Evaluating antibiotic occurrence, degradation, and environmental risks in poultry litter within Argentina's agricultural hub.

This study explores the relationship between poultry farming's antibiotic administration practices and residual antibiotic levels in the litter before its application onto agricultural soils. Twenty-three antibiotics were performed across 19 Argentinean farms representing diverse antibiotic management practices. Analysis revealed up to 20 antibiotics from eight chemical classes in poultry litter samples, with tylosin, enrofloxacin, and salinomycin being the most relevant drugs. Farms with restricted antibiotic use in feed exhibited lower residual concentrations. A self-heating treatment was tested to reduce litter antibiotic levels. Although a 60 % reduction of antibiotics was found after treatment, prevalent compounds persisted at residual levels. Regulatory measures and comprehensive litter treatments pre-application are crucial to mitigate environmental risks. This is the first study that provides insight on the occurrence of >20 drugs in real poultry production scenarios from Latin America and demonstrates how relatively simple treatments can be readily applied to decrease the associated environmental risks.

Research progress on the regulation of oxidative stress by phenolics: the role of gut microbiota and Nrf2 signaling pathway.

In recent years, the increase in high-calorie diets and sedentary lifestyles has made obesity a global public health problem. An unbalanced diet promotes the production of proinflammatory cytokines and causes redox imbalance in the body. Phenolics have potent antioxidant activity and cytoprotective ability. They can scavenge free radicals and reactive oxygen species, and enhance the activity of antioxidant enzymes, thus combating the body's oxidative stress. They can also improve the body's inflammatory response, enhance the enzyme activity of lipid metabolism, and reduce the contents of cholesterol and triglyceride. Most phenolics are biotransformed and absorbed into the blood after the action by gut microbiota; these metabolites then undergo phase I and II metabolism and regulate oxidative stress by scavenging free radicals and increasing expression of antioxidant enzymes. Phenolics induce the expression of genes encoding antioxidant enzymes and phase II detoxification enzymes by stimulating Nrf2 to enter the nucleus and bind to the antioxidant response element after uncoupling from Keap1, thereby promoting the production of antioxidant enzymes and phase II detoxification enzymes. The absorption rate of phenolics in the small intestine is extremely low. Most phenolics reach the colon, where they interact with the microbiota and undergo a series of metabolism. Their metabolites will reach the liver via the portal vein and undergo conjugation reactions. Subsequently, the metabolites reach the whole body to exert biological activity by traveling with the systemic circulation. Phenolics can promote the growth of probiotics, reduce the ratio of Firmicutes/Bacteroidetes (F/B), and improve intestinal microecological imbalance. This paper reviews the nutritional value, bioactivity, and antioxidant mechanism of phenolics in the body, aiming to provide a scientific basis for the development and utilization of natural antioxidants and provide a reference for elucidating the mechanism of action of phenolics for regulating oxidative stress in the body. © 2023 Society of Chemical Industry.

Enantioselective uptake and translocation of atenolol in higher plants.

The presence of pharmaceuticals in surface water and wastewater has been an increasing area of research since they can represent a possible route for human exposure when these waters are used to irrigate crops. The concentration of these drugs in crops depends on their uptake and translocation within plants. A less recognized question is that over 50 % of pharmaceuticals are chiral compounds, but there is little knowledge about their enantioselectivity in plants. In this study, we evaluated the uptake, bioconcentration, and translocation of enantiomers of atenolol, a commonly used beta-blocker, in Arabidopsis thaliana cells and Lactuca sativa plants under hydroponic conditions. Atenolol was taken up by Arabidopsis thaliana cells during 120 h of exposure to solutions with 1 mg/L of R/S-(±)-atenolol. A moderate preference for R-(+)-atenolol over S-(-)-atenolol was observed, with the enantiomeric fraction (EF) reaching 0.532 ± 0.002 for the R enantiomer. Atenolol was also taken up and translocated by Lactuca sativa after hydroponic cultivation in nutrient solutions containing 1 or 10 µg/L R/S-(±)-atenolol. Moderate enantioselectivity was detected in the treatment with 10 µg/L, and the EF after 168 h was 0.42 ± 0.01, suggesting that S-(-)-atenolol was preferentially accumulated. Selectivity was also observed in the translocation factor (TF), calculated as the ratio of the concentration in the leaves over that in the roots. As many emerging contaminants are chiral, our findings highlight the importance to consider their fate and risks in terrestrial ecosystems at the enantiomer scale.

