electronics materials. Here, we investigated the photodegradation of four BFRs including decabromobiphenylether (BDE-209), tetrabromobipsphenol A (TBBPA), tetrabromobisphenol A-bis(2,3-dibromopropylether) (TBBPA-DBPE) and tetrabromobisphenol A bis (allyl) ether (TBBPA-BAE). Experiments were carried out in polystyrene (PS) films using monochromatic and polychromatic irradiations. For comparison, irradiations were also carried in a solvent (tetrahydrofuran: THF). Monitoring of BFR degradation was performed using bulk and surface infrared (IR) measurements, as well as by extraction and HPLC-UV. Photoproducts were characterized using HPLC-high resolution electrospray ionization mass spectrometry (HPLC-ESI-Orbitrap-MS). All four BFRs underwent photochemical transformation in THF at 290 nm with a quantum yield (Phi) ranging from 0.05 for TBBPA to 0.27 for BDE-209, indicating an increase of photoreactivity with the number of Br atoms in BFRs. On the other hand, no major difference in the c values was observed when BFRs were embedded in PS films (Phi: 0.82-0.89). The higher photoreactivity in PS appears to be associated with a fast oxidation of PS as revealed by infrared (IR) analysis and yellowing of the films. Interestingly, the faster the yellowing occurred, the faster the BFR degradation was inhibited due to light screening effect. Several major photoproducts were identified for TBBPA and TBBPA-DBPE. Additional photoproducts possibly arising from PS oxidation and bromination by Br center dot were observed for the first time. This work provides a better understanding of the reactivity and fate of BFRs in polymers allowing for a better assessment of their environmental impacts. (C) 2018 Elsevier Ltd. All rights reserved.
Pesticides are between the major contaminants that invade aquatic environments.Pesticides monitoring programs were usually conducted using active sampling method in environmental water sites to evaluate the real state of the aquatic media.Polar Organic Chemical Integrative Sampler (POCIS) was recently used for the monitoring of polar pesticides residues in environmental water.The application requires its prior calibration in order to determine the sampling rate "Rs" needed to evaluate the real water concentration of analytes.This paper generates the "Rs" values in water for 24 pesticides never been generated previously.The POCIS laboratory-calibration was performed in glass beakers on the basis of static renewal exposure under stirred conditions for 25 days.The accumulation kinetics of these pesticides was evaluated and the Rs values found varied from 0.0186 to 0.316 L day-1 with RSD˂ 24%.The effect of hydrophobicity on sampling rates (Rs) was also evaluated.Furthermore, we evaluated the applicability of deuterated Atrazine (ATR d5) as Performance Reference Compounds (PRC) to account for between-site variation.High performance liquid chromatography (HPLC) coupled with triple quadrupole tandem mass spectrometry (LC-MS/MS) was used for the analysis.
Pesticides are between the major contaminants that invade aquatic environments Pesticides monitoring programs were usually conducted using active sampling method in environmental water sites to evaluate the real state of the aquatic media Polar Organic Chemical Integrative Sampler POCIS was recently used for the monitoring of polar pesticides residues in environmental water The application requires its prior calibration in order to determine the sampling rate rdquo Rs rdquo needed to evaluate the real water concentration of analytes This paper generates the ldquo Rs rdquo values in water for pesticides never been generated previously The POCIS laboratory ndash calibration was performed in glass beakers on the basis of static renewal exposure under stirred conditions for days The accumulation kinetics of these pesticides was evaluated and the Rs values found varied from to L day ndash with RSD The effect of hydrophobicity on sampling rates Rs was also evaluated Furthermore we evaluated the applicability of deuterated Atrazine ATR d as Performance Reference Compounds PRC to account for between ndash site variation High performance liquid chromatography HPLC coupled with triple quadrupole tandem mass spectrometry LC ndash MS MS was used for the analysis