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Simple models capable of describing spatial and temporal patterns of pollutants are needed to understand surface water quality and to identify the main processes that influence the fate and transport of pollutants. This study combines exploratory factor analysis with multilevel and structural equation modeling to: find spatial and temporal patterns of metal and metalloids in the Ctalamochita River Basin (Argentina); identify the processes responsible for the occurrence of these elements; and, establish relationships between latent variables of different aquatic compartments. For this purpose, the metal and metalloid concentration in different matrices was analyzed at sampling sites along 330 km of the river course, including seasonal variations. Our results indicate that the concentration of natural occurring elements in surface water increased downstream the catchment and during the warm-rainy season, as a consequence of surface runoff and groundwater discharge. In contrast, the spatial and seasonal variation in sediment showed an inverse pattern (negative correlation) compared to surface water. On the other hand, copper, zinc and lead were derived from anthropogenic sources, such as old mining areas and metal industries. Moreover, the input of these metals into the river evidenced a direct effect of surface water on sediment. Overall, the combined use of multilevel model and SEM allowed for a proper description of spatial and temporal patterns of metals and metalloids in the catchment, and successfully highlighted sources and processes influencing metal transport. The proposed methodological framework could be extended to wider spatial scales including nested regions, and could be applied to environmental studies dealing with repeated observations and multiple matrices.

Intracellular titanium dioxide nanoparticles (TiO2-NP) with rutile crystalline form and dimensions varying from 43 to 67 nm × 64 to 93 nm are reported for the first time as being sequestered from the environment. TiO2-NP were identified inside all organs/tissues (muscle, kidney, gonad, hepatopancreas and gill) in both the cytoplasm and nucleus of the neotropical fish Centropomus parallelus, captured in an area affected by metallurgical activity. Atmospheric particulate matter (PM) sampled in the same area showed the presence of TiO2-NP with the same rutile crystalline form and dimensions varying from 16 to 93 nm × 45 to 193 nm, thus indicating the smelting and iron processing industries as the most probable source of TiO2-NP. In any sample, chemical analyses identify and quantify Ti concentration and nanocrystallography identified the structure of TiO2-NP. The Ti concentration in the sediment and atmospheric PM varied between years and it was mirrored by the Ti concentration in the fish organs. The gill has a higher Ti concentration varying from 5.50 to 14.57 μg g−1 dry weight and the gonad was the organ with lowest Ti level, 0.25 to 0.87 μg g−1 dry weight. In the muscles, Ti concentration varied from 0.85 to 3.34 μg g−1 dry weight. This contamination may be likely to affect the surrounding biota and food uptake, including the humans living in the city close to the metallurgical complex. These findings emphasised the needs to improve methods to reduce PM (including nanoparticles) arising from human activities and to evaluate the toxicokinetic and effects of TiO2-NP in the biota and human health.

Emerging metallic contaminants (EMCs) are of concern due their presence in aquatic ecosystems and the lack of environmental regulations in several countries. This study verifies the presence of EMCs in two neotropical mangrove estuarine ecosystems (Espirito Santo Brazil) by evaluating abiotic and biotic matrices across six trophic levels (plankton, oyster, shrimp, mangrove trees, crabs and fish) and hence interrogates the trophic transfer of these elements and their possible input sources. Using the oyster Crassostrea rhizophorae as a biomonitor, ten EMCs (Bi, Ce, La, Nb, Sn, Ta, Ti, W, Y and Zr) were determined. Bi input was from iron export and pelletizing industries; Ce, La and Y inputs were mainly associated with solid waste from steel production, while Zr, Nb and Ti were related to atmospheric particulate matter emissions. EMCs were detected at various trophic levels, showing biomagnification for most of them in the Santa Cruz estuary but biodilution in Vitoria Bay. These contrasting results between the estuaries could be attributed to different pollution degrees, needing further research to be fully understood. This is the first report demonstrating EMCs trophic pathways in situ, constituting an essential baseline for future research and safety regulations involving EMCs in the environment.