Effect of geographical location, processing and simulated digestion on antioxidant characteristics of quince (Cydonia oblonga).

Quince fruit (Cydonia oblonga Miller) is an important source of bioactive compounds, especially of phenolic compounds, that's why it is considered a good source of antioxidants. However, it is known that the antioxidant characteristics and the beneficial effect of foods are affected by the variety, geographical origin, processing and gastrointestinal digestion. In this work, the effects of the geographical origin, processing, and simulated digestion of quince jam on its antioxidant characteristics were studied. Phenolic composition and antioxidant capacity were determined in quince fruit and jam from four different locations in San Juan, Argentina. The results showed that quince fruit samples from St. Lucia had the highest total phenolic content (5.13 mg GAE/g; p < 0.05) and in vitro antioxidant capacity measured by ferric-reducing antioxidant power assay (FRAP) and radical-scavenging capacity assay (DPPH· and ABTS·+ ). With regard to quince jam, a positive effect was observed on its antioxidant characteristics after processing. Twenty-one phenolics were detected in jam, being most of them derivatives of hydroxycinnamic acids (eg. 5-caffeoylquinic acid; 4-caffeoylquinic acid and quinic acid). Studies on stability and bioaccessibility of quince phenolics showed that less than 25% of the initial phenolics in jam were detected after digestion being quinic acid and hydroxycinnamic acids the most resistant. The in vitro antioxidant capacity showed, in general, a similar trend to the phenolics content throughout the digestion process. The results obtained showed that the antioxidant activity of quince and jam is related to the type and amount of phenolics in the samples, which depends on the geographical origin, processing, and gastrointestinal digestion. These variables are not always taken into account when studying the probable antioxidant activity of food, even though they should be considered for a complete nutritional evaluation of a food.

Comparative metabolite fingerprinting of chia, flax and sesame seeds using LC-MS untargeted metabolomics.

Chia, flax, and sesame seeds are well known for their nutritional quality and are commonly included in bakery products. So far, the development of methods to verify their presence and authenticity in foods is a requisite and a raised need. In this work we applied untargeted metabolomics to propose authenticity markers. Seeds were analyzed by HPLC-MS/MS and 9938 features in negative mode and 9044 in positive mode were obtained by Mzmine. After isotopes grouping, alignment, gap-filling, filtering adducts, and normalization, PCA was applied to explore the dataset and recognize pre-existent classification patterns. OPLS-DA analysis and S-Plots were used as supervised methods. Twenty-five molecules (12 in negative mode and 13 in positive mode) were selected as discriminant for the three seeds, polyphenols and lignans were identified among them. To the best of our knowledge, this is the first approach using non-target HPLC-MS/MS for the authentication of chia, flax and sesame seeds.

Identification of key phenolic compounds responsible for antioxidant activities of free and bound fractions of blackberry varieties' extracts by boosted regression trees.

BACKGROUND: Free fractions of different blackberry varieties' extracts are high in phenolic compounds with antioxidant activities. However, the phenolic profiles and antioxidant activities against peroxyl radicals of bound fractions of different blackberry varieties' extracts have not been previously reported. In addition, what the key antioxidant phenolic compounds are in free and bound fractions of blackberry extracts remain unknown. This study aimed to investigate the phenolic profiles and antioxidant activities of free and bound fractions of eight blackberry varieties' extracts and reveal the key antioxidant phenolic compounds by boosted regression trees. RESULTS: Fifteen phenolics (three anthocyanins, four flavonols, three phenolic acids, two proanthocyanidins, and three ellagitannins) were identified in blackberry by ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry. Ferulic acid, ellagic acid, procyanidin C1, kaempferol-O-hexoside, ellagitannins hex, and gallic acid were major bound phenolics. Bound fractions of eight blackberry varieties' extracts were high in phenolics and showed great antioxidant activity. Boosted regression trees analysis showed that cyanidin-3-O-glucoside and chlorogenic acid were the most significant compounds, contributing 48.4% and 15.9% respectively to the antioxidant activity of free fraction. Ferulic acid was the most significant antioxidant compound in bound fraction, with a contribution of 61.5%. Principal component analysis showed that Kiowa was the best among the eight varieties due to its phenolic profile and antioxidant activity. CONCLUSION: It was concluded that blackberry varieties contained high amounts of bound phenolics, which confer health benefits through reducing oxidative stress. Ferulic acid was the key compound to explain the antioxidant activities of bound fractions. © 2021 Society of Chemical Industry.

