Human health risks associated to trace elements and metals in commercial fish from the Brazilian Amazon.

Fish constitutes the main protein source for the Amazonian population. However, the impact of different anthropogenic activities on trace element and metal accumulation in fish and their risks for human health at a regional scale remain largely unexplored. Here we assessed exposure levels of 10 trace elements and metals (Cr, Mn, Fe, Ni, Cu, Zn, As, Cd, Pb, and Hg) in 56 samples belonging to 11 different species of fish from the Brazilian Amazon. We studied the relationship between exposure levels, fish origin, and fish feeding habits, and assessed toxicological and carcinogenic risks for the Amazonian population. No significant correlation was found between sampling site and exposure levels to the studied elements, but a significant difference was found between the accumulation of some metals and the position of the fish species in the food chain. The concentrations of Cr and Hg in fish flesh were found to exceed the Brazilian limits for human consumption. This study shows that current fish consumption patterns can lead to estimated daily intakes of Hg, As and Cr that exceed the oral reference dose, thus posing a toxicological concern. Furthermore, carcinogenic risks may be expected due to the continued exposure to Cr and As. The results of this study show that the consumption of wild caught fish in the Amazon region should be controlled. Moreover, continued monitoring of trace element and metal contamination in fish and on the health of the Amazonian population is recommended, particularly for riverine and indigenous communities.

Investigation of fraud in the production of butter: a forensic case study of criminal association.

Butter is among the most popular and commercially valuable dairy products. Its high commercial value makes it a major target for adulteration, which aims to reduce production costs by using lower-quality fats and oils from other sources. The annual global market is around USD 30 billion (2023), expected to reach USD 36 billion in 2028, which also justifies the enormous interest in adulteration. In this work, a confirmed case of butter adulteration was studied by Nuclear Magnetic Resonance (NMR) and Stable Carbon Isotopic Ratio Analysis (SCIRA) techniques, employed to detect the inclusion in butter production of vegetable oils, such as soybean and palm oils. A total of 21 samples seized by the Brazilian Federal Police were analysed by NMR and SCIR, and compared to original butter obtained from commercial sources. The composition of all the seized samples was a mixture of butter (dairy fat of animal origin) with fat of vegetable origin (soybean and palm oil) and did not contain milk as a major component. While NMR was an unequivocal choice to discriminate the chemical composition of food samples, identifying the short-chain saturated fatty acids present in milk fat, including the butyryl alkyl chain, SCIRA was able to discriminate the origin of fat present in the butter samples as C3 sources, such as palm vegetable oils.

Selective Detection of Paraquat in Adulterated and Complex Environmental Samples Using Raman Spectroelectrochemistry.

Growing demand for pesticides has created an environment prone to deceptive activities, where counterfeit or adulterated pesticide products infiltrate the market, often escaping rapid detection. This situation presents a significant challenge for sensor technology, crucial in identifying authentic pesticides and ensuring agricultural safety practices. Raman spectroscopy emerges as a powerful technique for detecting adulterants. Coupling the electrochemical techniques allows a more specific and selective detection and compound identification. In this study, we evaluate the efficacy of spectroelectrochemical measurements by coupling a potentiostat and Raman spectrograph to identify paraquat, a nonselective herbicide banned in several countries. Our findings demonstrate that applying -0.70 V during measurements yields highly selective Raman spectra, highlighting the primary vibrational bands of paraquat. Moreover, the selective Raman signal of paraquat was discernible in complex samples, including tap water, apple, and green cabbage, even in the presence of other pesticides such as diquat, acephate, and glyphosate. These results underscore the potential of this technique for reliable pesticide detection in diverse and complex matrices.

Factors influencing fumonisin B1 contamination in maize: insights from two production regions in Costa Rica.