Rio Tercero Reservoir (RTR) is the largest artificial reservoir in the province of Cordoba (Argentina). Water, sediment, plankton, shrimp (Palaemonetes argentinus), and fish (Odontesthes bonariensis) were collected during the wet season (WS) and dry season (DS) from this reservoir. Concentrations of Ag, Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, P, Pb, Se, U, and Zn were determined to investigate their respective bioaccumulation pattern and trophic transfer in the food chain. Results showed that their concentrations in water were rather low except Pb, which exceed the limits considered as hazardous for aquatic life. The enrichment factor (EF) in sediments showed that most of the element were derived from anthropogenic sources. Furthermore, the bioaccumulation factor (BAF) determined that the elements undergo bioaccumulation, especially in organisms such as plankton. The invertebrates were characterized by the highest BAF for Cu, P, and Zn in both seasons; Ag, As, and Hg during WS; and Se during DS. Fish muscle registered the highest BAF for Hg (DS) and Se (WS). A significant decrease in Al, As, Cd, Cr, Cu (DS) Fe, Mn, Ni, Pb, Se, U, and Zn (DS) concentrations through the trophic chain was observed, indicating biodilution. Some notable exceptions were found as Cu (WS), Hg (DS), and P (both season) that showed biomagnification. Further studies are needed to establish differential behavior with different species and pollutant, particularly when the potential transfer is to edible organisms.

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. Fil: Souza, Iara da C.. Universidade Federal do São Carlos; Brasil Fil: Morozesk, Mariana. Universidade Federal do São Carlos; Brasil Fil: Bonomo, Marina M.. Universidade Federal do São Carlos; Brasil Fil: Azevedo, Vinicius C.. Universidade Federal do São Carlos; Brasil Fil: Sakuragui, Marise M.. Universidade Federal do São Carlos; Brasil Fil: Elliott, Michael. University of Hull; Reino Unido Fil: Matsumoto, Silvia T.. Universidade Federal do Espírito Santo; Brasil Fil: Wunderlin, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina Fil: Baroni, María Verónica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina Fil: Monferran, Magdalena Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina Fil: Fernandes, Marisa N.. Universidade Federal do São Carlos; Brasil

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. Fil: Griboff, Julieta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina Fil: Horacek M. Blt Wieselburg Lehr- und Forschungszentrum Francisco Jo; Austria. Universidad de Viena; Austria Fil: Wunderlin, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina Fil: Monferran, Magdalena Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina

Multi-element concentrations (Al, As, Cd, Cr, Hg, Ni, Pb, Se, and Sr) were analyzed in the muscle of six fish species (Hoplias malabaricus, Oligosarcus jenynsii, Rhamdia quelen, Bryconamericus iheringii, Astyanax fasciatus, and Odontesthes bonariensis) with different diets and habits from the Rio Tercero Reservoir (RTR) in Cordoba, Argentina, during the wet and dry seasons. Besides, potential human health risks, associated with the consumption of these elements, have been assessed considering the average daily intake (EDI) in children and adults. Additionally, the target hazard quotient (THQ) and carcinogenic risk (CR) were evaluated taking into account the intake by the general population, fishermen, and consumption frequency recommended by the American Heart Association (AHA), the maximum scientific reference in cardiology in the USA and worldwide. All species presented quantifiable values in muscle for all the analyzed elements (Al, As, Cr, Hg, Ni, Se, and Sr), except for Cd and Pb, being Al and Sr the most accumulated elements in all species in both seasons. The consumption of edible muscles of the species studied in this reservoir represents a toxicological risk to humans. Mercury and As were the main elements that presented a health risk through the consumption of fish. Their concentrations in most fish species were above the maximum daily allowable concentrations, and THQ values were several times greater than 1. In addition, according to AHA recommendations, the cancer risk caused by As was greater than the acceptable value of 10-4 in all species studied, and in both seasons, with the exception of A. fasciatus, in the rainy season. These results indicate that the consumption of fish from the RTR exposes the inhabitants to possible health risks, especially when considering the consumption frequency recommended by the AHA. Therefore, fish intake from this reservoir should be limited to minimize potential risks to the health of consumers. Finally, the results of this study are useful for controlling pollution and developing preventive and palliative policies to protect populations in contact not only with the reservoir but also with other areas of the world with similar conditions.

The concentration of Ag, As, Cd, Cu, Cr, Hg, Ni, Pb, Se, U, V, and Zn was analyzed in water, sediment, and different organs of Prochilodus lineatus (muscle, liver and gill) in three most commercially important catch areas along La Plata Basin, namely High Parana River (HPR), Middle Parana River (MPR) and Rio de la Plata Estuary (RPE). The concentration of As, Cu and Zn (RPE) and Se (HPR) in water and As (RPE), Ni (HPR and MPR), Cu and Cr (all sites) in sediments exceeded the limits considered as hazardous for aquatic life. With the exception of Se (sediment-liver) and Pb (sediment-liver and sediment-gill), it was not observed a significant correlation between the element concentration in tissues and that found in water and sediment. No correlation was found between the size fish and element concentrations. Liver appeared to be the main storage tissue of trace elements and was classified as a macroconcentrator of Ag, Cu, Hg and Zn. Levels of trace elements in muscle of streaked prochilod were below recommended maximum levels established by national and international guidelines. According to Target Hazard Quotient (THQ), the consumption of muscle of P. lineatus from three sampling sites did not present toxicological risk for general and fishermen populations. Multivariate analyses suggest that the three groups studied remain with an important degree of geographical segregation, indicating that regulations should be revised according to the presence of contaminants in the different fishing areas.

