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.
•Plankton showed the greatest capacity to bioaccumulate inorganic elements.•Aluminium, Cr, Mn, Fe, Ni, Cu, Zn, Ag, Cd, Pb, As and Se showed biodilution.•Mercury showed biomagnification throughout different components of the food web.•Elements thrown into environment can be biomagnified being back into human food.
Glyphosate (GLY) and AMPA concentrations were determined in sandy soil profiles, during pre- and post-application events in two agricultural soybean fields (S1 and S2). Streamwater and sediment ...samples were also analyzed. Post-application sampling was carried out one month later from the event. Concentrations of GLY+AMPA in surface soils (0–5cm depth) during pre-application period showed values 20-fold higher (0.093–0.163μg/g d.w.) than control area (0.005μg/g d.w.). After application event soils showed markedly higher pesticide concentrations. A predominance of AMPA (80%) was observed in S1 (early application), while 34% in S2 for surface soils. GLY+AMPA concentrations decreased with depth and correlated strongly with organic carbon (r between 0.74 and 0.88, p<0.05) and pH (r between −0.81 and −0.76, p<0.001). The slight enrichment of pesticides observed from 25cm depth to deeper layer, in addition to the alkaline pH along the profile, is of high concern about groundwater contamination. Sediments from pre-application period showed relatively lower pesticide levels (0.0053–0.0263μg/g d.w.) than surface soil with a predominance of glyphosate, indicating a limited degradation. Levels of contaminants (mainly AMPA) in streamwater (ND-0.5ng/mL) denote the low persistence of these compounds. However, a direct relationship in AMPA concentration was observed between sediment and streamwater. Despite the known relatively short half-life of glyphosate in soils, GLY+AMPA occurrence is registered in almost all matrices at different sampling times (pre- and post-application events). The physicochemical characteristics (organic carbon, texture, pH) and structure of soils and sediment in addition to the time elapsed from application determined the behavior of these contaminants in the environment. As a whole, the results warn us about vertical transport trough soil profile with the possibility of reaching groundwater.
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•The fate of GLY+AMPA was studied in agricultural soil profiles from soybean fields.•GLY+AMPA in soil profile were well correlated with organic carbon content and pH.•GLY was concentrated in the upper soil layer after application.•GLY and AMPA were detected in streamwater and sediment at lower levels than soils.
There is a growing interest in evaluating the presence of pharmaceutical residues and their metabolites in aquatic biota. In this study, twenty pharmaceuticals, including carbamazepine (CBZ) and two ...metabolites, were analyzed in homogenates of two fish species (Gambusia affinis and Jenynsia multidentata) captured in polluted areas of the Suquía River (Córdoba, Argentina). The twenty target pharmaceuticals were found in G. affinis, while only fifteen were detected in J. multidentata. We observed a noticeable difference in the accumulation pattern of both fish species, suggesting different pathways for the bioaccumulation of polar pharmaceuticals in each fish.
In order to investigate uptake and tissue distribution of pharmaceuticals, a detailed study was performed under controlled laboratory conditions in J. multidentata, exposed to CBZ. CBZ and two of its metabolites (carbamazepine-10,11-epoxide – CBZ-EP and 2-hydroxycarbamazepine – 2-OH-CBZ) were monitored in five organs of fish under laboratory exposure. To our knowledge, this is the first report on the presence of CBZ and its metabolite 2-OH-CBZ in gills, intestine, liver, brain and muscle of fish, while the metabolite carbamazepine-10,11-epoxide (CBZ-EP) was detected in gills and muscle. A ratio CBZ-EP/CBZ close to 0.1 suggests that gills and muscle of J. multidentata could metabolize CBZ through the CBZ-EP pathway.
Our results reinforce the need of analyzing multiple species to account for the environmental impact of pollutants, negating the simplification of a single, “representative model” during ecotoxicological biomonitoring. To our knowledge, the biotransformation of CBZ to its metabolites (CBZ-EP, 2-OH-CBZ) in fish, under controlled laboratory in vivo exposures, is reported for the first time.