Maize (Zea mays L.) is an important cereal crop worldwide. Contaminated maize kernels pose a significant mycotoxin exposure risk for humans in Latin America. Fumonisins, the most prevalent mycotoxin in maize, typically occur during pre-harvest conditions leading to significant economic losses. Various factors, including weather conditions, may influence this contamination. This study aimed to determine the association between fumonisin B1 (FB1) contamination, prevalence of Fusarium verticillioides, weather conditions and kernel quality in the two primary maize production areas in Costa Rica (Brunca and Chorotega). All maize samples (100%) showed FB1 contamination, with higher concentrations in samples from Brunca region, consistent with the presence of F. verticilliodes. Weather conditions appeared to play an important role in this contamination, since Brunca region had the highest mean temperature and relative humidity after maize silking (R1) and the total monthly rainfall in this region was significantly higher during the last two months of maize cultivation (grain-filling and physiological maturity stages R3 to R6). Interestingly, this study found a negative correlation between grain damage and kernel contamination with FB1 and F. verticillioides. The concentration of mineral nutrients in kernels from both regions was largely similar. Most nutrients in kernels exhibited a negative correlation with FB1, particularly nitrogen. Zinc and phosphorus were the only nutrients in kernels showing a positive correlation with FB1 in samples from the Brunca region. The results highlight elevated levels of FB1 contamination in maize and contribute to a better understanding of pre-harvest factors influencing FB1 contamination in tropical conditions.

Occurrence of modified mycotoxins in Latin America: an up-to-date review.

The Latin America region has a considerable extent of varied climate conditions: from tropical, subtropical, and warm temperate to temperate. Among the surface territory, different agricultural products are produced, making them an important food source for human consumption. Fungal species commonly colonize those important agricultural products and often contaminate them with mycotoxins that have a major impact on health, welfare, and productivity. Nowadays, special attention is paid to modified mycotoxins, which are those that cannot be detected by conventional analytical methods. However, little data about their natural occurrence in food and feed is available, especially in Latin American countries, where, among all the countries in this region, only a few of them are working on this subject. Thus, the present review summarizes the published information available in order to determine the possible human exposure risk to these toxins.

Comprehensive dynamics of bacterial and fungal diversity throughout concentrated chicken broth processing: Integrating culture-dependent and independent techniques.

This study presents comprehensive insights into the microbiological profile across all concentrated chicken broth processing stages, utilizing a combination of amplicon sequencing based on metataxonomic and culturing techniques. Samples were systematically collected throughout the production chain, with each batch yielding 10 samples per day across eight different dates. These samples underwent thorough analysis, including 16S rRNA and ITS sequencing (n = 30), culture-dependent microbiological tests (n = 40), and physical-chemical characterization (n = 10). Culturing analysis revealed the absence of Listeria monocytogenes and Salmonella spp. at any stage of processing, counts of various microorganisms such as molds, yeasts, Enterobacteria, and others remained below detection limits. Notably, spore counts of selected bacterial groups were observed post-processing, indicating the persistence of certain species, including Bacillus cereus and Clostridium perfringens, albeit in low counts. Furthermore, the study identified a diverse array of bacterial and fungal species throughout the processing chain, with notable occurrence of spore-forming bacteria. The presence of spore-forming bacteria in the final product, despite thermal processing, suggests the need for enhanced strategies to mitigate their introduction and persistence in the processing premises. Thus, this study offers valuable insights into microbial dynamics and diversity through processing concentrated chicken broth.

Simultaneous determination of 11 water-soluble synthetic colorants in foods consumed in Chile by high-performance liquid chromatography with diode Array detection.

In Chile, limited information is available on colorants in commonly consumed foods among vulnerable age groups. We developed and validated a rapid HPLC-DAD method to simultaneously evaluate 11 synthetic colorants in candies, beverages, ice cream, and cereals. The method exhibited excellent analytical performance for all 11 colorants with LOD (0.44 - 1.55 mgL-1), LOQ v(1.32 - 4.70 mgL-1), precision (4.0 and 7.3% RSD), and recovery (80 - 105%) in fortified matrices (10-50-100 mgL-1). The highest detection frequencies were as follows: cereals > candies > beverages > ice cream. Sunset Yellow was the most prevalent colorant in all food matrices, followed by Allura Red and Azorubine. Positive samples contained between 1 and 5 synthetic colorants. With the exception of cereals, the colorant concentrations in the remaining matrices exceeded the Codex Alimentarius regulations and the values reported in other studies worldwide, indicating the Chilean population is at risk.