The presence of numerous and diverse pollutants and natural toxins has been reported in the Suquia River Basin over 20 years. The fate of these toxic compounds can be mainly attributed to anthropic activities, starting with the release of nutrients from untreated sewage, causing eutrophication, cyanobacteria, and cyanotoxins in the upper basin, followed by poorly treated city sewage, which results in high loads of both inorganic and organic contaminants at the end of the middle basin. Last, but not least, intensive agriculture contributes with agrochemicals and veterinary medicines in the low river basin. Consequently, the inhabiting biota is exposed to a complex mixture of xenobiotics and natural toxins. In this chapter, we discuss on the deleterious effect caused by these toxic compounds on this biota, including the uptake, organ distribution, bioaccumulation, variations in different endpoints (biomarkers), and even changes at community level observed in some cases. The main goal of this chapter is to present a typical basin from a developing country in Latin America, showing both augmented levels and increased sophistication of pollutants found throughout the studied period. Unfortunately, this is a quite common situation in other developing countries, not only from Latin America; thus, this chapter could serve as a guide for future studies in other river basins affected by a complex contaminant mixture elsewhere.

Mangroves are complex ecosystems with widely varying abiotic factors such as salinity, pH, redox potential, substratum particle size, dissolved organic matter and xenobiotic concentrations, and a high biodiversity. This paper presents the trophodynamic pathways of accumulation and transfer of metals and metalloids (B, Al, V, Cr, Mn, Fe, Ni, Cu, Zn, Ag, As, Se, Rb, Sr, Pb and Hg), in three trophic chains (plant-crab-fish, plankton-shrimp-fish and plankton-oyster) of similar food webs, corresponding to two mangrove estuaries (Santa Cruz and Vitoria Bay, separated by 70 km) in the Espirito Santo State (Brazil). Although the trophic transfer patterns are affected by physical variables, metal and metalloids were found in all trophic levels. We observed similar trophodynamics between both estuaries with some elements, but unequal transfer patterns in other cases, thus questioning the effectiveness of 15N to determine the food chain when the aquatic biota is affected by anthropogenic contaminants. Thus, in the Santa Cruz estuary, most metals were biomagnified through the food web. Conversely, Vitoria Bay presented mostly biodilution, suggesting that metal/metalloid transference patterns in mangrove ecosystems may be affected by different anthropogenic contamination inputs. These results indicate the importance of knowing the complete food web when evaluating the trophic transfer of elements, including an evaluation of the differential impact of pollution on diverse components of the food chain.

Air pollution legislation and control worldwide is based on the size of particulate matter (PM) to evaluate the effects on environmental and human health, in which the small diameter particles are considered more dangerous than larger sizes. This study investigates the composition, stability, size and dispersion of atmospheric settleable particulate matter (SePM) in an aqueous system. We aimed to interrogate the changes in the physical properties and characteristics that can contribute to increased metal uptake by aquatic biota. Samples collected in an area influenced by the steel and iron industry were separated into 8 fractions (425 to ≤10 μm) and analysed physically and chemically. Results from ICP-MS and X-ray showed that the PM composition was mainly hematite with 80% of Fe, followed by Al, Mn and Ti. Among 27 elements analysed we found 19 metals, showing emerging metallic contaminants such as Y, Zr, Sn, La, Ba and Bi. Scanning electron microscopy (SEM) showed that SePM fractions are formed by an agglomeration of nanoparticles. Furthermore, dynamic light scattering (DLS), zeta potential and nanoparticle tracking analysis (NTA) demonstrated that SPM were dissociated in water, forming nanoparticles smaller than 200 nm, which can also contribute to water pollution. This study highlights that SePM contamination may be substantially higher than expected under that allowed in atmospheric regulatory frameworks, thereby extending their negative effect to water bodies upon settling, which is an underexplored area of our knowledge. We therefore provide important insights for future investigations on safety regulations involving SePM in the environment, indicating the need to revise the role of SePM, not solely associated with air pollution but also considering their deleterious effects on water resources.

