From data to insight: Exploring contaminants in different food groups with literature mining and machine learning techniques.

Food remains a major source of human exposure to chemical contaminants that are unintentionally present in commodities globally, despite strict regulation. Scientific literature is a valuable source of quantification data on those contaminants in various foods, but manually summarizing the information is not practicable. In this review, literature mining and machine learning techniques were applied in 72 foods to obtain relevant information on 96 contaminants, including heavy metals, polychlorinated biphenyls, dioxins, furans, polycyclic aromatic hydrocarbons (PAHs), pesticides, mycotoxins, and heterocyclic aromatic amines (HAAs). The 11,723 data points collected from 254 papers from the last two decades were then used to identify the patterns of contaminants distribution. Considering contaminant categories, metals were the most studied globally, followed by PAHs, mycotoxins, pesticides, and HAAs. As for geographical region, the distribution was uneven, with Europe and Asia having the highest number of studies, followed by North and South America, Africa and Oceania. Regarding food groups, all contained metals, while PAHs were found in seven out of 12 groups. Mycotoxins were found in six groups, and pesticides in almost all except meat, eggs, and vegetable oils. HAAs appeared in only three food groups, with fish and seafood reporting the highest levels. The median concentrations of contaminants varied across food groups, with citrinin having the highest median value. The information gathered is highly relevant to explore, establish connections, and identify patterns between diverse datasets, aiming at a comprehensive view of food contamination.

Occurrence of polycyclic aromatic hydrocarbons, microplastics and biofilms in Alqueva surface water at touristic spots.

Freshwater pollution is a huge concern. A study aiming to evaluate physico-chemical characteristics, microbiota, occurrence of two groups of persistent environmental pollutants with similar chemical properties (polycyclic aromatic hydrocarbons- PAHs and microplastics - MPs) in Alqueva's surface water was performed during 2021. Water samples were collected at three spots related to touristic activities (two beaches and one marina) during the Winter, Spring, Summer and Autumn seasons. In addition, the presence of biofilms on plastic and natural materials (stone, wood/ vegetal materials) were assessed and compared. Water quality based on physicochemical parameters was acceptable with a low eutrophication level. PAHs concentration levels were lower than the standard limits established for surface waters by international organizations. However, carcinogenic compounds were detected in two sampling locations, which can pose a problem for aquatic ecosystems. PAHs profiles showed significant differences when comparing the dry seasons with the rainy seasons, with a higher number of different compounds detected in Spring. Low molecular weigh compounds, usually associated with the atmospheric deposition and petroleum contamination, were more prevalent. MPs were detected in all samples except one during the Winter season. The polymers detected were poly(methyl-2-methylpropenoate), polystyrene, polyethylene terephthalate, polyamide, polypropylene, styrene butadiene, polyvinyl chloride and low /high density polyethylene with the last being the most frequent. Biofilms were more often detected on plastics than on natural materials. In addition, biofilms detected on plastics were more complex with higher microbial diversity (e.g., bacteria, fungi/yeast and phytoplancton organisms) and richer in extrapolymeric material. Based on morphological analysis a good agreement between microbiota and microorganism present in the biofilms was found. Among microbiota were identified microorganisms previously linked to plastic and PAHs detoxification suggesting the need for further studies to evaluate the viability of using biofilms as part of a green bioremediation strategy to mitigate water pollution.

Mineralocorticoid Receptor Antagonists Eplerenone and Spironolactone Modify Adrenal Cortex Morphology and Physiology.