Adulterated dietary supplements commercialized in Brazil: development of a screening method and a preliminary study of cytotoxicity.

The high consumption of dietary supplements was a fundamental driver for the creation of the regulatory framework by the Brazilian governmental authorities. However, the regulatory agencies lack official low-cost methodologies to evaluate the quality of food supplements. A preliminary screening method by HPLC-DAD was proposed and validated for screening and quantification of adulterants in dietary supplements. The limits of detection and quantification were <0.11 and 0.37 µg.g-1, respectively. The method was applied for the investigation of ten unauthorized substances (spironolactone, hydrochlorothiazide, furosemide, clenbuterol, testosterone, testosterone propionate, yohimbine, vardenafil, tadalafil, and sildenafil) with a time of analysis of <5 min. Sixteen percent of the 44 samples analyzed had at least one adulterant at or above therapeutic concentrations. Subsequently, in vitro evaluations were performed of the potential cytotoxicity to evaluate the cell viability, DNA damage, determination of nitric oxide levels, and quantification of reactive oxygen species. Despite the necessity of further studies, the results indicate a relationship between the presence of adulterants in food supplements and a potential cytotoxic effect.

Hazardous Elements in the Edible Portion of Perna perna Mussels: Relation with the COVID-19 Pandemic Period and Assessment of the Risk to Human Health.

In this work, the concentrations of hazardous elements (As, Cd and Pb) in the edible portion of the Perna perna mussel from Southeast Brazil were analyzed to understand the effects of the COVID-19 pandemic on the coastal environment and to evaluate the quality of this fishery resource. Decreases in anthropogenic chemical outputs to the environment were expected to occur during the COVID-19 pandemic, with decreases in element concentrations in mussels. The ranges of median concentrations (µg g-1 dw) in the pre- and pandemic periods were 5.4-16.1 and 2.2-10.6 for As; 0.2-0.6 and 0.1-0.5 for Cd; and 1.2-3.2 and 0.7-1.8 for Pb, respectively. Temporal variations (prepandemic x pandemic) were more significant than spatial variations (five sampling sites). The relationships between the concentrations of hazardous elements and isotopic ratios (δ15N and δ13C) suggested that food sources were more diverse across the sampling sites during the pandemic period, when individuals exhibited less efficient trophic transfer. The concentrations of Cd and Pb were below the tolerable maximum limit, whereas for As, they were above the limit; however, these concentrations are not a risk to human health, as most As was present in the least toxic organic form. The intake estimates were below the tolerable intake limits, and only Pb concentrations are at risk of causing concern if the intake of mussels increases. This is the first study in Brazil that presents a spatial-temporal comparison of hazardous elements in marine fauna considering COVID-19 as a temporal landmark. The results are of interest for both public health and environmental health management in a post-COVID-19 scenario.

Analysis of Maillard reaction precursors and secondary metabolites in Chilean potatoes and neoformed contaminants during frying.

Southern Chile native potatoes are an interesting raw material to produce novel snacks like colored potato chips. These novel products should be comprehensively evaluated for the presence of undesirable compounds such as acrylamide, 5-hydroxymethylfurfural and furan, the main neoformed contaminants in starchy rich fried foods. This study evaluated the neoformed contaminant levels and oil content on chips made from eleven Chilean potato accessions and compared them with commercial samples. The neoformed contaminant contents were related to Maillard reaction precursor levels (reducing sugars and asparagine) and secondary metabolites (phenolic compounds and carotenoids). Neoformed contaminants correlated well among them and were weakly correlated with reducing sugars and asparagine. Acrylamide level in native potato chips ranged from 738.2 to 1998.6 µg kg-1 while from 592.6 to 2390.5 µg kg-1 in commercial samples. Thus, there is need to implement neoformed contaminant mitigation strategies at different steps of the production chain of colored potato chips.