The increasing contamination of water bodies with mercury (Hg) raises concerns about the possible effects of this metal on native fish species. Our current understanding of its dynamics in fish organs remains limited. In this study, adult individuals of the native species Astyanax eigenmanniorum were exposed to three environmentally relevant HgCl2 concentrations (5, 100, and 170 μg L−1) for 96 h. To evaluate total Hg (THg) elimination, new individuals were exposed to 100 μg L−1 of HgCl2 (96 h), and at the end of the exposure period, half of the fish were placed in tanks with clean water for 168 h. In both assays, the organs were removed, and THg levels were measured using ICP-MS. The uptake of IHg in A. eigenmanniorum showed a differential accumulation in the organs. Gills, intestine, and brain were the tissues with the highest THg levels. Finally, no elimination of THg in the water was observed, but intestine and gills significantly removed the THg accumulated. Probably a Hg redistribution through the tissues could take place.

Anthropogenic inputs are affecting freshwaters. Stable isotope ratios of nitrogen (δ15N) are useful to track anthropogenic pollution in food webs across different habitats, species and trophic levels. Cordoba province (Argentina) has serious problems of eutrophication and pollution in some of its freshwater reservoirs. To evaluate the different anthropogenic inputs in the three most important reservoirs in Cordoba: San Roque Lake (SRL), Los Molinos Lake (LML) and Rio Tercero Reservoir (RTR), δ15N was measured in water, plankton, shrimp (Palaemonetes argentinus) and fish (Odontesthes bonariensis) muscle samples. Results show that δ15N values of SRL samples (δ15N values between 14.9 and 20.0‰) are higher than those of the analogous samples from the other reservoirs, and denote a high influence of sewage discharge in this lake. The results show that the sewage isotopic signals in water were transferred to primary producers, then to mobile consumers, including fish. The findings of this study suggest that this reservoir is a source apparently not safe for food production, like edible fish. Finally, biota has proven to be a sensitive organism whose δ15N value can be used as bioindicator for pollution and human impact on the ecosystem in which it lives.

The aim of this work was to verify the usefulness of multielemental and isotopic fingerprint to differentiate the origin of milk samples from different areas, linking milk fingerprint with those corresponding to soil, water, and forage. Samples from four production areas in Argentina were analysed: 26 elements, δ2H, δ13C, δ15N and δ18O. Milk provenance was assessed using 16 variables (Na, Mg, Al, V, Co, Ni, As, Se, Rb, Sr, Mo, Hg, δ2H, δ18O, δ13C and K/Rb). Generalized Procrustes Analysis (GPA) demonstrated the consensus between soil, water, forage and milk, in addition to differences between studied areas. Canonical Correlation Analysis (CCA) demonstrated significant correlations between the milk-drinking water, milk-forage, and milk-soil. So far, we report a feasible method to establish the milk provenance, assessing the follow up from environmental matrixes (soil + water) to dairy products through the food web (forage) by a combined chemical-isotopic fingerprint.

Espírito Santo estuaries (Brazil) are impacted by industrial activities, resulting in contamination of water and sediments. This raise questions on biological uptake, storage and consequences of metal contamination to mangrove plants. The goal of this work was evaluating accumulation and translocation of metals from sediment to roots and leaves of Avicennia schaueriana, growing in areas with different degrees of contamination, correlating bioaccumulation with changes in its root anatomy. Highest bioconcentration factors (BCFs) were observed in plants growing in less polluted areas. Conversely, highest translocation factors were found in plants from highest polluted area, evidencing an adaptive response of A. schaueriana to less favourable conditions. Namely, the absorption of metals by roots is diminished when facing highest levels of metals in the environment; alternatively, plants seem to enhance the translocation to diminish the concentration of toxic metals in roots. Root also responded to highly polluted scenarios with modifications of its anatomy. Fil: Souza, Iara da C.. Universidade Federal do São Carlos; Brasil Fil: Rocha, Lívia D.. Universidade Federal do Espírito Santo; Brasil Fil: Morozesk, Mariana. Universidade Federal do São Carlos; Brasil Fil: Bonomo, Marina M.. Universidade Federal do São Carlos; Brasil Fil: Arrivabene, Hiulana P.. Universidade Federal do Espírito Santo; Brasil Fil: Duarte, Ian D.. Universidade Federal do Espírito Santo; Brasil Fil: Furlan, Larissa M.. Universidade Federal do Espírito Santo; Brasil Fil: Monferran, Magdalena Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina Fil: Mazik, Krysia. University of Hull; Reino Unido Fil: Elliott, Michael. University of Hull; Reino Unido Fil: Matsumoto, Silvia T.. Universidade Federal do Espírito Santo; Brasil Fil: Milanez, Camilla R.D.. Universidade Federal do Espírito Santo; Brasil Fil: Wunderlin, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina Fil: Fernandes, Marisa N.. Universidade Federal do São Carlos; Brasil