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•Wild G. affinis and J. multidentata bioaccumulated 20 pharmaceuticals.•Laboratory exposed fish biotransformed CBZ to 2-OH-CBZ and CBZ-EP.•CBZ and 2-OH-CBZ were preferentially bioconcentrated in brain and liver.•CBZ-EP was only detected in gills and muscle.
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•Targeted metabolomics allowed the differentiation of chia, flax and sesame seeds.•Polyphenols served as biomarkers to differentiate seeds.•Some biomarkers resisted the events that ...occur during processing of food.•The biomarkers were found in sweet cookies with whole chia, flax and sesame seeds.
Food fraud is perpetrated with increasing frequency along the food chain, triggering the need for new and modern tools to detect food authenticity. Chia, flax and sesame seeds are well known for the good nutritional characteristics of their oils, but there is a lack of knowledge regarding the authenticity of these seeds and food products containing them as well. In the present work, we propose a method based on targeted metabolomics to identify the polyphenols present in seeds, which can be used as markers of authenticity. We tentatively identified 44 polyphenols in the different seeds by HPLC-DAD-ESI-qTOF (MS/MS). Chemometrics allowed the selection of 12 compounds, which are nominated as novel markers for seed authentication. Some of these compounds were also found in a lab-scale preparation of cookies supplemented with the studied seeds. The proposed chemical markers resisted the baking process, representing good candidates to be used in the authentication of raw material and bakery products containing these seeds.
An improved and greener protocol for the synthesis of benzimidazole derivatives, starting from
-phenylenediamine, with different aldehydes is reported. Double-condensation products were selectively ...obtained when Er(OTf)
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.
RAMSAR sites are determined by specific characteristics of the environment in terms of ecological productivity as well services for human development, but they are also one of the most threatened ...ecosystems. Thus, the objective of this work was to evaluate the dynamic of Persistent Organic Pollutants (POPs) in different biotic and abiotic matrixes of the RAMSAR site (wetlands with international importance), Mar Chiquita Lake. Sampling was performed according to land use (agricultural, urban, and industrial) at two stations: Laguna del Plata and Campo Mare. POPs were analyzed in superficial water (Sw), suspended particulate material (SPM), bottom sediment (Bs) and fish tissues (Odontesthes bonariensis). Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were analyzed by GC-ECD. HCHs, Endosulfans, DDTs, PCBs and PBDEs were found in all matrixes at both stations. The high persistence and transport processes are responsible for the occurrence of HCHs, DDTs and PCBs in Bs, SPM and fish tissues, even many years after their prohibition. PBDEs showed lower levels according to the scarcity of punctual sources in the area. Endosulfan showed variable amounts in agreement with application periods since this pesticide was used until a few years ago in this area. Finally, PCB levels overpassed the acceptable daily intake for human consumption being a risk for human health Thus, the present report confirms the occurrence of POPs in Mar Chiquita lake, alerting on the contribution of agricultural and urban pollutants in a RAMSAR site. Current results also raise concerns on biomagnification processes through the food web.
•OCPs, PCBs and PBDEs were found in water, sediments, SPM, and fish.•Endosulfan was the main pesticide found in all matrixes.•γ- HCH and endosulfans overpassed quality guidelines and represent a risk to aquatic biota.•PCB levels overpassed the AID for human consumption being a risk for human health.
•Hg showed consistent biomagnification throughout different components of the food web.•Most elements were bioaccumulated from water to plankton with further biodilution to higher trophic ...levels.•Differential accumulation of studied elements among diverse fish tissues was observed.•Hg, As and Cr were bioaccumulated in fish from food.•Toxic elements freely put into the environment can be biomagnified and reach human food.
The concentration of Mn, Fe, Zn, Cu, Cd, Cr, Ni, Ag, Mo, Nd, Al, Ce, As, Sr, Pb, Pt and Hg was analysed in water, sediments, and aquatic organisms from the San Roque Reservoir (Córdoba-Argentina), sampled during the wet and dry season, to evaluate their transfer through the food web. Stable nitrogen (δ15N) isotopes were used to investigate trophic interactions. According to this, samples were divided into three trophic groups: plankton, shrimp (Palaemonetes argentinus) and fish (Silverside, Odontesthes bonariensis). Liver and gills are the main heavy metal storage tissues in fish. Hg and As concentrations in the muscle of O. bonariensis exceed the Oral Reference doses for metals established by USEPA (2009). Trophic magnification factors (TMFs) for each element were determined from the slope of the regression between trace element concentrations and δ15N. Calculated TMFs showed fundamental differences in the trophodynamics of the studied elements during the wet and dry season in the San Roque Reservoir. Concentrations of Ni, Cd, Cr, Al, Mn, Fe, Mo, Ce, Nd, Pt and Pb during both seasons, and Sr during the dry season, showed statistically significant decreases (TMF<1) with increasing trophic levels. Thus these elements were trophically diluted in the San Roque food chain. Conversely, Cu, Ag and As (dry season) showed no significant relationships with trophic levels. Among the elements studied, Hg in the wet season, and Zn in the dry season were the only ones showing a statistically significant increase (TMF>1) in concentration with trophic level. Current results trigger the need for further studies to establish differential behaviour with different species within the aquatic web, particularly when evaluating the transfer of toxic elements to edible organisms, which could pose health risks to humans.
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.
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•Some elements in water exceeded the limits consider as hazardous for aquatic life.•The San Roque Reservoir poses a low potential ecological risk in sediments.•Most elements concentration were sediment > fish muscle > water.•Cr, Zn, Hg and As concentration were fish muscle > sediment > water.•As and Hg in muscle of silverside pose a potential risk for consumers.
This field study assessed water quality of Salado River basin by using a set of biomarkers in the fish
Prochilodus lineatus. Multiple biomarkers were measured, including morphological indexes ...(condition factor, liver somatic index), hematological (red and white blood cells) and biochemical (glucose, total protein and cholinesterase activity) parameters. Besides, detoxication and oxidative stress markers (antioxidant enzymes, lipid peroxidation) were measured in liver, gills and kidney. Despite water quality assessment did not show marked differences among sites, biomarkers responses indicate that fish are living under stressful environmental conditions. According to multivariate analysis glucose, glutathione S-transferase activity, lipid peroxidation levels and the count of white blood cells are key biomarkers to contribute to discrimination of sites. So, we suggest use those biomarkers in future monitoring of freshwater aquatic systems.
A battery of biomarkers was successfully applied to assess the health of the fish Prochilodus lineatus from Salado River basin.
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•The bioaccesibility of polyphenols from grape is compared to those from wine.•In grapes, polyphenols are released during mouth and stomach digestion.•In wine, polyphenols are already ...bioaccesible.•Less than 52% of polyphenols would be potentially bioaccesible.•Anthocyanins were among the most resistant polyphenols to GI digestion.
The aim of this study was to evaluate the effect of the simulated gastro-intestinal (GI) digestion on the phenolic profile and the antioxidant capacity (AC) of grapes and red wines. Mouth and stomach digestion increased the bioaccesibility of TP (total polyphenols) in grapes, while in wine these compounds were already bioaccessible. Intestinal digestion reduced the bioaccessible polyphenols of grapes and wines, mainly due to the alkaline pH of the digestive fluid. Only 16% and 52% of the initial TP in grapes and wine, respectively, were found after assay (dialysed plus nondialysed fractions). Moreover, 21% and 39% of grape and wine AC, respectively, was conserved. In spite of the significant loss of polyphenols during digestion, both grapes and red wine still retain AC. Anthocyanins were less affected by human GI tract. Therefore, they could be the most relevant compounds to explain the AC of both grapes and red wine after GI.
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