Wheat debranning: effects on mycotoxins, phenolic content, and antioxidant activity.

The debranning process, at an industrial scale, was applied to grains of two wheat cultivars to determine its effect on Fusarium mycotoxin content and antioxidant activity. Grain samples from the BRS Marcante and BRS Reponte wheat cultivars, naturally contaminated by Fusarium, were used in the study. The dry wheat samples were processed on the polisher once or twice and evaluated by hardness index, chemical composition (moisture, protein, and ash), deoxynivalenol (DON) and zearalenone (ZON) levels, phenolic content, and antioxidant activity. In the BRS Marcante cultivar, the debranning process only slightly reduced the DON and ZON contents in whole-wheat flours compared with the previous cleaning treatment (no-debranned). In the BRS Reponte cultivar, the DON concentration decreased by 36% at a debranning ratio of 5%, obtained by polishing, compared with prior cleaning treatment (no-debranned). In addition, the polishing reduced the ZON level by 56% compared with the cleaned wheat. The debranning process did not reduce the antioxidant capacity. Therefore, debranning is a suitable technology to obtain safer and healthier food by minimizing the mycotoxin content and retaining antioxidant capacity.

Increased Dissemination of Aflatoxin- and Zearalenone-Producing Aspergillus spp. and Fusarium spp. during Wet Season via Houseflies on Dairy Farms in Aguascalientes, Mexico.

Crops contamination with aflatoxins (AFs) and zearalenone (ZEA) threaten human and animal health; these mycotoxins are produced by several species of Aspergillus and Fusarium. The objective was to evaluate under field conditions the influence of the wet season on the dissemination of AF- and ZEA-producing fungi via houseflies collected from dairy farms. Ten dairy farms distributed in the semi-arid Central Mexican Plateau were selected. Flies were collected in wet and dry seasons at seven points on each farm using entomological traps. Fungi were isolated from fly carcasses via direct seeding with serial dilutions and wet chamber methods. The production of AFs and ZEA from pure isolates was quantified using indirect competitive ELISA. A total of 693 Aspergillus spp. and 1274 Fusarium spp. isolates were obtained, of which 58.6% produced AFs and 50.0% produced ZEA (491 ± 122; 2521 ± 1295 µg/kg). Houseflies and both fungal genera were invariably present, but compared to the dry season, there was a higher abundance of flies as well as AF- and ZEA-producing fungi in the wet season (p < 0.001; 45.3/231 flies/trap; 8.6/29.6% contaminated flies). These results suggest that rainy-weather conditions on dairy farms increase the spread of AF- and ZEA-producing Aspergillus spp. and Fusarium spp. through houseflies and the incorporation of their mycotoxins into the food chain.

Cloud point method applied to the extraction and preconcentration of thiabendazole pesticide from whole grape juice samples and amperometric detection by HPLC.

A cloud point method was developed and applied for the first time to extract and preconcentrate thiabendazole (TBZ) from commercial whole grape juice samples, with determination by high performance liquid chromatography coupled to electrochemical detection (HPLC/EC), using a cathodically pretreated boron-doped diamond electrode (BDD). The best conditions for extraction and preconcentration of TBZ by cloud point extraction (CPE) were performed at pH 6.0, by adding 1 mL of the surfactant Tergitol TMN-6 at 10% (mass-to-mass ratio), without heating (at 27 °C) and ultrasonic stirring time of (20 kHz) for 60 min. The HPLC/EC determination was duly validated in a C8 column, in mobile phase with a 69 : 31 ratio (V/V) of phosphate buffer (pH 7.0):ACN, at a flow rate of 1.2 mL min-1 and electrochemical detection with BDD electrode by applying 1.40 V × Ag/AgCl (3.0 mol L-1). Under these conditions, the procedure showed a preconcentration factor (FC) of 21.7, and limits of detection (LOD) and quantification (LOQ) of 6.64 × 10-9 mol L-1 (or 1.33 µg L-1) and 1.66 × 10-8 mol L-1 (or 3.34 µg L-1), respectively. The method provided a percent recovery of 81% to 98%, with a coefficient of variation between 3% and 15%.