Aquatic invertebrates take up and accumulate essential and non-essential trace metals even when both are likely to be poisonous. In order to study the potential of the metallothioneins (MTs) as biomarkers of metal contamination in native shrimp Palaemonetes argentinus, organisms have been exposed at 0, 5, 50 and 500 μg L−1 of zinc for 96 h. Moreover, accumulation and subcellular distribution of this essential metal were evaluated. A significant Zn accumulation was observed in different body sections. Higher Zn levels occurred in cephalothorax compared to abdomen, especially at the highest exposure concentration (500 μg Zn L−1). A clear differential subcellular metal distribution between cephalothorax and abdomen was also observed. In cephalothorax Zn was similarly distributed between the soluble and insoluble fractions; while in abdomen, when total Zn increased, insoluble metal augmented more markedly than the soluble one. Cytosolic Zn levels increased more in cephalothorax than in abdomen of shrimps exposed to 500 μg Zn L−1 when compared to control. Finally, a significant induction of MTs was observed in cephalothorax at 500 μg Zn L−1. A potential role for MTs as biomarkers in P. argentinus should be further studied to enhance the sensitivity of the response, although it is likely that MTs play a key role in metal detoxification since the increase of these proteins is linked to metal challenge.

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. Fil: da Souza, Lara. Universidade Federal do São Carlos; Brasil Fil: Marques Bonomo, Marina. Universidade Federal do Espírito Santo; Brasil Fil: Morozesk, Mariana. Universidade Federal do Espírito Santo; Brasil Fil: Dorsch Rocha, Livia. Universidade Federal do Espírito Santo; Brasil Fil: Drumond Duarte, Ian. Universidade Federal do Espírito Santo; Brasil Fil: Furlan, Larissa Maria. Universidade Federal do Espírito Santo; Brasil Fil: Pereira Arrivabene, Hiulana. Universidade Federal do Espírito Santo; Brasil Fil: Monferran, Magdalena Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina Fil: Matsumoto, Silvia Tamie. Universidade Federal do Espírito Santo; Brasil Fil: Dias Milanez, Camila Rozindo. Universidade Federal do Espírito Santo; Brasil Fil: Wunderlin, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina Fil: Narciso Fernandes, Marisa. Universidade Federal do São Carlos; Brasil

Two neotropical estuaries affected by different anthropogenic factors were studied. We report levels of metals and metalloids in water and sediment as well as their influence on genetic, biochemical and morphological biomarkers in the native fish Centropomus parallelus. Biomarkers reflected the fish health status. Multivariate statistics indicated both spatial and temporal changes in both water and sediment, which are linked to the elemental composition and health status of inhabitant fish, showing the biggest influence of surface water, followed by sediments and interstitial water. Bioaccumulation in fish muscle was useful to identify elements that were below detection limits in water, pointing out the risk of consuming fish exceeding allowance limits for some elements (As and Hg in this case). Multivariate statistics, including physical, chemical and biological issues, presents a suitable tool, integrating data from different origin allocated in the same estuary, which could be useful for future studies on estuarine systems. Fil: Souza, Iara C.. Universidade Federal do Sao Carlos; Brasil Fil: Duarte, Ian D.. Universidade Federal do Espírito Santo; Brasil Fil: Pimentel, Natieli Q.. Universidade Federal do Sao Carlos; Brasil Fil: Rocha, Lívia D.. Universidade Federal do Espírito Santo; Brasil Fil: Morozesk, Mariana. Universidade Federal do Espírito Santo; Brasil Fil: Bonomo, Marina M.. Universidade Federal do Espírito Santo; Brasil Fil: Azevedo, Vinicius C.. Universidade Federal do Sao Carlos; Brasil Fil: Pereira, Camilo D.S.. Universidade Santa Cecília; Brasil Fil: Monferran, Magdalena Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina Fil: Milanez, Camilla R. D.. Universidade Federal do Espírito Santo; Brasil Fil: Matsumoto, Silvia T.. Universidade Federal do Espírito Santo; Brasil Fil: Wunderlin, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina Fil: Fernandes, Marisa N.. Universidade Federal do Sao Carlos; Brasil