Assessment of phytotoxic effects, uptake and translocation of diclofenac in chicory (Cichorium intybus).

Pharmaceuticals in the environment have been an increasing research topic over the past decade, since they can be found in both natural and drinking water, including irrigation of crops and edible plants with contaminated water. Our main goal was to evaluate the phytotoxic effect of diclofenac (DCF), a widely used pharmaceutical, on chicory (Cichorium intybus) seedlings. Additionally, we verified the uptake, bioconcentration and translocation of DCF from soil to chicory tissues. Results show that DCF induces different physiological changes in chicory seedlings. On the other hand, the soil-chicory experiment showed the activation of the detoxification system in plants treated with DCF (1 mg L-1). Finally, we found the migration of DCF from the irrigation water to the soil, followed by its uptake through the root, and its translocation to the aerial part of the chicory. However, DCF does not bioaccumulate in chicory leaves, being scarcely translocated from roots to aerial parts. This last result, along with the estimation of a daily intake of chicory, show that irrigation with water containing DCF (≤1 mg L-1) does not represent a threat to human health. To our knowledge, this is the first report on the effect of DCF on chicory seedlings, including the evaluation of its uptake and translocation.

Assessment of bioactive compounds and their in vitro bioaccessibility in whole-wheat flour pasta.

We studied the polyphenol profile and antioxidant properties of cooked whole-wheat pasta to evaluate its effective antioxidant capacity, including changes produced by its production and in vitro digestion. The polyphenol profile was studied by HPLC-ESI-MS/MS, while the antioxidant capacity was measured by TEAC and FRAP assays. Results show that the polyphenol profile and antioxidant capacity change along the elaboration of cooked pasta, being the cooking step important to increase the release of bound polyphenols, enhancing their antioxidant properties. On the other hand, the study of the bioaccessibility of polyphenols, using an experimental model that simulates human gastrointestinal digestion and subsequent absorption, showed that only a small fraction of the starting polyphenolic compounds, mainly free polyphenols, could be absorbed by the small intestine; thus, reducing their effective antioxidant capacity. To our knowledge, this is the first report showing the bioaccessibility of hydroxybenzoic acid glucoside, hydroxybenzoic acid diglucoside, tryptophan, 6-C-glucosyl-8-C-arabinosyl-apigenin and diferulic acids.

Relation between polyphenol profile and antioxidant capacity of different Argentinean wheat varieties. A Boosted Regression Trees study.

We report the polyphenol profile and antioxidant capacity (AC) of 12 Argentinean wheat varieties from different regions. The polyphenol profile was studied by HPLC-MS. The AC was measured by TEAC and FRAP. Twenty-five polyphenols were identified. ACA 315 and KLEIN GUERRERO varieties showed the highest content of polyphenols, whereas BIOINTA 3004, KLEIN CAPRICORNIO and LE 2330 showed the lowest one. ACA 315 presented the highest AC, while BIOINTA 3004 and KLEIN CAPRICORNIO showed the lowest one. Boosted Regression Trees (BRT) analyses helped finding significant correlations between AC and polyphenol profile, being hydroxybenzoic acid diglucoside, tryptophan, chrysoeriol-6,8-di-C-pentoside and isomers 4, 5, 9 and 12 of diferulic acids key compounds to explain the observed AC. To our knowledge, this is the first report on the interaction between the environment and wheat genotypes evaluated by BRT, showing how the whole polyphenol profile can explain the AC in wheat.

Matching in Vitro Bioaccessibility of Polyphenols and Antioxidant Capacity of Soluble Coffee by Boosted Regression Trees.

The aim of this study was to evaluate changes in polyphenol profile and antioxidant capacity of five soluble coffees throughout a simulated gastro-intestinal digestion, including absorption through a dialysis membrane. Our results demonstrate that both polyphenol content and antioxidant capacity were characteristic for each type of studied coffee, showing a drop after dialysis. Twenty-seven compounds were identified in coffee by HPLC-MS, while only 14 of them were found after dialysis. Green+roasted coffee blend and chicory+coffee blend showed the highest and lowest content of polyphenols and antioxidant capacity before in vitro digestion and after dialysis, respectively. Canonical correlation analysis showed significant correlation between the antioxidant capacity and the polyphenol profile before digestion and after dialysis. Furthermore, boosted regression trees analysis (BRT) showed that only four polyphenol compounds (5-p-coumaroylquinic acid, quinic acid, coumaroyl tryptophan conjugated, and 5-O-caffeoylquinic acid) appear to be the most relevant to explain the antioxidant capacity after dialysis, these compounds being the most bioaccessible after dialysis. To our knowledge, this is the first report matching the antioxidant capacity of foods with the polyphenol profile by BRT, which opens an interesting method of analysis for future reports on the antioxidant capacity of foods.

Linking soil, water, and honey composition to assess the geographical origin of argentinean honey by multielemental and isotopic analyses.

The objective of this research was to investigate the development of a reliable fingerprint from elemental and isotopic signatures of Argentinean honey to assess its geographical provenance. Honey, soil, and water from three regions (Córdoba, Buenos Aires, and Entre Ríos) were collected. The multielemental composition was determined by ICP-MS. δ(13)C was measured by isotopic ratio mass spectrometry, whereas the (87)Sr/(86)Sr ratio was determined using thermal ionization mass spectrometry. The data were analyzed by chemometrics looking for the association between the elements, stable isotopes, and honey samples from the three studied areas. Honey samples were differentiated by classification trees and discriminant analysis using a combination of eight key variables (Rb, K/Rb, B, U, (87)Sr/(86)Sr, Na, La, and Zn) presenting differences among the studied regions. The application of canonical correlation analysis and generalized procrustes analysis showed 91.5% consensus between soil, water, and honey samples, in addition to clear differences between studied areas. To the authors' knowledge, this is the first report demonstrating the correspondence between soil, water, and honey samples using different statistical methods, showing that elemental and isotopic honey compositions are related to soil and water characteristics of the site of origin.

Elemental and isotopic fingerprint of Argentinean wheat. Matching soil, water, and crop composition to differentiate provenance.

The aim of this study was to investigate if elemental and isotopic signatures of Argentinean wheat can be used to develop a reliable fingerprint to assess its geographical provenance. For this pilot study we used wheat cultivated at three different regions (Buenos Aires, Córdoba, and Entre Ríos), together with matching soil and water. Elemental composition was determined by ICP-MS. δ(13)C and δ(15)N were measured by isotopic ratio mass spectrometry, while (87)Sr/(86)Sr ratio was determined using thermal ionization mass spectrometry. Wheat samples from three sampling sites were differentiated by the combination of 11 key variables (K/Rb, Ca/Sr, Ba, (87)Sr/(86)Sr, Co, Mo, Zn, Mn, Eu, δ(13)C, and Na), demonstrating differences among the three studied regions. The application of generalized Procrustes analysis showed 99.2% consensus between cultivation soil, irrigation water, and wheat samples, in addition to clear differences between studied areas. Furthermore, canonical correlation analysis showed significant correlation between the elemental and isotopic profiles of wheat and those corresponding to both soil and water (r(2) = 0.97, p < 0.001 and r(2) = 0.96, p < 0.001, respectively). To our knowledge, this is the first report demonstrating the correspondence between soil, water, and wheat samples using different statistical methods, showing that wheat elemental and isotopic compositions are mainly related to soil and irrigation water characteristics of the site of growth.

How much do soil and water contribute to the composition of meat? A case study: meat from three areas of Argentina.

The main goal of this study was to propose a reliable method to verify the geographical origin of meat, establishing the influence of soil and water on its isotopic and elemental composition. Thus, beef meat, soil, and water samples were collected from three major cattle-producing regions of Argentina (Buenos Aires, Córdoba, and Entre Ríos). Multielemental composition was determined on these three matrices by inductively coupled plasma mass spectrometry (ICP-MS), δ(13)C and δ(15)N by isotope-ratio mass spectrometry (IRMS), and the (87)Sr/(86)Sr ratio by thermal ionization mass spectrometry (TIMS). Soil and drinking water samples could be characterized and clearly differentiated by combining the isotopic ratios and elements, demonstrating differences in geology and climatic conditions of three regions. Similarly, meat originating at each sampling area was characterized and differentiated using only five key variables (Rb, Ca/Sr, δ(13)C, δ(15)N, and (87)Sr/(86)Sr). Generalized procrustes analysis (GPA), using the three studied matrices (soil, water, and meat) shows consensus between them and clear differences between studied areas. Furthermore, canonical correlation analysis (CCA) demonstrates significant correlation between the chemical-isotopic profile of meat with those corresponding to both soil and water (r(2) = 0.93, p < 0.001; and r(2) = 0.83, p < 0.001, respectively). So far, there are clear coincidences between the meat fingerprint and those from soil/water where cattle grew, presenting a good method to establish beef provenance. To the authors' knowledge this is the first report linking the influence of soil and water all together on the composition of beef, presenting the basis for the authentication of Argentinean beef, which could be extended to meat from different provenances.

Fingerprints for main varieties of argentinean wines: terroir differentiation by inorganic, organic, and stable isotopic analyses coupled to chemometrics.

Our main goal was to investigate if robust chemical fingerprints could be developed for three Argentinean red wines based on organic, inorganic, and isotopic patterns, in relation to the regional soil composition. Soils and wines from three regions (Mendoza, San Juan, and Córdoba) and three varieties (Cabernet Sauvignon, Malbec, and Syrah) were collected. The phenolic profile was determined by HPLC-MS/MS and multielemental composition by ICP-MS; (87)Sr/(86)Sr and δ(13)C were determined by TIMS and IRMS, respectively. Chemometrics allowed robust differentiation between regions, wine varieties, and the same variety from different regions. Among phenolic compounds, resveratrol concentration was the most useful marker for wine differentiation, whereas Mg, K/Rb, Ca/Sr, and (87)Sr/(86)Sr were the main inorganic and isotopic parameters selected. Generalized Procrustes analysis (GPA) using two studied matrices (wine and soil) shows consensus between them and clear differences between studied areas. Finally, we applied a canonical correlation analysis, demonstrating significant correlation (r = 0.99; p < 0.001) between soil and wine composition. To our knowledge this is the first report combining independent variables, constructing a fingerprint including elemental composition, isotopic, and polyphenol patterns to differentiate wines, matching part of this fingerprint with the soil provenance.

Main flavonoids, DPPH activity, and metal content allow determination of the geographical origin of propolis from the Province of San Juan (Argentina).

The chemical characterization as well as the assessment of geographical origin of propolis from several areas of the Provincia de San Juan (Argentina) is reported. Chemical characterization of propolis was performed by measuring total phenolic (TP), total flavonoids (FL), free radical scavenging capacity (DPPH bleaching), and metal content in samples of six different districts. Methanolic propolis extracts (MEP) showed TP ranging from 25.7 to 39.3 g of gallic acid equivalents per 100 g of MEP, whereas flavonoids ranged from 6.6 to 13.3 g of quercetin equivalents per 100 g of MEP. Six main flavonoids were isolated and identified from the propolis samples, comprising the flavanones 7-hydroxy-8-methoxyflavanone (1), pinocembrin (2), and pinobanksin (3), the flavones chrysin (4) and tectochrysin (5), and the flavonol galangin (6). Compounds 1-6 were quantified by HPLC-PDA. Free radical scavenging activity, measured as percent DPPH bleaching, ranged from 46.6 to 89.5 at 10 mug/mL. Moreover, propolis samples presented high contents of Ca, K, Fe, Na, and Mg, but low amounts of Mn and Zn. Linear discriminant analysis affords eight descriptors, galangin, pinocembrin, pinobanksin, chrysin, tectochrysin, DPPH, K, and Na, allowing a clear distinction with 100% accuracy among different origins within the Provincia de San Juan. A direct relationship of DPPH free radical scavenging activity with TP or with compounds 1-6 was not found, showing the need of further evaluation on the origin of free radical activity in propolis samples.