Mineralocorticoid receptor antagonists (MRAs) are a class of anti-hypertensive drugs that act by blocking aldosterone action. The aim of this study was to evaluate whether the MRAs spironolactone and eplerenone influence adrenal cortical physiology and morphology. Spontaneous hypertensive rats (SHR, n = 18) and normotensive rats (WKY, n = 18) were randomly exposed to a daily dose of spironolactone (n = 6), eplerenone (n = 6), or no drug (n = 6) over 28 days. After that, aldosterone, corticosterone, and 11-deoxycorticosterone plasma concentrations were quantified. Adrenal glands were subjected to morphological analysis to assess lipid droplets content, capsular width, cell proliferation, and steroidogenic proteins expression. The adrenal cortex in untreated SHR showed higher lipid droplet content as than in WKY. In SHR, MRA treatment was associated with higher circulating aldosterone levels and Ki-67 expression in aldosterone-secreting cells. In WKY, the only difference observed after MRA spironolactone treatment was a narrower capsule. There was no difference in abundance of steroidogenic enzyme between groups. In conclusion, MRAs modify adrenal gland function and morphology in SHR. The effects observed within the adrenal glomerulosa with aldosterone-secreting cell proliferation and higher circulating aldosterone levels suggests that MRA treatment provokes activation of the renin angiotensin system. The prognostic value of hyperaldosteronism secondary to MRAs blockade requires further investigation.

Nutritional quality of protein concentrates from Moringa Oleifera leaves and in vitro digestibility.

The nutritional value and digestibility of leaf proteins is still a major issue. Therefore, the goal of this work was to optimize the production of a protein concentrate (PC) from Moringa Oleifera defatted leaves (MODL) by enzymatic extraction using Viscozyme L and evaluate its nutritional quality and digestibility. Protein extraction conditions were screened using a factorial design. Enzyme/Substrate ratio and pH had no significant effect, whereas, the significant variables, temperature (°C), enzyme concentration and incubation time (h) were optimized by central composite design (CCD). PC contained 55.7% of proteins with a balanced amino acid profile when compared with MODL and higher content of essential amino acids (EAAs) (488.6-402.9 mg/g of protein respectively). Improvement on protein digestibility was observed for MODL compared to PC (64.75-99.86% respectively) and higher protein digestibility corrected amino acid score (PDCAAS) (62.10-91.41% respectively). PC meets FAO protein quality expectations.

Simultaneous determination of melatonin and trans-resveratrol in wine by dispersive liquid-liquid microextraction followed by HPLC-FLD.

The discovery of melatonin (Mel) in wines triggered a new interest in the paradigm of health benefits and wine consumption, usually ascribed to trans-resveratrol (trans-RSV). In this context, a dispersive liquid-liquid microextraction for the analysis of Mel and trans-RSV in wines by LC-FLD was developed. A 26-1 factorial design was used to identify the significant variables (p < 0.05) and Central Composite Design was used to achieve the optimal conditions: 300 µL of chloroform (extracting solvent), 1500 µL of acetonitrile (disperser solvent) and 1500 mg of NaCl (ionic strength). Excellent linearity (R2 > 0.9999), repeatability (<3.55%), and accuracy (<7.18%) were obtained using a blank matrix and recoveries (>91.9%) using wines. The method was successfully applied to the analyses of Mel (0.63-7.44 ng mL-1) and trans-RSV (169-2616 ng mL-1) in different wine varieties. Comparison with literature point the overall advantages of the new method.

Acute and chronic toxicity assessment of haloacetic acids using Daphnia magna.

Haloacetic acids (HAAs) are undesirable disinfection by-products (DBPs), released into aquatic ecosystems from various anthropogenic and natural sources. The aim of this study was to examine the ecological risk of exposure to three HAAs commonly detected in water, such as monobromoacetic acid (MBA), monochloroacetic acid (MCA), and trichloroacetic acid (TCA), in in vivo acute and chronic toxicity tests using Daphnia magna as a model. Acute tests showed that MBA was the most toxic of these compounds followed by MCA and TCA as evidenced by immobilization. Aquatic organisms in natural conditions might be exposed simultaneously to numerous compounds; thus, binary mixtures of selected HAAs and a ternary mixture of these were tested. Concentration addition (CA) and independent action (IA) models were used for a predictive assessment of mixture toxicity. Data demonstrated that CA appeared to be the most reliable indicator for HAAs binary and ternary mixtures suggestive of an additive behavior. Median effective concentration (EC50) values from the mixed exposure tests were significantly lower than results obtained from single tests for all three HAAs where an increase of toxicity greater than 50%. Multigenerational chronic tests were also performed exposing daphnids to the ternary mixture of HAAs. A markedly decreased sexual maturity and number of offspring and broods per daphnid especially in the second generation were noted.