The Suquía River lower-middle basin (Córdoba, Argentina) is subject to a strong anthropic impact because it receives pollutants from different sources (industries, wastewaters, heavy traffic, agricultural land use, etc.) We have assessed the degree of watershed degradation of Suquía River lower-middle sections through the analysis of different ecosystem compartments (air, water, riparian soil, sediments and biota), in order to provide useful data to be considered in future river restoration programs. Four study sites were selected along the river (La Calera city, Córdoba city, Corazón de María village and Río Primero city) which were sampled during the low- and high-water flow periods. We analyzed: a) chemical and physical characteristics of water, sediments, and riparian soil; b) heavy metal content of water and sediments, and c) semi-volatile organic compounds in air. Besides, pollutant bioindicators such as fish assemblages, lichens (Usnea amblyoclada), vascular plants (Tradescantia pallida), and microorganisms (fecal coliform and Escherichia coli) were used to further assess the status of the river. All analyzed ecological compartments were affected by water pollution, particularly, fish assemblages, sediments and riparian soils by heavy metal and coliform bacteria. Moreover, we detected a possible contribution of sulfur and a high pollutant content in air that merit further research about other air-water exchanges. Accordingly, we strongly suggest that an action to restore or remediate the anthropic effect on the Suquía River be extended to all possible compartments along the river.

We report a combined two-year seasonal monitoring of Suquía River basin using both chemical parameters and biomarkers measured in Jenynsia multidentata, aiming to correlate external levels of contaminants with the response of oxidative stress biomarkers in this fish. Identified pollution sources correspond to city sewage as well as agricultural and small industry activities downstream from Córdoba city. Physicochemical parameters integrated into a water quality index (WQI) were measured in Suquía River during dry and wet seasons. Ag, Mn, Cu, Cr, Ni, Fe, Pb and Zn were also monitored in water and sediment samples. Biomarkers include detoxication and antioxidant enzymes: catalase (CAT), glutathione peroxidase (GPX), glutathione S-transferase (GST) and glutathione reductase (GR). Enzymes showed a pollution dependent response, with increased activities in fish collected close to the sewage exit and progressive drop further downstream, matching changes in the Water Quality index. The combined use of biomarkers with water quality parameters allowed both the identification of pollution sources and the evaluation of effects of contaminants on the aquatic biota.

The golden mussel Limnoperna fortunei was used as a biomonitor of environmental pollution in the Suquía River basin around Córdoba City (Argentina). The sampling sites along the river were chosen according to their increasing levels of pollutants (e.g. heavy metals) as well as biological oxygen demand (BOD) and chemical oxygen demand (COD). A water quality index (WQI) was constructed from the interaction of several normalized factors that affect the aquatic environment, such as the mentioned pollutants and physico-chemical characteristics of the sampling sites. Activity changes of biotransformation enzyme glutathione S-transferase (GST) and the antioxidant enzymes glutathione peroxidase (GPx), glutathione reductase (GR) and catalase (CAT), after exposure to pollutants, served as biomarkers. Membrane bound GST and antioxidant enzymes responded at the most polluted sampling site within 1 day showing increased activities lasting for 4 days. Further sampling was restricted due to no survival of the animals. Antioxidant enzymes GPx, GR and CAT were sensitive responding to the different pollution scenarios, showing good correlation to the chemical characterization.

Bioaccumulation and toxicity of copper was evaluated on Potamogeton pusillus L. The effect of copper (5-100 microg L(-1)) applied for several days was assessed by measuring changes in the chlorophyll's, phaeophytin's, malondialdehyde, electrical conductivity, glutathione peroxidase (GPX), glutathione reductase (GR) and guaiacol peroxidase (POD) activities. Plants accumulated copper with a maximum of 162 microg g(-1) dw after 7-days exposure at 100 microg L(-1), however most of the metal was accumulated after 1-day exposure. The toxic effect caused by Cu was evident by the reduction of photosynthetic pigments, increase of malondialdehyde and electrical conductivity. P. pusillus shows Cu-induced oxidative stress by modulating antioxidant enzymes like GPX, GR and POD. Antioxidant enzymes activity increased significantly after exposure to 40 microg L(-1) during 24 h, followed by a drop at longer times. Thus, P. pusillus is proposed as a good biomonitor for the assessment of metal pollution in aquatic ecosystems.

