A Review on the Use of Deep Eutectic Solvents in Protection Reactions.

Given the recent research on the application of eco-sustainable methods in organic chemistry, we have focused our attention on the derivatization processes for fundamental functional groups in organic chemistry, such as amino, hydroxyl and carbonyl groups. Protection reactions are needed to temporarily block a certain reactive site on a molecule. The use of green solvents in this context has made an excellent contribution to the development of eco-sustainable methods. In recent years, deep eutectic solvents (DESs) have had great success as a new class of green solvents used in various chemical applications, such as extraction or synthetic processes. These solvents are biodegradable and nontoxic. In this framework, a list of relevant works found in the literature is described, considering DESs to be a good alternative to classic toxic solvents in the protection reactions of important functional groups.

Dietary supplementation with chia polyphenols alleviates oxidative stress and improves egg nutritional quality in Japanese quails under heat stress.

Heat stress in poultry is a major concern, especially in regions with hot summers and scarce cooling infrastructure. Dietary supplementation with antioxidants, such as polyphenols, has risen as a strategy to mitigate the physiological consequences of heat stress. A by-product of the extraction of oil from chia seeds, which is discarded if not used, could be a possible source of polyphenols. The aim of the present study was to evaluate the effects of dietary supplementation with polyphenols from defatted chia seed cake on the general performance, and oxidative status of Japanese quail exposed to heat stress. Furthermore, productive performance, egg quality and yolk fatty acid composition were also assessed. A total of 36 females (96 days of age) were randomly assigned to different diets: BASAL (control), LDCP (low dose of chia polyphenols), or HDCP (high dose of chia polyphenols). Half the animals in each diet group were exposed to 34 °C for 9 h a day (Heat Stress; HS), while the other half remained at the standard 24 °C (No Heat Stress; NHS). After 23 days of experimental conditions, animals under HS showed higher body temperatures and time spent panting, but lower egg laying rate. Moreover, HS modulated the activity of catalase and glutathione peroxidase enzymes, increasing lipid peroxidation in serum and liver; and increased saturated fatty acids in egg yolk. Supplementation with chia polyphenols helped to mitigate the HS effects, especially on glutathione peroxidase activity, decreasing lipid peroxidation. In addition, supplementation with HDCP showed the highest proportion of polyunsaturated fatty acids in liver and egg yolk. In conclusion, the use of defatted chia seed cake could represent a sustainable strategy to mitigate heat stress effects on Japanese quail, due to its capacity to decrease oxidative stress and improve the nutritional quality of egg, while decreasing the amount of waste generated by the food industry.

Food inauthenticity: Authority activities, guidance for food operators, and mitigation tools.

Historically, food fraud was a major public health concern which helped drive the development of early food regulations in many markets including the US and EU market. In the past 10 years, the integrity of food chains with respect to food fraud has again been questioned due to high profile food fraud cases. We provide an overview of the resulting numerous authoritative activities underway within different regions to counter food fraud, and we describe the guidance available to the industry to understand how to assess the vulnerability of their businesses and implement appropriate mitigation. We describe how such controls should be an extension of those already in place to manage wider aspects of food authenticity, and we provide an overview of relevant analytical tools available to food operators and authorities to protect supply chains. Practical Application: Practical Application of the provided information by the food industry in selecting resources (guidance document, analytical methods etc.).

Influence of the extraction conditions on chia oil quality and partially defatted flour antioxidant properties.

Partially defatted chia flour (PDCF) is a by-product of oil extraction from chia seeds (Salvia hispanica L.). It may be used as an ingredient to improve food products, especially due to its antioxidant properties. In this work, we studied the best screw press extraction conditions that allow preserving the antioxidant properties of PDCF. A central composite design was applied to perform a response surface analysis in order to optimize the oil extraction. The variables considered for optimization were seed moisture content and pressing temperature. Besides the oil quality indicators, the study was focused on the assessment of PDCF properties, including total polyphenol content and antioxidant capacity determined by chemical methods. Our results show that, within the range of screw press conditions evaluated, the chemical quality of the oil and the antioxidant properties of PDCF are both preserved. The best results (highest oil yield and stability) were obtained under a seed moisture content of 10.2% and a pressing temperature of 58.5 °C. In general, our results indicate that screw press methodology can be applied to process chia seeds, using a wide range of conditions, to concurrently produce good quality oil and a PDCF with beneficial properties.