The Use of Feathers from Racing Pigeons for Doping Control Purposes.

The development of accurate and reliable analytical methodologies to detect the abuse of doping agents in sport animals is crucial to ensure their welfare, as well as to support continuing social acceptance of these sports. The detection of doping agents in racing pigeons is difficult, especially owing to the disadvantages and limitations of obtaining samples from conventional matrices. The present study aimed to develop and validate an analytical methodology combining a two-step extraction procedure (liquid-liquid extraction and solid-phase extraction) in feathers from racing pigeons with analysis by liquid chromatography tandem mass spectrometry (LC-MS-MS) that enabled the simultaneous detection of a beta-agonist drug (clenbuterol) and three corticosteroids (prednisolone, betamethasone and budesonide). The method was validated concerning linearity (with coefficients of determination always higher than 0.99), accuracy (87.3-112.4%), precision (repeatability and intermediate precision coefficient of variation (CV%) always below 15%), recovery (71.6-98.2%), limits of detection (0.24-0.52 ng/g) and quantification (0.79 and 0. 1.74 ng/g) and specificity. The applicability of the method was performed using feathers from pigeons administered orally with a daily dose of 0.075 mg of betamethasone. The drug was administered during 60 days and successive analyses of feathers were performed, at the end of the administration protocol and also after ceasing the oral administration of the drug, for a three weeks period.

Modeling of α-acids and xanthohumol extraction in dry-hopped beers.

The practice of dry-hopping has been used by the brewing industry to obtain beers with increased contents of flavor and bitterness compounds. Notwithstanding this, other compounds such as α-acids (AA) and xhanthohumol (XN) are co-extracted influencing the final characteristics of the beer, particularly its beneficial bioactivity. In this context a model for the understanding of AA and XN extraction by dry-hopping is proposed. The varieties Chinook (CHI), East Kent Goldings (EKG) and Tettnanger (TET) were assayed and robust statistical approaches were applied for data interpretation. Concentration of AA in beers post-maturation reached values higher than 20 mg/L using 2.8 g/L of CHI hops and 10 days of maturation. For XN, a similar behavior was verified. The maximum efficiency of AA and XN extraction (transfer rate) were reached at 13.5 days with dose rates of 147 and 13.9 mg/L, respectively.

Simultaneous Extraction and Determination of Preservatives and Antioxidants in Juice Samples by an Optimized Microextraction Method Using Central Composite Design and Validated with Accuracy Profile.

>Background: Food additives are widely used in industries. Overall, these additives have a beneficial role, but if their concentration exceeds certain limits, they may have an adverse effect on human health. Objective: This study outlines the determination of benzoic acid (BA), sorbic acid (SA), butylated hydroxyanisole (BHA), and butylated hydroxytoluene (BHT) in juices using dispersive liquid-liquid microextraction and HPLC-diode-array detection. Methods: Different parameters that significantly affect the extraction efficiency were optimized. The disperser and extraction solvents were acetone and chloroform, respectively. The other parameters were selected and optimized using two-level (2k) factorial and central composite designs, respectively. A full method validation using an accuracy profile for the total measurement error was carried out. Results: The optimized conditions were 625 µL acetone, 350 µL chloroform, 0.85 g NaCl, and pH 2. The validated method demonstrated good linearity with R² ≥ 0.99 and good precision with the RSD of repeatability and intermediate precision at 1.97-10.7% and 2.31-11.9%, respectively. The relative recoveries were 96.2-105.4%, and the LODs were around 0.03 µg/mL for all compounds. The analysis of 41 samples revealed that BA and SA were quantified in 25 and 20 samples, respectively. BHA and BHT were not detected. Conclusions: The proposed methodology is an appropriate tool to determine important food additives in juices to ensure their compliance with the food additives legislation. Highlights: The work has demonstrated that the method can be successfully used in the simultaneous determination of four food additives in fruit juices.