We report changes in activities of detoxification and antioxidant enzymes as well as lipid peroxidation levels in liver, gills, and brain of Jenynsia multidentata exposed to 1,2- and 1,4-dichlorobenzene (DCB). Fish were captured at an unpolluted area, transported to the laboratory, and acclimated previous to experiments. Exposures were carried out using 1,2-DCB at 0.5, 1, 5, and 10 mg L−1 and 1,4-DCB at 0.05, 0.1, 1, and 5 mg L−1. After 24-h exposure, fish were sacrificed and dissected separating liver, gills, and brain of each fish. Organs were used for enzyme extractions, evaluating antioxidant system through the assay of glutathione reductase, guaiacol peroxidase, glutathione peroxidase, catalase as well as detoxification system by measuring glutathione-S-transferase (GST) activity. Additionally, thiobarbituric acid reactive substances (TBARS) method was used to evaluate the peroxidation of lipids. No changes in GST activity were found in liver of fish exposed to DCBs but in gills and brain of exposed fish. The detoxification system was activated at lower concentrations of 1,2-DCB than 1,4-DCB. Antioxidant response is activated in liver at low DCB concentrations, followed by a drop at highest levels. We also found activation of the antioxidant system in gills and brain of exposed fish. On the other hand, we did not observe changes in TBARS concentrations in liver or gills of exposed fish with respect to controls, but in brain of fish exposed to 1,2-DCB (≥0.5 mg L−1) and 1,4-DCB (5 mg L−1). Responses of both detoxification and antioxidant systems of J. multidentata suggest that 1,2-DCB is more toxic than 1,4-DCB to this specie. To the extent of our knowledge, this is the first report of oxidative stress induced by DCBs in fish. Our results evidence that the brain is the organ most severely affected by the oxidative stress caused by DCBs. Fil: Monferran, Magdalena Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; Argentina Fil: Pesce, Silvia Fabiana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; Argentina Fil: Cazenave, Jimena. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas, Físicas y Naturales. Cátedra de Diversidad Animal I; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Wunderlin, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; Argentina

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. Fil: Monferran, Magdalena Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina Fil: Garnero, Paola Lorena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Diversidad y Ecología Animal. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Instituto de Diversidad y Ecología Animal; Argentina Fil: Wunderlin, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina Fil: Bistoni, Maria de Los Angeles. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Diversidad y Ecología Animal. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Instituto de Diversidad y Ecología Animal; Argentina

Metals, metalloids and nonmetals concentrations along the Suquia River basin have been monitored in sediment and surface water, during the wet and dry season, at different points and by different authors since 1997 until 2014. The potential ecological risk (PER) in surface sediments along some studied stations is presented on the basis of measured data.

Roots of mangrove trees have an important role in depurating water and sediments by retaining metals that may accumulate in different plant tissues, affecting physiological processes and anatomy. The present study aimed to evaluate adaptive changes in root of Rhizophora mangle in response to different levels of chemical elements (metals/metalloids) in interstitial water and sediments from four neotropical mangroves in Brazil. What sets this study apart from other studies is that we not only investigate adaptive modifications in R. mangle but also changes in environments where this plant grows, evaluating correspondence between physical, chemical and biological issues by a combined set of multivariate statistical methods (pattern recognition). Thus, we looked to match changes in the environment with adaptations in plants. Multivariate statistics highlighted that the lignified periderm and the air gaps are directly related to the environmental contamination. Current results provide new evidences of root anatomical strategies to deal with contaminated environments. Multivariate statistics greatly contributes to extrapolate results from complex data matrixes obtained when analyzing environmental issues, pointing out parameters involved in environmental changes and also evidencing the adaptive response of the exposed biota.

The use of phytoremediation for restoration or amelioration of soils polluted with heavy metals is a promising technique for the near future. Generally, if a plant can accumulate more than 1000 mg kg−1 (or 1000 ppm) of Cu, Co, Cr, Ni, or Pb, or more than 10,000 mg kg−1 (or 10,000 ppm) of Mn or Zn, it is defined as a hyperaccumulator. The discovery and elucidation of the mechanism used by hyperaccumulators to take up, translocate, and fix heavy metals in aerial parts is of great interest to understand the role of such plants in biorestoration. The performance of plants for heavy metals phytoremediation depends on several factors, starting from the bioavailability of metals in the soil, which is conditioned by cation exchange capacity, soil pH and organic matter content, the oxidation state of the metal, presence of both natural and synthetic chelants, interaction with soil microorganisms, etc. The mechanism used by roots to uptake bioavailable metals from the soil is also crucial for the success of bioaccumulation, in addition to mechanisms used to translocate metals from root to shoots after absorption. Significant progress in understanding the mechanisms governing metal hyperaccumulation has been made in the last decade through comparative physiological, genomic, and proteomic studies of hyperaccumulators and related non-hyperaccumulator plants. Parts of these studies are discussed here. Finally, the efficiency in detoxification and sequestration is a key property of hyperaccumulators, allowing them to concentrate huge amounts of heavy metals in aerial organs without apparent phytotoxic effect. This exceptionally high heavy metal accumulation becomes even more surprising considering that it mainly occurs in leaves where photosynthesis, essential for plant survival, is accomplished, and that the photosynthetic apparatus is a major target for most of these contaminants. Although extensive laboratory studies on phytoextraction by plants have been reported, less research has been dedicated to evaluate the performance in field studies, which seems necessary to both validate laboratory studies and fully demonstrate the usefulness of this technique for site restoration.