Antioxidant properties and phenolic composition of "Composed Yerba Mate".

Yerba mate contains bioactive compounds, and is widely consumed as a decoction beverage in several Southern American countries. At present, the consumption of mate with added herbal blends and flavors, called "composed yerba mate", has increased; however, no studies on the antioxidant characteristics of these products have been published. In this sense, the main objective was to assess the antioxidant characteristics of "composed yerba mate" compared to "traditional yerba mate", in the form it is traditionally consumed. Total polyphenols content ranged from 15 to 45 mg/g GAE in all decoctions analyzed. Seventeen phenolic compounds were identified and quantified by HPLC-DAD-MS/MS, mainly belonging to the caffeoylquinic acids group. The antioxidant capacity was measured using in vitro assays, Ferric reducing ability of plasma (FRAP) and Trolox equivalent antioxidant capacity (TEAC), and with Saccharomyces cerevisiae as the in vivo model organism. All decoctions displayed antioxidant activity and were capable of rescuing yeast cells between 10.68 and 18.38% from oxidative stress. Multiple regression analysis showed a high correlation between phenolic composition and activity of samples, where different compounds indicate a significant contribution to the observed activity. Significant differences were found in the content, profile and antioxidant activity of polyphenols when "traditional yerba mate" and "composed yerba mate" were compared. In some cases, the antioxidant capacity was similar or higher in composed yerba mate; while the rest displayed lower biological activity. Based on these findings, it would be possible to assume that the addition of herb mixtures modifies the antioxidant and biological properties of mate. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at (10.1007/s13197-020-04961-x).

Proteomic analysis of Saccharomyces cerevisiae to study the effects of red wine polyphenols on oxidative stress.

Understanding the molecular mechanisms underlying the "French paradox" has contributed to a growing interest in the investigation of the biological activity of red wine polyphenols (RWP). The main goal of this research is to provide valuable information on how RWP could exert their biological action at the cellular level. So, we report a proteomic analysis of S. cerevisiae exposed to both pro-oxidant (H2O2) and antioxidant (wine) agents. Cellular proteome analysis shows that RWP modify the level of certain proteins. Under both normal conditions (Wine treatment) and oxidative stress situations (Wine + H2O2 treatment), the proteins involved in the metabolism and biosynthesis of biomolecules were down-regulated, while one ribosomal protein was up-regulated, probably performing its ribosome-independent functions, and so contributing to the stress defense system. Considering this action mechanism, we suggest that RWP may be acting as mild pro-oxidants and, therefore, exerting a hormetic effect that leads to the strengthening of cells' antioxidant capacity.

Bioaccumulation and trophic transfer of metals, As and Se through a freshwater food web affected by antrophic pollution in Córdoba, Argentina.

The concentration of metals (Al, Cr, Mn, Fe, Ni, Cu, Zn, Ag, Cd, Hg, Pb, U), As and Se in different ecosystem components (water, sediment, plankton, shrimp, and fish muscle) has been determined in a eutrophic reservoir in the Province of Córdoba (Argentina). Los Molinos Lake (LML) was sampled during the dry (DS) and wet seasons (WS) in order to examine the bioaccumulation and transfer of these inorganic elements through the food web. Stable nitrogen isotope (δ15N) was used to investigate trophic interactions. According to this, samples were divided into three categories: plankton, shrimp (Palaemonetes argentinus) and fish (Silverside, Odontesthes bonariensis). The bioaccumulation factor (BAF) was calculated for the organisms, and it was determined that the elements analyzed undergo bioaccumulation, especially in organisms such as plankton. The invertebrates were characterized by the highest BAF for Cu and Zn in both seasons, As (DS), and Cd and Hg (WS). The fish muscle was characterized by the highest BAF for Se (WS), Ag and Hg (DS). On the other hand, a significant decrease in Al, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Cd and U concentrations through the analyzed trophic web during both seasons was observed. Moreover, a significant increase in Hg levels was observed with increasing trophic levels in the DS, indicating its biomagnification. Despite the increasing impact of metals, As and Se pollution in the studied area due to urban growth and agricultural and livestock activities, no previous study has focused on the behavior and relationships of these pollutants with the biotic and abiotic components of this aquatic reservoir. We expect that these findings may be used for providing directions or guidance for future monitoring and environmental protection policies.

Differential biochemical responses to metal/metalloid accumulation in organs of an edible fish (Centropomus parallelus) from Neotropical estuaries.

Metal/metalloid accumulation in fish organs elicits biochemical responses indicating the overall fish and environmental health status. This study evaluated the bioaccumulation of metals and metalloid in relation to a suite of biochemical biomarkers (superoxide dismutase, catalase, glutathione-S-transferase, Na+/K+-ATPase, H+-ATPase, acetylcholinesterase activities and the levels of glutathione, metallothionein, lipid peroxidation and oxidized protein) in different organs of fish, Centropomus parallelus, in Vitória Bay and Santa Cruz estuaries (State of Espírito Santo, Brazil) with distinct contamination levels. Metal and metalloid concentrations differ in each organ and were significantly higher in winter than in summer. Chemometric evaluation performed between metal/metalloid accumulation and the biomarkers revealed a complex scenario in which the biomarker responses depend on both metal accumulation and organ/tissue sensitivity. The metal levels in gills indicate fish contamination mainly via water and the low sensitivity of this organ to most metals. Biomarker responses suggested that the metal elimination pathway is through the gills and kidney. The hepatopancreas and kidneys were the most important detoxification organs while muscle was the less reactive tissue. In general, the finding suggested that, C. parallelus is partly able to tolerate such metal contamination. However, it is emphasized that the biomarker responses imply an energetic cost and may affect the growth rate and reproduction. Given the ecological and economic importance of C. parallelus, the level of toxic metals/metalloids in juvenile fish is an important early-warning for the maintenance, conservation and commercial use of this species.

Phytofiltration of As3+, As5+, and Hg by the aquatic macrophyte Potamogeton pusillus L, and its potential use in the treatment of wastewater.

The aim of this paper was to investigate the capacity of the aquatic macrophyte Potamogeton pusillus to remove As3+, As5+, and Hg from aqueous solutions. The plants were exposed to 0 mg.L-1, 0.1 mg.L-1, 0.5 mg.L-1, 1 mg.L-1, or 2 mg.L-1 of As3+, As5+, and Hg for 20 days. The results obtained for the individual removal of As3+, As5+, and Hg from water solutions, together with their accumulation in P. pusillus, indicate that this plant can be effectively used for the removal of Hg and of moderate concentrations of As3+ or As5+ (0.1 mg.L-1) from aquatic systems. Roots and leaves accumulated the highest amount of As when the plant was exposed to As5+, but when it was exposed to As3+, the root accumulated the highest amount of As, and the leaves, the highest amount of Hg. When compared to other aquatic plants species, the results showed that P. pusillus demonstrated a higher Hg accumulation (2465 ± 293 µg.g-1) when the transfer coefficient was 40,580 ± 3762 L.kg -1, showing the great potential of this macrophyte for phytoremediation of water contaminated with Hg. To the extent of our knowledge, this is the first report on bioaccumulation of As3+, As5+, and Hg by P. pusillus.

Behavioral swimming effects and acetylcholinesterase activity changes in Jenynsia multidentata exposed to chlorpyrifos and cypermethrin individually and in mixtures.

The pesticides cypermethrin (CYP) and chlorpyrifos (CPF) were found together in water bodies located in agricultural and urban areas. However, the impact to non-target biota from exposure to mixtures has received little attention. In the current study, we evaluated changes in swimming behavior and cholinesterase enzymes activity in Jenynsia multidentata, to investigate the possible effects of these insecticides individually and in mixtures. Moreover, differences between technical and commercial mixtures of the pesticides were evaluated. Females of J. multidentata were exposed over 96-h to CYP (0.04 and 0.4µgL(-1)), CPF (0.4 and 4µgL(-1)), individually and in a technical and commercial mixtures. Swimming behavior was recorded after 24h and 96h of exposure. Also, we measured cholinesterase enzymes activity in brain and muscle after 96h of exposure. Exposure to CYP increased the exploratory activity of J. multidentata in the upper area of the aquarium. Fish exposed to CPF (4µg L(-1)) showed a decrease in swimming activity and an increase in the time spent at the bottom of the aquarium. Interestingly, fish exposed to the technical and commercial mixture of CYP and CPF displayed a different behavior based on the concentration of exposure. Low concentration of pesticides elicited an increase in J. multidentata swimming activity with preference for the upper area of the aquarium, and high concentrations caused decrease in swimming activity with preference for the bottom area of the aquarium. Based on the response of cholinesterase enzymes, acetylcholinesterase in muscle was more sensitive to exposure to CYP, CPF and their mixtures than in brain. A decrease in swimming behavior correlates significantly with the inhibition of acetylcholinesterase activity in muscle of J. multidentata exposed to high concentrations of pesticides. These results draw attention to the need of more studies on the potential ecotoxicological impact of pesticides and its mixtures at environmental relevant concentrations.

Potential human health risks from metals and As via Odontesthes bonariensis consumption and ecological risk assessments in a eutrophic lake.

The concentration of Al, Cr, Fe, Mn, Ni, Cu, Zn, Hg, Sr, Mo, Ag, Cd, Pb and As was analyzed in water, sediment, and muscle of Odontesthes bonariensis from the eutrophic San Roque Lake (Córdoba-Argentina). The monitoring campaign was performed during the wet, dry and intermediate season. The concentration of Cr, Fe, Pb, Zn, Al and Cd in water exceeded the limits considered as hazardous for aquatic life. The highest metal concentrations were observed in sediment, intermediate concentrations, in fish muscle, and the lowest in water, with the exception of Cr, Zn, As and Hg, which were the highest in fish muscle. Potential ecological risk analysis of heavy metal concentrations in sediment indicated that the San Roque Lake posed a low ecological risk in all sampling periods. The target hazard quotients (THQs) and carcinogenic risk (CR) for individual metals showed that As in muscle was particularly hazardous, posing a potential risk for fishermen and the general population during all sampling periods. Hg poses a potential risk for fishermen only in the intermediate season. It is important to highlight that none of these two elements exceeded the limits considered as hazardous for aquatic life in water and sediment. This result proves the importance of performing measurements of contaminants, in both abiotic and biotic compartments, to assess the quality of food resources. These results suggest that the consumption of this fish species from this reservoir is not completely safe for human health.

Argentinian pistachio oil and flour: a potential novel approach of pistachio nut utilization.

In order to searching a potential novel approach to pistachio utilization, the chemical and nutritional quality of oil and flour from natural, roasted, and salted roasted pistachios from Argentinian cultivars were evaluated. The pistachio oil has high contents of oleic and linoleic acid (53.5 - 55.3, 29 - 31.4 relative abundance, respectively), tocopherols (896 - 916 µg/g oil), carotenoids (48 - 56 µg/g oil) and chlorophylls (41 - 70 µg/g oil), being a good source for commercial edible oil production. The processing conditions did not affect significantly the fatty acid and minor composition of pistachio oil samples. The content of total phenolic (TP) and flavonoids (FL) was not significantly modified by the roasting process, whereas free radical scavenging (DPPH radical) and antioxidant power decreased in a 20% approximately. Furthermore, salted roasted pistachio flour (SRPF) showed a significant decrease in TP and FL content in comparison to others samples. The phenolic profile of pistachio flours evaluated by LC-ESI-QTOF-MS. The major compounds identified were (+)-catechin (38 - 65.6 µg/g PF d.w.), gallic acid (23 - 36 µg/g PF d.w.) and cyanidin-3-O-galactoside (21 - 23 µg/g PF d.w.). The treatments effects on the phenolics constituents of pistachio flour. Roasting caused a significant reduction of some phenolics, gallic acid and (+)- catechin, and increased others, naringenin and luteolin. Salting and roasting of pistachio increased garlic acid and naringenin content.

In order to searching a potential novel approach to pistachio utilization, the chemical and nutritional quality of oil and flour from natural, roasted, and salted roasted pistachios from Argentinian cultivars were evaluated. The pistachio oil has high contents of oleic and linoleic acid (53.5­55.3, 29­31.4 relative abundance, respectively), tocopherols (896­916 µg/g oil), carotenoids (48­56 µg/g oil) and chlorophylls (41­70 µg/g oil), being a good source for commercial edible oil production. The processing conditions did not affect significantly the fatty acid distribution and minor components of pistachio oil samples. The roasting process not diminish total phenolic (TP) and flavonoids (FL) content significantly compared to natural pistachio flour (NPF), even so reduced the DPPH antioxidant capacity (approximately 20 %) in the roasted pistachio flour (RPF). Furthermore, salted roasted pistachio flour (SRPF) showed a slight and significant decrease on TP and FL content in relation to the others samples. The phenolic profile of pistachio flours were evaluated by LC-ESI-QTOF-MS. The major compounds were (+)-catechin (38­65.6 µg/g PF d.w.), gallic acid (23­36 µg/g PF d.w.) and cyanidin-3-O-galactoside (21­23 µg/g PF d.w.). The treatments have different effects on the phenolics constituents of pistachio flour. Roasting caused a significant reduction of some phenolics, gallic acid and (+)-catechin, and increased others, naringenin and luteolin. Otherwise, salting and roasting of pistachio increased levels of gallic acid and naringenin. These results suggest that Argentinian pistachio oil and flour could be considered as ingredients into applications that enhance human health.

Selective and eco-friendly procedures for the synthesis of benzimidazole derivatives. The role of the Er(OTf)3 catalyst in the reaction selectivity.

An improved and greener protocol for the synthesis of benzimidazole derivatives, starting from o-phenylenediamine, with different aldehydes is reported. Double-condensation products were selectively obtained when Er(OTf)3 was used as the catalyst in the presence of electron-rich aldehydes. Conversely, the formation of mono-condensation products was the preferred path in absence of this catalyst. One of the major advantages of these reactions was the formation of a single product, avoiding extensive isolation and purification of products, which is frequently associated with these reactions. Theoretical calculations helped to understand the different reactivity established for these reactions. Thus, we found that the charge density on the oxygen of the carbonyl group has a significant impact on the reaction pathway. For instance, electron-rich aldehydes better coordinate to the catalyst, which favours the addition of the amine group to the carbonyl group, therefore facilitating the formation of double-condensation products. Reactions with aliphatic or aromatic aldehydes were possible, without using organic solvents and in a one-pot procedure with short reaction time (2-5 min), affording single products in excellent yields (75-99%). This convenient and eco-friendly methodology offers numerous benefits with respect to other protocols reported for similar compounds.

Screening concentration of E1, E2 and EE2 in sewage effluents and surface waters of the "Pampas" region and the "Río de la Plata" estuary (Argentina).