Biological activities of peptide concentrates obtained from hydrolysed eggshell membrane byproduct by optimisation with response surface methodology.

The increase of hen egg consumption demands profitable applications for eggshells, including their membranes, in order to minimize environmental and public health problems that could result from their accumulation. This work presents an innovative application for eggshell membranes to obtain an added-value food ingredient that combines maximized ACE-inhibitory and antioxidant activities. Firstly, the use of acetic acid 5% (v/v); and 3-mercaptopropionic acid 1.25 M enabled 63% recovery of eggshell membrane proteins. Secondly, the extracted proteins were hydrolysed by alcalase from Bacillus licheniformis, viscozyme L and protease from Bacillus amyloliquefaciens. Hydrolysis conditions were optimized using response surface methodology experimental design. The ACE-inhibitory activity (IC50) was 34.5 ± 2.1 µg mL-1, 63.0 ± 4.2 µg mL-1 and 43.0 ± 8.5 µg mL-1 for each enzyme, respectively, and the antioxidant activity was ca. 4.0 µmoltrolox equivalent mg-1hydrolysed protein. The combination of both bioactive properties is of potential interest to control cardiovascular diseases.

Identification and quantification of anthocyanins in fruits from Neomitranthes obscura (DC.) N. Silveira an endemic specie from Brazil by comparison of chromatographic methodologies.

Neomitranthes obscura (DC.) N. Silveira is a Brazilian fruit belonging to the Myrtaceae family that contains anthocyanins in the peel and was studied for the first time in this work. Delphinidin-3-O-galactoside, delphinidin-3-O-glucoside, cyanidin-3-O-galactoside, cyanidin-3-O-glucoside, cyanidin-3-O-arabinoside, petunidin-3-O-glucoside, pelargonidin-3-O-glucoside, peonidin-3-O-galactoside, peonidin-3-O-glucoside, cyanidin-3-O-xyloside were separated and identified by LC/DAD/MS and by co-elution with standards. Reliable quantification of anthocyanins in the mature fruits was performed by HPLC/DAD using weighted linear regression model from 0.05 to 50mg of cyaniding-3-O-glucoside L(-1) because it gave better fit quality than least squares linear regression. Good precision and accuracy were obtained. The total anthocyanin content of mature fruits was 263.6 ± 8.2 mg of cyanidin-3-O-glucoside equivalents 100 g(-1) fresh weight, which was in the same range found in literature for anthocyanin rich fruits.

Application of a fast and cost-effective in situ derivatization method prior to gas chromatography with mass spectrometry to monitor endocrine disruptors in water matrices.

This work deals with the optimization of a rapid, cost-effective, and eco-friendly gas chromatography with mass spectrometry method for the simultaneous determination of four endocrine disruptor compounds in water matrices: estrone, 17ß-estradiol, 17α-ethinylestradiol, and bisphenol A, that are currently considered to be of main concern in the field of water policy and that could became candidates for future regulations. The method involves simultaneous derivatization and extraction of compounds by dispersive liquid-liquid microextraction followed by gas chromatography with mass spectrometry analysis. Derivatization and extraction parameters were optimized with the aid of experimental design approach. An excellent linear response was achieved for all analytes (r(2) ≥ 0.999). Limits of detection and quantification are 0.003-0.005 and 0.0094-0.0164 µg/L, respectively. Intraday precision ranged between 1.1 and 12.6%, whereas interday precision ranged between 0.5 and 14.7%. For accuracy, bias values varied between -15.0 and 13.7%. Recoveries at three concentration levels ranged from 86.4 to 118.2%. The proposed method can be applied to the routine analysis of groundwater, river, sea, tap, and mineral water samples with excellent sensitivity, precision, and accuracy.