The Suquia River middle-lower basin (Cordoba, Argentina) is subject to a strong anthropogenic impact because it receives pollutants from different sources. Recent studies have shown the importance and the need of approaching the monitoring process of water quality from integral perspectives through the use of chemical as well as biological methods. The main goal of this study was to evaluate the fish species Jenynsia multidentata as a bioindicator of environmental pollution in the middle-lower basin of the Suquia River using biotransformation and antioxidant enzymes as well as gill and liver histopathology as biomarkers. We also studied the fish-assemblage characteristics through the fish species pattern variation and the application of a biotic index based on fish data. Our study also included the analysis of a water-quality index, heavy-metal concentrations in sediment and water, and pesticide concentrations in sediment. The chemical analyses of the middle-lower Suquia River basin showed a water-quality degradation gradient. Fish-assemblage structure changed with increasing water pollution, showing a simpler structure at the most polluted area. According to the bioitc index, the variation pattern of fish assemblages reflected the aquatic environmental deterioration. Both molecular and histopathological biomarkers reflected the same trend in relation to water quality. However, enzymes varied with more acute precision between seasons. In addition, each enzyme presented with different sensibility. At tissue level, the histopathological analysis detected chronic contamination at both stations and seasons. The present work, which comprises different levels of biological organization together with chemical analyses, generated particular although complementary information, thus evidencing the same trend of aquatic contamination. Thus, the development of integral investigations gives a comprehensive approach and becomes the most effective tool to construct policies both preventive and palliative. Our study constitutes a good model to be applied in other endorheic basins of South America.

The aquatic macrophyte, Potamogeton pusillus was evaluated for the removal of Cu 2+ and Cr +6 from aqueous solutions during 15 days phytoextraction experiments. Results show that P. pusillus is capable of accumulating substantial amount of Cu and Cr from individual solutions (either Cu 2+ or Cr +6 ). Significant correlations between metal removal and bioaccumulation were obtained. Roots and leaves accumulated the highest amount of Cu and Cr followed by stems. The bioaccumulation of Cr was significantly enhanced in the presence of Cu, showing a synergic effect on Cr +6 removal, presenting a good alternative for the removal of these metals from polluted aquifers. To the extent of our knowledge, this is the first report on both enhanced phytoextraction of Cr +6 in presence of Cu +2 and bioaccumulation of these heavy metals by P. pusillus .

A subsurface microbial community was isolated from a polluted site of Suquía River (Córdoba—Argentina), acclimated during 15 days in aerobic conditions using 1,2-dichlorobenzene (1,2-DCB) as the sole carbon source. From this acclimated community, we isolated and identified by 16S rDNA analysis a strain of Acidovorax avenae, which was able to perform the complete biodegradation of 1,2-DCB in two days affording stoichiometric amounts of chloride. This pure strain was also tested for biodegradation of chlorobenzene (CB); 1,3-DCB and 1,4-DCB, giving similar results to the experiments using 1,2-DCB. The aromatic-ring-hydroxylating dioxygenase (ARHDO) α-subunit gene core, encoding the catalytic site of the large subunit of chlorobenzene dioxygenase, was detected by PCR amplification and confirmed by DNA sequencing. These results suggest that the isolated strain of A. avenae could use a catabolic pathway, via ARHDO system, leading to the formation of chlorocatecols during the first steps of biodegradation, with further chloride release and subsequent paths that showed complete substrate consumption. Fil: Monferran, Magdalena Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina Fil: Echenique, Jose Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; Argentina Fil: Wunderlin, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina

Three dichlorobenzene isomers (DCBs) were monitored in water and sediment from the Suquía River basin by Solid Phase Microextraction (HS-SPME), coupled to Gas Chromatography-Mass Spectrometry (GC-MS). DCBs were not detected in water or sediments corresponding to the upper basin. Pollution with DCBs became evident when the river flows through small cities. As expected, Córdoba city causes the most severe pollution, presenting up to 764.7 μg kg-1 DW DCBs in the sediment of urban areas. Results show that DCBs mainly originate in domestic activities, reaching the river by non-point sources such as urban run-off or sewage discharge, resulting in a widespread distribution in the basin. The high level of DCBs found in sediments involves absorption of these xenobiotics in the natural organic matter of sediments. This organic layer could be responsible for transporting DCBs downstream from their discharge, thus spreading the pollution throughout the basin. Fil: Monferran, Magdalena Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina Fil: Cortina, Pablo Ramiro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Santiago, Ana Noemi. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Wunderlin, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentina