Evaluation of the Bioactive Compounds of Apis mellifera Honey Obtained from the Açai (Euterpe oleracea) Floral Nectar.

The biodiversity of Brazil provides an excellent climate and favorable pollination conditions for Apis mellifera L., especially in the Eastern Amazon region, which boasts vast floral wealth, including an abundance of açaí (Euterpe oleracea) flowers and fruits. In the present study, seven types of honey were evaluated: three containing floral nectar from açaí (Açaí honey) collected in the Eastern Amazon region (Açaí honey from Breu Branco (AH1 and AH2) and Açaí honey from Santa Maria (AH3), both from the state of Pará, Brazil) and four honeys from different regions of Brazil (Aroeira honey from Minas Gerais, Cipó-Uva honey from Distrito Federal, Mangue honey from Pará, and Timbó honey from Rio Grande do Sul). The characteristics of these honeys were evaluated by examining their physicochemical properties, melissopalynological aspects, color, antioxidant potential, and their constituent compounds, which were confirmed through GC-MS analysis. Açaí floral nectar honeys presented physicochemical results similar to those of other honeys, aligning with Brazilian legislation norms, but differed in their high values of free acidity, apparent sugars, and lower reducing sugars, which are directly related to their botanical origin. These differences correlate with unique flavor and distinct aroma characteristics. Melissopalynological analysis confirmed the botanical origin of the honeys containing açaí floral nectar, which had a color range from amber to dark amber. The three açaí honeys demonstrated high antioxidant capacity and superior flavonoid and polyphenol content compared to other honeys, particularly the açaí honey from Breu Branco (AH1), which had four times the content to combat free radicals compared to the honey with the highest potential (Aroeira honey). GC-MS analysis confirmed the presence of antioxidant properties as well as potential anti-inflammatory, antibacterial, antimicrobial, and antitumor capabilities in açaí honeys, which have not yet been fully studied.

Anise essential oil immobilized in chitosan microparticles: a novel bactericidal material for food protection.

Foodborne infections in humans are one of the major concerns of the food industries, especially for minimally processed foods (MPF). Thereby, the packaging industry applies free chlorine in the sanitization process, ensuring the elimination of any fecal coliforms or pathogenic microorganisms. However, free chlorine's propensity to react with organic matter, forming toxic compounds such as trihalomethanes and haloacetic acid. Therefore, the present work aimed to synthesize a novel organic biomaterial as an alternative to free chlorine. Chitosan microparticles were produced, with Pimpinella anisum (anise) essential oil immobilized in the biopolymer matrix (MPsQTO). The characterization of this biomaterial was done through GC-MS/MS, FT-IR, and SEM. Antimicrobial assays proved that the MPsQTO presented antibacterial activity for Escherichia coli, Salmonella typhi, Pseudomonas aeruginosa, and Bacillus subtilis at 300 µL mL-1 of concentration. The fluorescence microscope also showed the MPsQTO targets the cytoplasmatic membrane, which is responsible for cell death in the first minutes of contact. Studies with the mutant B. subtilis (amy::pspac-ftsZ-gfpmut1) and the Saccharomyces cerevisiae D7 also proved that the biomaterial did not affect the genetic material and did not have any mutagenic/carcinogenic effect on the cells. The sanitization assays with pumpkin MPF proved that the MPsQTO is more effective than free chlorine, increasing the shelf-life of the MPF. Consequently, the novel biomaterial proposed in this work is a promising alternative to traditional chemical sanitizers.

Determination of pesticide residues in urine by chromatography-mass spectrometry: methods and applications.