Sensitive quantitation of polyamines in plant foods by ultrasound-assisted benzoylation and dispersive liquid-liquid microextraction with the aid of experimental designs.

A new method involving ultrasound-assisted benzoylation and dispersive liquid-liquid microextraction was optimized with the aid of chemometrics for the extraction, cleanup, and determination of polyamines in plant foods. Putrescine, cadaverine, spermidine, and spermine were derivatized with 3,5-dinitrobenzoyl chloride and extracted by dispersive liquid-liquid microextraction using acetonitrile and carbon tetrachloride as dispersive and extraction solvents, respectively. Two-level full factorial design and central composite design were applied to select the most appropriate derivatization and extraction conditions. The developed method was linear in the 0.5-10.0 mg/L range, with a R(2) ≥ 0.9989. Intra- and interday precisions ranged from 0.8 to 6.9% and from 3.0 to 10.3%, respectively, and the limit of detection ranged between 0.018 and 0.042 µg/g of fresh weight. This method was applied to the analyses of six different types of plant foods, presenting recoveries between 81.7 and 114.2%. The method is inexpensive, versatile, simple, and sensitive.

Monitoring pesticide residues in greenhouse tomato by combining acetonitrile-based extraction with dispersive liquid-liquid microextraction followed by gas-chromatography-mass spectrometry.

A multiclass and multiresidue method for pesticide analysis in tomato was validated. Extraction and pre-concentration of the pesticide residues from acetonitrile extracts was performed by using dispersive liquid-liquid microextraction (DLLME) technique, followed by gas chromatography-mass detection. DLLME was performed using carbon tetrachloride as extractive solvent and acetonitrile extract as dispersive solvent, in order to increase enrichment factor of the extraction procedure. Validation parameters indicated the suitability of the method for routine analyses of thirty pesticides in a large number of samples. In general, pesticide recoveries ranged between 70% and 110% and repeatability ranged between 1% and 20%. The proposed method was applied to the monitoring of pesticides in tomatoes grown during winter in greenhouses. Among the compounds considered in this work, cyprodinil was found in tomato at concentrations of 0.33mg/kg, other pesticides like azoxystrobin, fenhexanid, tolyfluanid, λ-cyhalothrin and trifloxystrobin were also detected, but, not quantified.

Impact of intensive horticulture practices on groundwater content of nitrates, sodium, potassium, and pesticides.

A monitoring program of nitrate, nitrite, potassium, sodium, and pesticides was carried out in water samples from an intensive horticulture area in a vulnerable zone from north of Portugal. Eight collecting points were selected and water-analyzed in five sampling campaigns, during 1 year. Chemometric techniques, such as cluster analysis, principal component analysis (PCA), and discriminant analysis, were used in order to understand the impact of intensive horticulture practices on dug and drilled wells groundwater and to study variations in the hydrochemistry of groundwater. PCA performed on pesticide data matrix yielded seven significant PCs explaining 77.67% of the data variance. Although PCA rendered considerable data reduction, it could not clearly group and distinguish the sample types. However, a visible differentiation between the water samples was obtained. Cluster and discriminant analysis grouped the eight collecting points into three clusters of similar characteristics pertaining to water contamination, indicating that it is necessary to improve the use of water, fertilizers, and pesticides. Inorganic fertilizers such as potassium nitrate were suspected to be the most important factors for nitrate contamination since highly significant Pearson correlation (r = 0.691, P < 0.01) was obtained between groundwater nitrate and potassium contents. Water from dug wells is especially prone to contamination from the grower and their closer neighbor's practices. Water from drilled wells is also contaminated from distant practices.

Optimization of conditions for anthocyanin hydrolysis from red wine using response surface methodology (RSM).

Optimization of conditions for anthocyanin hydrolysis from red wine was investigated using response surface methodology. The aglycon forms of the anthocyanins were quantified by high-performance liquid chromatography with diode array detection. The combined effects of three independent variables, HCl amount, heating temperature, and hydrolysis time, were studied using a 2(3) full-factorial central composite design. Anthocyanin hydrolysis yield depended mainly on the heating temperature and time of hydrolysis. HCl amount was the factor that least influenced the hydrolysis of anthocyanins. From experimental results, the maximum yield of anthocyanidins was reached with 9.8 mL of HCl (32% v/v), a heating temperature of 166.2 °C, and a hydrolysis time of 46.6 min. Five anthocyanidins, namely, delphinidin, cyanidin, petunidin, peonidin, and malvidin, were quantified in red wine. The reliability of the method was confirmed by recovery experiments, performed under optimal conditions. Recoveries indicated that anthocyanidins resisted the hydrolysis conditions.

Heterocyclic aromatic amine formation in barbecued sardines (Sardina pilchardus) and Atlantic salmon (Salmo salar).

The formation of heterocyclic aromatic amines (HAs) during barbecuing of sardines ( Sardina pilchardus ) and Atlantic salmon ( Salmo salar ) to various degrees of doneness and grilling conditions was evaluated by HPLC-diode array (DAD)/fluorescence (FLD) detection. Additionally, the influences of charcoal and electric heat sources on formation of HAs in grilled salmon were compared. With regard to sardine samples barbecued at 280-300 degrees C, "rare" samples produced nondetectable amounts of HAs, "medium" sardines presented IQ, MeIQx, PhIP, and AalphaC at levels of 1.9, 4.4, 3.3, and 2.0 ng/g, respectively, and "well done" sardines presented IQ, MeIQx, Trp-P-1, Trp-P-2, PhIP, AalphaC, and MeAalphaC at levels of 0.9, 2.2, 1.8, 8.2, 6.5, 17.7, and 10.6 ng/g, respectively. Different qualitative and quantitative profiles of HAs were observed in sardine and salmon samples cooked under similar conditions of temperature and doneness. Levels of 13.3, 3.5, 1.13, and 3.18 ng/g were obtained, respectively, for PhIP, AalphaC, MeAalphaC, and Glu-P-1 in salmon samples barbecued at 280-300 degrees C. The contents of HAs were significantly higher in these samples than in salmon samples barbecued at 180-200 degrees C or in the electric device. However, MeIQx content (0.5 ng/g) was lower in salmon samples barbecued at 280-300 degrees C than in the other samples.

Effect of beer/red wine marinades on the formation of heterocyclic aromatic amines in pan-fried beef.

The effect of beer or red wine marinades on the reduction of heterocyclic aromatic amines (HAs) formation in pan-fried beef was compared. The cooking experiments were performed under well-controlled temperature and time conditions. The samples were analyzed for HAs contents using solid-phase extraction and high-performance liquid chromatography-diode array detection/fluorescence detection. Unmarinated samples cooked in similar conditions provided reference HAs levels. Marinating with beer or with red wine resulted in decreased levels of HAs. The amount of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine and 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline reduced significantly, respectively, around 88 and 40% after 6 h of marinating with beer or with wine. High variations were observed for reductions of AalphaC, ranging between 7 and 77%. Only beer marinade significantly reduced the levels of 4,8-DiMeIQx at 1, 2, and 4 h of marinating. Multivariate statistical treatment of results indicated that beer can be more efficient on the reduction of some HAs formation. In addition, results from descriptive sensory analysis of unmarinated and 2 h marinated beef samples, tested for by two trained sensory panels, pointed to beer marinade as the most adequate for maintaining the usual overall appearance and quality of the pan-fried steaks.