Concentrations of estrone (E1), 17ß-estradiol (E2) and 17α-ethinylestradiol (EE2) were investigated for the first time in sewage effluents and receiving waters of the "Río de la Plata" estuary and neighboring areas by means of LC-MS/MS. E2 and EE2 were ubiquitous in the evaluated sewage effluent samples showing concentrations ranging between 122-631 and 65-187 ng/L, respectively. In surface waters, these estrogens were only detected in the "Girado" stream (Chascomús) at 369 and 43 ng/L, respectively. No significant relationship was found among the size of the served population and the concentration of the estrogens in the sewage effluent. The detection of these estrogens in receiving waters was dependent on the dilution capacity of the system. The studied estrogens were undetectable at the La Plata City water supply station. Conversely, concentrations found at the "Girado" stream indicate a potential ecotoxicological risk of these estrogens to the local aquatic biota.

Oxidative stress response induced by atrazine in Palaemonetes argentinus: the protective effect of vitamin E.

The widespread contamination and persistence of the herbicide atrazine residues in the environment resulted in the exposure of non-target organisms. The present study was undertaken to investigate the effect of atrazine in the response of oxidative stress biomarkers in the freshwater shrimp Palaemonetes argentinus and the protective effect of vitamin-E against atrazine-induced toxicity. Therefore, two batches of P. argentinus were fed for 21 days with a commercial food enriched in proteins (D1) or with D2, composed of D1 enriched with vitamin-E (6.8 and 16.0mg% of vitamin-E, respectively). Subsequently, half of the individuals of each group were exposed to atrazine (0.4mgL(-1)) for 24h and the others remained as controls. Atrazine promoted oxidative stress response in P. argentinus fed with D1 as indicated by enhanced H2O2 content and induction of superoxide dismutase, glutathione-S-transferases and glutathione reductase. This antioxidant activity would prevent the increment of thiobarbituric acid reactive substances in the shrimp tissues. P. argentinus fed with D2 reversed the response of the biomarkers measured. However, the activation of antioxidants response had an energetic cost, which was revealed by a decrease in lipids storage in shrimps. These results show the modulatory effect of vit-E on oxidative stress and its potential use as an effective antioxidant to be applied in chemoprotection strategies during aquaculture.

Adaptive plasticity of Laguncularia racemosa in response to different environmental conditions: integrating chemical and biological data by chemometrics.

Mangroves are dynamic environments under constant influence of anthropic contaminants. The correlation between environmental contamination levels and possible changes in the morphology of plants, evaluated by multivariate statistics helps to highlight matching between these variables. This study aimed to evaluate the uptake and translocation of metals and metalloids in roots and leaves as well as the changes induced in both anatomy and histochemistry of roots of Laguncularia racemosa inhabiting two estuaries of Espírito Santo (Brazil) with different pollution degrees. The analysis of 14 elements in interstitial water, sediments and plants followed by multivariate statistics, allowed the differentiation of studied sites, showing good match between levels of elements in the environment with the corresponding in plants. L. racemosa showed variations in their root anatomy in different collection areas, with highest values of cortex/vascular cylinder ratio, periderm thickness and air gap area in Vitória Bay, the most polluted sampling area. These three parameters were also important to differentiate the mangrove areas by linear discriminant analysis. The development stage of aerenchyma in roots reflected the oxygen availability in the water, being found a negative correlation between these variables. The combined use of chemical and biological analyses responded quite well to different pollution scenarios, matching morphological responses to physical and chemical parameters, measured at different partitions within the estuary. Thus, L. racemosa can be confirmed as a reliable sentinel plant for biomonitoring of estuaries impacted by anthropic pollution.

The Effects of Chia Defatted Flour as a Nutritional Supplement in C57BL/6 Mice Fed a Low-Quality Diet.

Today, consumption of diets rich in saturated fat and fructose, associated with a variety of metabolic deregulations, has increased. The aim of this study was to evaluate the effect of dietary supplementation with a residue of defatted chia seed on a diet with low nutritional quality. To do this, C57BL/6 male mice were fed with the Control (C), Low-Nutritional-Quality (LNQ), or supplemented-with-chia-defatted-flour (LNQ+C) diets. After 12 weeks, the glucose and lactate levels were determined in the serum, liver, and kidney, along with reactive oxygen species (ROS) levels, antioxidant enzyme activity, reduced glutathione (GSH), and protein oxidation (AOPP). The LNQ diet increased the glucose and lactate levels (+25% and +50% approx. in the liver, with respect to the control group) and generated oxidative stress by modifying the levels of ROS and the activity of antioxidant enzymes, causing oxidative damage to proteins (+12% in the liver, with respect to the control). Chia supplementation helped to restore the glucose to control levels and modulate the endogenous antioxidant system, resulting in a decrease in protein oxidation products with no differences compared to the control group. In conclusion, supplementation with chia showed beneficial effects on the general health of mice, even when fed a low-nutritional-quality diet.

Antioxidant activity of chia flour as a food supplement in a cellular model: Repercussions of processing and in vitro digestion.

Food processing and digestion can alter bioactive compound composition of food, affecting their potential biological activity. In this study, we evaluated the direct and protective antioxidant effects of polyphenols extracted from defatted chia flour (DCF) (salviaflaside, rosmarinic and fertaric acid as major compounds), sweet cookies supplemented with DCF (CFC) (same major compounds), and their digested fractions (rosmarinic acid, salviaflaside, fertaric and salvianolic E/B/L acid as major compounds) in HepG2 cells in basal and in oxidative stress conditions. DCF showed protective antioxidant effects by decreasing reactive oxygen species (ROS) and protein oxidation products (POP) while increasing reduced glutathione (GSH). Additionally, CFC revealed similar protective effects and even showed enhanced modulation of the antioxidant system due to the activation of antioxidant enzymes. However, the digested fractions only decreased ROS, indicating continued antioxidant effects. This study underscores the importance of evaluating manufacturing and digestion effects to confirm a food's antioxidant properties.

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.

Effect of acute exposure to settleable atmospheric particulate matter emitted by the steel industry on hematology and innate immunity of fat snook (Centropomus parallelus).

The steel industry is a significant worldwide source of atmospheric particulate matter (PM). Part of PM may settle (SePM) and deposit metal/metalloid and metallic nanoparticles in aquatic ecosystems. However, such an air-to-water cross-contamination is not observed by most monitoring agencies. The region of Vitoria City is the main location of iron processing for exports in Brazil, and it has rivers, estuaries, and coastal areas affected by SePM. We have evaluated the effects of SePM on a local representative fish species, the fat snook, Centropomus parallelus. After acclimation, 48 fishes (61.67 ± 27.83 g) were individually exposed for 96 h to diverse levels of SePM (0.0, 0.01, 0.1 and 1 g/L-1). The presence of metals in the blood and several blood biomarkers were analyzed to evaluate the impact of SePM on stress signaling, blood oxygen transport capacity, and innate immune activity. Metal bioaccumulation was measured from blood in two separately analyzed compartments: intracellular (erythrocytes plus white blood cells) and extracellular (plasma). The major metals present at all contamination levels in both compartments were Fe and Zn, followed by Al and Cu, plus traces of 'Emerging metals': Ba, Ce, La, Rb, Se, Sr, and Ti. Emerging metals refer to those that have recently been identified in water as contaminants, encompassing rare earth elements and critical technology elements, as documented in previous studies (See REEs and TCEs in Cobelo-García et al., 2015; Batley et al., 2022). Multivariate analysis revealed that SePM had strong, dose-dependent correlations with all biomarker groups and indicated that blood oxygen-carrying capacity had the highest contamination responsiveness. Metal contamination also increased cortisol and blood glucose levels, attesting to increased stress signaling, and had a negative effect on innate immune activity. Knowledge of the risks related to SePM contamination remains rudimentary. However, the fact that there was metal bioaccumulation, causing impairment of fundamental physiological and cellular processes in this ecologically relevant fish species, consumed by the local human population, highlights the pressing need for further monitoring and eventual control of SePM contamination.