Introduction: Pollution has emerged as a significant threat to humanity, necessitating a thorough evaluation of its impacts. As a result, various methods for human biomonitoring have been proposed as vital tools for assessing, managing, and mitigating exposure risks. Among these methods, urine stands out as the most commonly analyzed biological sample and the primary matrix for biomonitoring studies. Objectives: This review concentrates on exploring the literature concerning residual pesticide determination in urine, utilizing liquid and gas chromatography coupled with mass spectrometry, and its practical applications. Method: The examination focused on methods developed since 2010. Additionally, applications reported between 2015 and 2022 were thoroughly reviewed, utilizing Web of Science as a primary resource. Synthesis: Recent advancements in chromatography-mass spectrometry technology have significantly enhanced the development of multi-residue methods. These determinations are now capable of simultaneously detecting numerous pesticide residues from various chemical and use classes. Furthermore, these methods encompass analytes from a variety of environmental contaminants, offering a comprehensive approach to biomonitoring. These methodologies have been employed across diverse perspectives, including toxicological studies, assessing pesticide exposure in the general population, occupational exposure among farmers, pest control workers, horticulturists, and florists, as well as investigating consequences during pregnancy and childhood, neurodevelopmental impacts, and reproductive disorders. Future directions: Such strategies were essential in examining the health risks associated with exposure to complex mixtures, including pesticides and other relevant compounds, thereby painting a broader and more accurate picture of human exposure. Moreover, the implementation of integrated strategies, involving international research initiatives and biomonitoring programs, is crucial to optimize resource utilization, enhancing efficiency in health risk assessment.

Pesticide residues on lettuce (Lactuca sativa L.) in Cundinamarca-Colombia.

Lettuce is Colombia's most widely cultivated leafy vegetable, but in the absence of good agricultural practices, there is the risk of some pesticide residues that affect its safety and quality. This work aimed to identify the pesticides used by farmers for the lettuce crop, the iceberg variety (Lactuca sativa var. capitata), in some municipalities of Cundinamarca (Colombia) and to investigate their residues by sampling and analysis. The farmers reported in the survey 44 active ingredients, most fungicides (54%), while the laboratory analysis showed 23 chemical compounds (52% insecticides, 39% fungicides and 9% herbicides). In addition, dithiocarbamates, procymidone and some organophosphates were among the active ingredients that exceeded the maximum residue limits (MRLs). About 80% of the identified pesticides were not registered with the regulatory entity Instituto Colombiano Agropecuario (ICA) for their use in lettuce, but some were in commercial products legally registered in Latin American and Caribbean countries.

Agrochemical Residues in Fish and Bivalves from Sepetiba Bay and Parnaiba River Delta, Brazil.

Accumulation of pesticides has a harmful impact on the environment and human health. The main goal of this work was to develop a method to determine and quantify the residues of thirteen pesticides in edible fish and bivalves such as parati (Mugil curema), seabass (Centropomus ssp.), mullet (Mugil brasiliensis), clams (Anomalocardia brasiliana) and mussel (Mytilus galloprovincialis) collected from Sepetiba Bay and Parnaiba River Delta (Brazil) between 2019 and 2020. Matrix solid-phase dispersion (MSPD) was used for extraction and quantification through gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). The method was validated (linearity, accuracy and precision) for fatty fish (Salmo salar), lean fish (Mugil curema) and bivalves (Mytilus edulis). The survey found linear correlation coefficients (r) equal to or greater than 0.9 for almost all analytes. The relative standard deviations (RSD) of five replicates were less than 20% for almost all analytes at different concentrations in lean fish, fatty fish and bivalves. Most analytes showed satisfactory accuracy. Alachlor herbicide was found in samples of seabass, mussels, clams and parati with levels ranging between 0.55 to 420.39 µg kg-1 dw. Ethion was found in parati (maximum 211.22 µg kg-1 dw), mussels (15.1 µg kg-1 dw) and clams (maximum 44.50 µg kg-1 dw). Alachlor was found in clams (maximum 93.1 µg kg-1 dw), and bifenthrin was found in parati (maximum 43.4 µg kg-1 dw) and clams (maximum 42.21 µg kg-1 dw). The validated method was satisfactory for the determination of eleven pesticides in the fatty fish matrix, and thirteen pesticides in the samples of lean fish and bivalves. The presence of alachlor, ethion and bifenthrin stands out.

Essential Oil from Croton blanchetianus Leaves: Anticandidal Potential and Mechanisms of Action.

Antimicrobial drugs are becoming ineffective given the resistance acquired by microorganisms. As such, it is imperative to seek new antimicrobial molecules that could provide a basis for the development of new drugs. Therefore, this work aimed to evaluate the antimicrobial potential and the mechanisms of action of the essential oil extracted from leaves of Croton blanchetianus (named CbEO) on different fungi and bacteria of clinical importance in both planktonic and biofilm lifestyles. GC-MS/MS analysis revealed the presence of twenty-two different compounds in the CbEO, which were identified using the Kovats retention index. Among these, the most abundant were amorphene (20.03%), spathulenol (5%), bicyclogermacrene (1.49%), caryophyllene oxide (4.55%), and eucalyptol (5.62%). CbOE (50 µg mL-1) barely inhibited the growth of Bacillus subtilis (23%), Pseudomonas aeruginosa (27%), and Salmonella enterica (28%), and no inhibition was obtained against Enterobacter aerogenes and Klebsiella pneumoniae. Additionally, no activity against bacterial biofilm was detected. In contrast, CbEO was active against Candida species. C. albicans and C. parapsilosis were inhibited by 78 and 75%, respectively. The antibiofilm potential also was favorable against C. albicans and C. parapsilosis, inhibiting 44 and 74% of biofilm formation and reducing around 41 and 27% of the preformed biofilm, respectively. CbOE caused membrane damage and pore formation, overproduction of ROS, and apoptosis on C. albicans and C. parapsilosis cells, as well as not inducing hemolysis in human red cells. The results obtained in this work raise the possibility of using the essential oil of C. blanchetianus leaves as an alternative to fight infections caused by C. albicans and C. parapsilosis.

Pesticide residues analysis in passion fruit and its processed products by LC-MS/MS and GC-MS/MS: Method validation, processing factors and dietary risk assessment.

A method for the determination of 80 pesticides (including five metabolites) in passion fruit using ethyl acetate extraction and dispersive solid-phase extraction followed by LC-MS/MS and GC-MS/MS was validated at LOQ of 0.005 or 0.010 mg kg-1 (70 to 120% recovery; RSD ≤ 20%). Fifty-five passion fruit samples were obtained from producers, and 30 samples of frozen pulp and 12 samples of flour purchased. About 27% of the pesticides were detected; at least one in 60% of the peel samples, mainly imidacloprid and carbendazim (max. of 0.274 mg kg-1). Median processing factor was 0.5 for washed peel and 6.5 for dried peel (flour). About 63% of frozen pulp samples were positive, and 4 flour samples contained residues, mainly methamidophos. About 70% of the detected pesticides are not authorized in passion fruit in Brazil. Chronic and acute exposure from the consumption of passion fruit products did not indicate a health concern.

Dispersive liquid-liquid microextraction of 11-nor-Δ9-tetrahydrocannabinol-carboxylic acid applied to urine testing.

Aim: THC-COOH is the major metabolite of Δ9-tetrahydrocannabinol commonly tested in urine to determine cannabis intake. In this study, a method based on dispersive liquid-liquid microextraction was developed for testing THC-COOH in urine. Materials & methods: Hydrolyzed urine specimens were extracted via dispersive liquid-liquid microextraction with acetonitrile (disperser solvent) and chloroform (extraction solvent). Derivatization was performed with N,O-Bis(trimethylsilyl)trifluoroacetamide with 1% trichloro(chloromethyl)silane. Analysis was performed by GC-MS/MS. Results: The method showed acceptable linearity (5-500 ng/ml), imprecision (<10.5%) and bias (<4.9%). Limits of detection and quantitation were 1 and 5 ng/ml, respectively. Twenty-four authentic samples were analyzed, with 22 samples being positive for THC-COOH. Conclusion: The proposed method is more environmentally friendly and provided good sensitivity, selectivity and reproducibility.

Tweetable abstract Green analytical toxicology: Dispersive liquid­liquid microextraction applied to the analysis of THC-COOH in urine by GC­MS/MS.

Microextraction by packed sorbent of selected pesticides in coffee samples employing ionic liquids supported on graphene nanosheets as extraction phase.

This paper describes the synthesis, characterization, and use of ionic liquids supported on silica, functionalized with graphene oxide through covalent bonding (ILz/Si@GO), as sorbents for microextraction by packed sorbent (MEPS). Seven selected pesticides (diazinon, heptachlor, aldrin, endrin, dieldrin, endosulfan, and methoxychlor), used for the prevention of pests in coffee crops, and endosulfan sulfate-an endosulfan metabolite-were selected for this study as model compounds for evaluating the sorbent performance of the synthesized materials in the MEPS device. The cycles of each of the stages were previously optimized through univariate experiments to carry out the extraction. The ILz/Si@GO phase was compared to other sorbents used in MEPS (GO, DVB-MMA, C4/SiO2, C8/SiO2, ILz/SiO2, and bare silica) and also with graphene functionalized through other methodologies, where ILz/Si@GO showed the best results. The material was characterized using a range of techniques. The selectivity of the sorbent material and its adsorption capacity were evaluated by gas chromatography coupled with tandem mass spectrometry. The precision and accuracy of the method showed a relative standard deviation lower than 10% and recoveries from 35 to 97%. Finally, the proposed method was employed for the determination of pesticide residues in coffee samples.

Phthalic acid esters and adipates in herbal-based soft drinks: an eco-friendly method.

Phthalic acid esters (PAEs) and adipates are plasticizers with high applicability in several products and building materials (e.g. cosmetics, packing) very persistent in the environment, features which render them ubiquitous pollutants. These substances can contaminate food through the environment (water, air, and soil) and/or migration from packaging materials, which creates a health concern due to their toxicity. This paper describes an eco-friendly dispersive liquid-liquid microextraction (DLLME) procedure to extract five phthalates and bis(2-ethylhexyl) adipate (DEHA) from bottled herbal-based beverages followed by GC-MS/MS quantification. The method showed low limits of detection (5.0-13 µg L-1) and quantification (20-35 µg L-1), good inter- and intraday precision (RSD < 19%), and recoveries ranging from 82 to 111%. It was applied to 16 real samples, of which 13 showed the presence of at least one of the analytes under study. Additionally, an exposure assessment was performed, and resulted in a hazard quotient less than 1 (HQ < 1) for all analytes. Therefore, PAEs and DEHA found in samples do not pose a health issue.

Persistent organic pollutants (POPs) and personal care products (PCPs) in the surface sediments of a large tropical bay (Todos os Santos Bay, Brazil).

The occurrence and spatial distribution of persistent organic pollutants (POPs) and personal care products (PCPs) were investigated in surface sediments of Todos os Santos Bay. Samples were Soxhlet-extracted and analyzed by gas chromatography coupled with tandem mass spectrometry. Quantification limits (QL) ranged from 0.0025 ng g-1 for POPs to 0.25 ng g-1 for PCPs. Of the POPs studied, only PCBs and DDTs were detectable, with concentrations ranging from

Optimization of Method for Pesticide Detection in Honey by Using Liquid and Gas Chromatography Coupled with Mass Spectrometric Detection.

This study aimed to optimize and validate a multi-residue method for identifying and quantifying pesticides in honey by using both gas and liquid chromatographic separation followed by mass spectrometric detection. The proposed method was validated to detect 168 compounds, 127 of them by LC-MS/MS (liquid chromatography tandem mass spectrometric detection) and 41 by GC-MS/MS (gas chromatography tandem mass spectrometric detection). The limit of detection (LOD) and limit of quantification (LOQ) values for the analytes determined by LC-MS/MS were 0.0001-0.0004 mg/kg and 0.0002-0.0008 mg/kg, respectively. For GC-MS/MS analyses, the LOD and LOQ values were 0.001-0.004 mg/kg and 0.002-0.008 mg/kg. In total, 33 samples of commercial honey produced by apiaries in six Brazilian states were analyzed with the validated method. Residual amounts of 15 analytes were detected in 31 samples (93.9%). The method described in the present study was able to detect an extensive and broad range of pesticides with very high sensitivity.

Multiresidue method for triazines and pyrethroids determination by solid-phase extraction and gas chromatography-tandem mass spectrometry.

This research aimed at implementing and validating a method for analysis of pesticide residues in crops. QuEChERS extraction method with PSA purification was used following analyzes by gas chromatography with tandem mass spectrometry in Selected Reaction Monitoring mode. A short run method was successfully developed for the determination of 41 pesticides, confirmed by two precursor-products for each analyte. The calibration curve for each analyte was linear at concentration range from 1 to 500 µg kg-1 with correlation coefficients higher than 0.99, low limits of detection (0.03 - 10.22 µg kg-1) and satisfactory precision. The developed method was used to investigate apples; mangos; strawberries; cucumbers and tomatoes from the Rio de Janeiro Food Distribution Center (CEASA).Most of the targeted pesticides (78%) were below detection limits. Apple and strawberry presented the highest pesticide contamination levels, many of which are not authorized by tthe Brazilian national regulatory agency (ANVISA).

Triple quadrupole-mass spectrometry protocols for the analysis of NBOMes and NBOHs in blotter papers.

NBOMe and NBOH are new psychoactive substances with potent activity on serotonin 5-HT2a receptors causing serious toxic effects, including serotonin toxidrome and death. The aim of this work was to develop a comprehensive MS/MS protocol, using triple quadrupole mass spectrometers coupled to LC and GC, for rapid screening and quantitation of NBOMes and NBOHs in seized blotter papers. Different scan methods (neutral loss, precursor ion or multiple reaction monitoring) were used to obtain structural information of phenylethylamine class. The developed protocol was validated for qualitative and quantitative analysis, showing a satisfactory limit of detection (1 ng/mL), with excellent selectivity, imprecision (intra and interday imprecision lower than 1.2 % RSD) and accuracy (between -7.1 and +5.6 %, n = 15), as well as bias values. The analysis of real samples shown that NBOH compounds were the most frequently detected, with concentrations ranging from 0.1 to 1,929 µg per blotter sample. Triple quadrupole mass spectrometers can be a useful tool for identification of new psychoactive substances. A comprehensive protocol using both LC-MS/MS and GC-MS/MS, with different scanning modes, have been developed and showed to be useful to screening NBOMe and NBOH in blotter papers.

Characterization of a multianalyte GC-MS/MS procedure for detecting and quantifying polycyclic aromatic hydrocarbons (PAHs) and PAH derivatives from air particulate matter for an improved risk assessment.

A correct description of the concentration and distribution of particle bound polycyclic aromatic hydrocarbons is important for risk assessment of atmospheric particulate matter. A new targeted GC-MS/MS method was developed for analyzing 64 PAHs including compounds with a molecular weight >300, as well as nitro-, methyl-, oxy- and hydroxyl derivatives in a single analysis. The instrumental LOD ranged between 0.03 and 0.7 pg/µL for PAHs, 0.2-7.9 pg/µL for hydroxyl and oxy PAHs, 0.1-7.4 pg/µL for nitro PAHs and 0.06-0.3 pg/µL for methyl-PAHs. As an example for the relevance of this method samples of PM10 were collected at six sampling sites in Medellin, Colombia, extracted and the concentration of 64 compounds was determined. The 16 PAHs from the EPA priority list contributed only from 54% to 69% to the sum of all analyzed compounds, PAH with high molecular weight accounted for 8.8%-18.9%. Benzo(a)pyrene equivalents (BaPeq) were calculated for the estimation of the life time cancer (LCR). The LCR according to the samples ranged from 2.75 × 10-5 to 1.4 × 10-4 by a calculation with toxic equivalent factors (TEF) and 5.7 × 10-5 to 3.8 × 10-4 with potency equivalent factor (PEF). By using the new relative potency factors (RPF) recommended by US Environmental Protection Agency (U.S.EPA) the LCR ranged from 1.3 × 10-4 to 7.2 × 10-4. Hence, it was around six times higher than the well-known TEF. The novel method enables the reliable quantification of a more comprehensive set of PAHs bound on PM and thus will facilitate and improve the risk assessment of them.

Development of an analytical methodology for the determination of organochlorine pesticides by ethylene-vinyl acetate passive samplers in marine surface waters based on ultrasound-assisted solvent extraction followed with headspace solid-phase microextraction and gas chromatography-tandem mass spectrometry.

A novel strategy for the analysis of 20 organochlorine pesticides (OCPs) monitoring in marine surface waters through ethylenevinyl acetate (EVA) passive samplers was developed and validated. The approach is based on the coupled of ultrasound-assisted solvent extraction (UASE) and headspace solid-phase microextraction (HS-SPME) as extraction method for OCPs from EVA samplers. The UASE-HS-SPME method was optimized with a 27-4 Plackett-Burman design, while the significant factors (salting out, temperature and extraction time) were optimized using a central composite design (CCD) combined with desirability function (DF). The OCPs detection was performed using multiple reaction monitoring (MRM) by gas chromatography-tandem mass spectrometry (GC-MS/MS). The optimum experimental conditions comprised: salting out: 23% wv-1 NaCl, temperature: 75°C and extraction time: 55 min. The optimized method was validated in terms of linearity (R2>0.9946), recovery (>61%) and inter-day and intra-day reproducibility (<19%) for 20 OCPs studied. The limits of detection (LODs) were ranging from 0.01 ng for α-hexachlorocyclohexane and 0.27 ng for endrin aldehyde. Finally, the methodology was tested in marine surface seawater of Southern Chile using EVA samplers, where twelve OCPs were detected at ultra-trace levels (ngL-1).

Avaliação da presença do 3-monocloro-1, 2-propanediol e glicidol em óleos vegetais comestíveis utilizando GC/MS/MS e seu risco toxicológico / Evaluation of the presence of 3-monochloro-1, 2-propanediol and glycidol in edible vegetable oils using GC/MS/MS and its toxicological risk

Cloropropanóis são um grupo conhecido de contaminantes relacionados ao processamento de alimentos. Eles são formados na reação entre lipídeos e cloretos quando submetidos ao tratamento térmico, e podem ser encontrados na forma livre ou ligada. O 3-monocloro-1,2-propanediol (3-MCPD), é classificado pela IARC como possível carcinógeno humano (grupo 2B). O glicidol (e seus ésteres), é classificado também pela IARC como uma substância provavelmente carcinogênica para seres humanos (grupo 2A), e, recentemente, vem sendo encontrado em alimentos. O objetivo deste trabalho foi avaliar a presença do 3-MCPD e do glicidol em óleos vegetais comestíveis utilizando a cromatografia gasosa com detector de massa triplo quadrupolo MS/MS. A técnica utilizada foi a preconizada pela AOCS Cd 29c-13, sendo uma análise indireta, e foi possível adaptá-la visando as determinações do 3-MCPD e glicidol através da construção de curvas de calibração e análises de amostras de referência. O método foi validado e os resultados indicaram o limite de detecção do composto 3-MCPD, de 42,4 µg/kg e o limite de quantificação de 50 µg/kg, e para o Glicidol indicaram o limite de detecção de 43,5 µg/kg e limite de quantificação de 50 µg/kg. Os resultados para 3-MCPD obtidos nos ensaios da curva de calibração e linearidade demonstraram que o método foi capaz de expressar resultados com boa linearidade (0 - 10 mg/kg , r2, = 0.9991). Os resultados obtidos nos ensaios de exatidão obedeceram aos critérios de 70 a 120% de recuperação, e ±20% de variação entre os resultados de acordo com SANTE (2017). O método em questão demonstrou ser seletivo, uma vez que não foram observados picos interferentes nos tempos de retenção dos compostos estudados. Os ensaios de precisão nos níveis baixos, médio e alto e robustez demonstraram que o método é robusto e preciso, portanto a validação foi considerada adequada ao uso pretendido. Foram analisadas 368 amostras de óleos vegetais (76 amostras de óleo de canola, 48 amostras de óleo de milho, 69 amostras de óleo de algodão, 33 amostras de óleo de palma, 10 amostras de óleo de palmiste, 50 amostras de oleína de palma, 30 amostras de óleo de soja e 51 amostras de óleo de girassol). As concentrações das amostras analisadas apresentaram resultados para 3-MCPD com valores médios entre 203 a 1205 µg/kg. Para o Glicidol os valores foram de 2 a 1198 µg/kg, com elevado o desvio padrão entre os resultados analíticos, onde o óleo de palma apresentou a maior variação de 1600 a 5260 µg/kg. Através da avaliação do risco realizada para o composto 3-MCPD foi possível detectar, utilizando o critério do pior cenário de exposição e resultados analíticos, os valores diários de consumo de óleo de algodão de 0,044 µg/kg p.c., de óleo de girassol 0,045 µg/kg p.c., óleo de canola 0,18 µg/kg p.c., óleo de palma de 0,28 µg/p.c, óleo de milho de 0,0462 µg/kg p.c., e o óleo de soja, de maior consumo no Brasil (72%) apresentou o valor de 0,27 µg/kg p.c. O consumo de todos estes óleos, pela a população brasileira, pode ser considerado seguro ao comparar com o valor de TDI Ingestão Diária Tolerável - de 2µg/kg p.c.. Através da avaliação do risco realizada também utilizando o critério de pior cenário de exposição e e resultados analíticos para o composto glicidol foi possível verificar que os valores diários de consumo de óleo de algodão de 0,061 µg/kg p.c., de óleo de girassol 0,03 µg/kg p.c., óleo de canola 0,13 µg/kg p.c. e de óleo de palma de 0,57 µg/p.c, de óleo de milho de 0,11 µg/kg p.c, e o óleo de soja de maior consumo no Brasil (72%) não ultrapassam o valor de 0,288 µg/kg p.c indicando consumo seguro destes óleos para a população brasileira baseado na TDI de 1000µg/kg p.c

Chloropropanols are a known group of contaminants related to food processing. They are formed during the reaction process between lipids and chlorides when submitted to heat treatment and can be found in free or bound form. The 3-monochloro-1,2-propanediol (3-MCPD), is classified by IARC as a possible human carcinogen (group 2B). Glycidol (and its esters), also classified by IARC as a substance likely to be carcinogenic to humans (group 2A), has recently been found in food. The present study aims to evaluate the presence of 3-MCPD and glycidol in edible vegetable oils using gas chromatography with triple quadrupole MS/MS mass detector. The technique applied is recommended by AOCS, guide Cd 29c-13, an indirect analysis, and allows quantification of 3-MCPD and glycidol by building the calibration curves and analysis of reference samples. The method was validated and the detection limit of the contaminant 3-MCPD of 42,4 µg/kg and the quantification limit of 50 µg/kg was established. For Glycidol the detection limit of was 43,5 µg/kg and quantification limit was 50 µg/kg. The results obtained in the calibration and linearity curves demonstrated that the method could express results with good linearity (0 10 mg/kg, r2, = 0.9991). The results obtained in the trueness trials agreed to the criteria of 70 to 120% of recovery, and ± 20% of variation between the results according to what is preconized by SANTE (2017). The method showed to be selective, since no interfering peaks were observed in the retention times of the studied compounds. The tests performed on low, medium and high values demonstrated the robustness and precision of the method, so the validation was considered completed and suitable for the purpose. A total of 368 vegetable oil samples were analyzed (76 samples of canola oil, 48 samples of corn oil, 69 samples of cottonseed oil, 33 samples of palm oil, 10 samples of kern palm oil, 50 samples of palm olein, 30 samples of soybean oil and 51 samples of sunflower oil). The results found in samples for 3-MCPD were within mean values between 203 and 1205 µg/kg. The results found in samples for glycidol were within mean values between 2 to 1198 µg/kg where palm oil presented the highest variation for glycidol from 1600 to 5260 µg/kg. Through the risk assessment for the contaminant 3-MCPD it was possible to detect the values based on exposed worst case scenario and analytical results. The results for cottom oil were 0,044 µg/kg bw, sunflower 0,045 µg/kg bw, canola 0,18 µg/kg bw and palm oil 0,28 µg/kg bw, corn oil 0,0462 µg/kg bw, and for soybean, which is the most consumed oil in Brazil (72%) the value of 0,27 µg/kg bw. These results indicates safe consumption for these oils based in the Theoretical Daily Ingestion - TDI of 2µg/kg bw. The risk assessment for the glycidol based on exposure worst case scenario and analytical results presented for cottom oil the value of 0,061 µg/kg bw, sunflower 0,03 µg/kg bw, canola oil 0,13 µg/kg bw , palm oil 0,57 µg/kg bw, corn oil 0,11 µg/kg bw and for soybean, which is the most consumed in Brazil - 72% the value of 0,27 µg/kg bw. These results indicates safe consumption for these oils based in the TDI of 1000µg/kg bw

Multiresidue Determination of the Anabolic-Agent Residues Steroids, Stilbenes, and Resorcylic Acid Lactones in Bovine Urine by GC-MS/MS with Microwave-Assisted Derivatization.

In this work, a GC-MS/MS method was developed for the determination of anabolic-agent residues in bovine urine. The optimized sample preparation was as follows: enzymatic hydrolysis by ß-glucuronidase-sulfatase enzyme from Helix pomatia for 16 h at 37.5 °C, liquid-liquid extraction with diethyl ether, solid-phase extraction with HLB and aminopropylsilane cartridges, and microwave-assisted derivatization using 25 µL of MSTFA/NH4I/ethanethiol and full microwave power for 2 min. The method was validated according to Decision 657/2002/EC, Codex Alimentarius, and Manual da Garantia da Qualidade Analítica guidelines. The acceptability criteria for quantitative analysis were met for α-ethinylestradiol, α-nandrolone, ß-estradiol, ß-zearalanol, ß-zearalenol, drostanolone, ethisterone, dienestrol, diethylstilbestrol, hexestrol, megestrol, methyltestosterone, and zearalenone. The analytes α-zearalenol, α-zearalanol, and norethandrolone were validated for qualitative analysis.

Evaluation of Mycotoxin Residues on Ready-to-Eat Food by Chromatographic Methods Coupled to Mass Spectrometry in Tandem.

Simultaneous determination of twenty-seven mycotoxins in ready-to-eat food samples using “Quick Easy Cheap Rough and Safe” (QuEChERS) extraction and chromatographic methods coupled to mass spectrometry in tandem is described in this study. Mycotoxins included in this survey were aflatoxins (B1, B2, G1, G2), enniatins (A, A1, B, B1), beauvericin (BEA), fumonisins (FB1, FB2), sterigmatocystin (STG), deoxynivalenol (DON), 3-acetyl-deoxynivalenol (3-ADON), 15-acetyl-deoxynivalenol (15-ADON), nivalenol (NIV), neosolaniol (NEO), diacetoxyscirpenol (DAS), fusarenon-X (FUS-X), zearalenone (ZEA), α-zearalanol (αZAL), β-zearalenone (βZAL), α-zearalenol (αZOL), β-zearalenol (βzol), T2, and HT-2 toxin. The method showed satisfactory extraction results with recoveries ranging from 63 to 119% for the different food matrix samples. Limits of detection (LODS) and quantification (LOQs) were between 0.15⁻1.5 µg/kg and 0.5⁻5 µg/kg, respectively. The method was successfully applied to the analysis of 25 ready-to-eat food samples. Results showed presence of deoxynivalenol at 36% of samples (2.61⁻21.59 µg/kg), enniatin B at 20% of samples (9.83⁻86.32 µg/kg), HT-2 toxin at 16% of samples (9.06⁻34.43 µg/kg), and aflatoxin G2 at 4% of samples (2.84 µg/kg). Mycotoxins were detected mainly in ready-to-eat food samples prepared with cereals, vegetables, and legumes, even at levels below those often obtained from raw food.

Bee pollen as a bioindicator of environmental pesticide contamination.

Honeybees and bee products are potential bioindicators of the presence of contaminants in the environment, enabling monitoring of large areas due to the long distances travelled by bees. This work evaluates the use of bee pollen as a bioindicator of environmental contamination by pesticides. A GC-MS/MS analytical method for multiresidue determination of 26 different pesticides in pollen was developed and validated in accordance with the recommendations of the European Union SANCO guide. Environmental monitoring was conducted using the analysis of 145 pollen samples collected from ten beehives in the experimental apiary of Embrapa in Jaguariúna (São Paulo State, Brazil). Bioallethrin and pendimethalin were identified in four and eighteen samples, respectively, at concentrations below the LOQ of the method (25 ng g(-1)). Passive sampling with polyurethane foam discs was used as a control, and no pesticides were found. The detection of pesticide residues in seven samples (33%) from commercial apiaries in Ribeirão Preto (São Paulo State) confirmed the efficiency of the analytical method and the need for environmental monitoring for the presence of pesticide residues. The results demonstrated the potential of bee pollen as a bioindicator of environmental contamination by pesticides.