Detection of foodborne pathogens in contaminated food using nanomaterial-based electrochemical biosensors.

Foodborne pathogens are a grave concern for the for food, medical, environmental, and economic sectors. Their ease of transmission and resistance to treatments, such as antimicrobial agents, make them an important challenge. Food tainted with these pathogens is swiftly rejected, and if ingested, can result in severe illnesses and even fatalities. This review provides and overview of the current status of various pathogens and their metabolites transmitted through food. Despite a plethora of studies on treatments to eradicate and inhibit these pathogens, their indiscriminate use can compromise the sensory properties of food and lead to contamination. Therefore, the study of detection methods such as electrochemical biosensors has been proposed, which are devices with advantages such as simplicity, fast response, and sensitivity. However, these biosensors may also present some limitations. In this regard, it has been reported that nanomaterials with high conductivity, surface-to-volume ratio, and robustness have been observed to improve the detection of foodborne pathogens or their metabolites. Therefore, in this work, we analyze the detection of pathogens transmitted through food and their metabolites using electrochemical biosensors based on nanomaterials.

Health risk assessment by consumption of commercial biota contaminated with heavy metals in Tampamachoco coastal lagoon, Gulf of Mexico.

Metal pollution is a significant environmental and health problem in aquatic ecosystems worldwide, particularly in coastal systems impacted by emissions from thermoelectric plants, as is the case of the Tampamachoco lagoon. To evaluate the seasonal contamination levels of Cd, Pb, Cr, and Cu in species of commercial interest in the Tampamachoco lagoon and estimate the health risk associated with their consumption, a total of 180 fish, 90 oysters (Crassostrea virginica), 27 crabs (Callinectes sapidus), and 24 shrimp (Litopenaeus setiferus) were sampled. Metal concentrations in the species analyzed were Cu > Pb > Cr > Cd. According to the Target Hazard Quotient and the health risk index, consumption of the marine species examined should be considered safe for human health, as both values are <1. However, Carcinogenic risk values for Pb and Cr indicated that consumers may be at risk of cancer (10-3), due to exposure from the thermoelectric emissions.

Spatiotemporal variability of pesticides concentration in honeybees (Apis mellifera) and their honey from western Mexico. Risk assessment for honey consumption.

The study conducted in the state of Colima, western Mexico, aimed to assess the 1) occurrence, 2) temporal variability, 3) spatial variability, and 4) potential risk for honeybees and human consumption of pesticide-contaminated honey. For that purpose, 48 pesticides were determined in bees and their honey during both dry and wet seasons. The research considered two variables: land use categorization (irrigated agriculture, rainfed agriculture, grassland, and forest area) and location (coastal, valley, and mountain). Bee and honey samples were collected, pre-treated using solid-phase extraction (SPE), and analyzed using LC-MS/MS and GC-MS techniques. Occurrence: of the total number of pesticides, 17 were detected in the bee samples and 12 in the honey samples. The pesticides with the highest concentrations in the bee samples were glufosinate ammonium, picloram, and permethrin, while in the honey samples, picloram, permethrin, and atrazine were the most prevalent. Temporal variability: analyses revealed significant differences between dry and wet seasons for glufosinate ammonium and DEET in bee samples and only for glufosinate ammonium in honey samples. Spatial variability: analyses showed a trend in the number of detected pesticides, with irrigated agriculture areas having the highest detection and grassland areas having the least. The human potential risk assessment of contaminated honey consumption indicated no risk. The bee's potential risk for consumption of pesticides contaminated honey revealed chronic effects due to permethrin in a general scenario, and carbofuran, diazinon and permethrin in the worst scenario, and potential risk of acute effects by permethrin. The findings of this study contribute to understanding the contamination levels of pesticides in bees and their honey, emphasizing the importance of monitoring and mitigating the adverse effects of pesticide exposure on bee populations and environmental health.

A miniaturized QuEChERS and UPLC-MS/MS method for the determination of mycotoxins in cashew nuts.

This study aimed to develop and validate a multi-mycotoxin analysis method applied to cashew nuts by employing a miniaturized QuEChERS method followed by determination by ultra-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). Satisfactory recoveries for the concentrations 1, 10 and 30 ng g-1, ranging from 66% (fumonisin B1) to 110% (ochratoxin A) and relative standard deviations lower than 9% (fumonisin B2) were obtained for the target compounds. Limits of quantification ranged from 0.004 ng g-1 (sterigmatocystin) to 0.59 ng g-1 (alternariol). The applicability of the analytical method was verified by analyzing 30 cashew nut samples from the city of Rio de Janeiro, RJ, southeastern Brazil. Aflatoxins M1, G2, G1, B2, B1, ochratoxin A and sterigmatocystin were detected, respectively, in 27%, 10%, 17%, 30%, 30%, 30% and 50% of the analyzed samples, at maximum concentrations of 0.56, 0.67, 1.43, 2.02, 4.93, 4.81, and 0.35 ng g-1. The maximum limit established by Brazilian legislation for aflatoxins was not exceeded by any of the analyzed samples.

Pesticides in vegetables and fruits from Brazil and risk assessment.

Levels of 237 pesticides were assessed in 1063 fruit and vegetable samples from 12 São Paulo markets spanning the period May 2015 to December 2022. The QuEChERS method was employed for extraction, followed by GC-MS/MS and LC-MS/MS analysis. Findings indicated that 30% of the samples contained residues below the Maximum Residue Limits (MRLs), while 6% exceeded these. Additionally, 23% exhibited excessive residues for their respective crops and 40% had no detectable residues. Health risk evaluation focused on tomatoes, cabbage and oranges, revealing exposure within 0.002-0.9% of the Acceptable Daily Intake (ADI), indicating no chronic risks. However, pyraclostrobin in orange presented a potential acute risk for adults (112%). These results underscore the necessity for continuous monitoring of pesticide residues in fruits and vegetables to safeguard consumer health, especially considering the significant levels of consumption.

Listeria monocytogenes in beef: a hidden risk.

Listeria monocytogenes in beef receives less attention compared to other pathogens such as Salmonella and Escherichia coli. To address this gap, we conducted a literature review focusing on the presence of L. monocytogenes in beef. This review encompasses the pathogenic mechanisms, routes of contamination, prevalence rates, and the laws and regulations employed in various countries. Our findings reveal a prevalence of L. monocytogenes in beef and beef products ranging from 2.5% to 59.4%. Notably, serotype 4b was most frequently isolated in cases of beef contamination during food processing, with the skinning and evisceration stages identified as critical points of contamination.

Essential and Non-Essential Elements Levels in Fish Species Highly Consumed in the Middle Miranda River, Brazilian Pantanal.

The present study investigated the levels of As, Ag, Al, Ba, Cd, Cr, Cu, Fe, Hg, Mn, Pb, Se, and Zn in muscle samples of six fish species (Pygocentrus nattereri, Serrasalmus marginatus, Mylossoma duriventre, Leporinus friderici, Pimelodus argenteus, and P. pantaneiro) highly consumed by local riverine and non-resident people in middle Miranda River, southern Brazilian Pantanal. Significant differences were detected for Ba, Fe, Mn, and Zn levels among the analyzed species. Pairwise comparison detected significant differences in element levels between species with similar diets, which implies that other factors, instead of species' feeding habits, could be involved in distinct levels of element bioaccumulation. Significant correlations between body size and concentrations were found for Ba in P. nattereri (moderate positive correlation), and for Mn in M. duriventre (weak positive correlation) and P. argenteus (moderate negative correlation). Levels exceeding tolerable daily intake (TDI) were found for Pb maximum concentrations in P. nattereri, M. duriventre, L. friderici, P. argenteus, and P. pantaneiro, and for Cd maximum concentration in P. argenteus. Health risk assessment indicated considerable risk only for the worst-case scenario (calculated from maximum concentrations) for all species. Adopting a Pb monitoring program in biotic and abiotic compartments in Miranda River is strongly recommended.