Determination of priority pesticides in water samples combining SPE and SPME coupled to GC-MS. A case study: Suquía River basin (Argentina)

This study reports a combined method using solid phase extraction (SPE), followed by solid phase microextraction (SPME) to concentrate different pesticides, including chlorinated, organophosphorus, triazines, pyretroids and chloroacetamides, present at trace levels in water samples. Identification and quantification was carried out by gas chromatography coupled to Mass Spectrometry (GC-MS). The optimized methodology showed LOQs at ngL-1 levels (ranging 0.2-3.5ngL-1) in addition to acceptable precision and robustness (recoveries ranged 63-104%, RSD from 4% to 23%), presenting a novel method to reach trace levels, similar to that obtainable using EC detector, with structural confirmation by MS during the analysis of a wide range of environmental pollutants.This method was applied to the study of temporal and spatial distribution of pesticides in the Suquía River basin (Córdoba-Argentina). As expected, highest levels of agrochemicals were observed in areas with intensive agricultural practices, being atrazine (max.=433.9ngL-1), alpha-cypermetrine (max.=121.7ngL-1) and endosulfan sulfate (max.=106.7ngL-1) predominant. In urban areas, the prevalent pesticide was alpha-cypermethrine. These results draw attention to the need of pesticide monitoring programs in rivers, considering both urban and rural sections.Fil: Bonansea, Rocio Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; ArgentinaFil: Amé, María Valeria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; ArgentinaFil: 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; Argentin

Usefulness of a freshwater macrophyte (Potamogeton pusillus) for an environmental risk assessment in a multi-source contaminated basin.

Chemical analysis of pollutants in environmental matrices cannot always offer powerful evidence on their impact and toxicity on the aquatic biota. This paper reports the ability of Potamogeton pusillus to highlight in an aquatic ecosystem those sites with higher environmental degradation through an active biomonitoring. Organisms were exposed for 96 h in seven sites along a river where variation in pollutants mixtures and levels could be expected due to different pollution sources. Different anthropogenic activities favoured the presence of pharmaceutical compounds along the basin (atenolol and carbamazepine showed the highest levels in water) as well as metals in water (Pb, Al, As, B, Hg) and sediments (Hg) surpassing local and international environmental guidelines. Through several biomarkers responses, P. pusillus showed sensitivity when exposed to different environmental scenarios and succeeded indicating the most contaminated sites. An integrative biomarker response index (IBR) confirmed to be a useful tool to obtain a holistic interpretation of response expressed by organism despite being little used for macrophyte studies. The Principal Components Analysis (PCA) analysis showed consistently a positive association between the IBR and pollutants concentrations, being this linkage strongest when a higher compounds levels occurred in the basin (cold period). Moreover, multivariate analysis indicated that IBR values were boosted when the concentration of metal in water and in the bioavailable fraction of sediments, increased. Finally, the obtained results indicate that the use of P. pusillus in combination with chemical analysis could be considered a promising tool for environmental management of aquatic ecosystems contaminated by multi-source.Fil: Bertrand, Lidwina. 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; ArgentinaFil: 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; ArgentinaFil: Valdés, María Eugenia. 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; ArgentinaFil: Amé, María Valeria. Universidad Nacional de Córdoba; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; Argentin

Ecological Risk Assessment (ERA) of pesticides from freshwater ecosystems in the Pampas region of Argentina: Legacy and current use chemicals contribution

Agricultural production in the Pampas region is one of the most important economic activities in Argentina. However, the possible environmental effects related to the growth of this activity in the last years have not been studied enough. Particularly, the effects of pesticides mixtures are a topic of great concern both for society and regulatory authorities worldwide, given the possible additive and synergistic relationships between these chemicals and their possible effects on aquatic biota. Based on a concentration addition model, this study developed an Ecological Risk Assessment (ERA) of pesticides from freshwater ecosystems in the Pampas region. For this purpose, reported pesticides concentrations available in public bibliography and a Risk Quotients (RQs) approach were used. A cumulative risk map was established to display RQs for current use pesticides (CUPs) and legacy chemicals. The ΣRQs were calculated for 66 sites, using available reported measured environmental concentrations (MECs) and predicted no effect concentrations (PNECs) of pesticides. While ΣRQ for only CUPs resulted in a high and very high risk (ΣRQ > 1) for 29% of the sites, when legacy pesticides were incorporated this percentage reached the 41% of the sites, increasing significantly the absolute values of RQ. Herbicides like glyphosate and atrazine contributed considerably to the ΣRQCUPs while organochlorines were the major contributors for ΣRQs when legacy pesticides were incorporated. Moreover, some active ingredients (acetochlor, carbendazim and fenitrothion) which are approved for their use in Argentina but banned in EU showed high contribution to ΣRQCUPs. The present study is the first attempt to develop an ERA in surface water of the Pampas region of Argentina and it provides a starting point for a more comprehensive pesticides monitoring and a further risk assessment program.Fil: Iturburu, Fernando Gastón. Universidad Nacional de Mar del Plata; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Marinas y Costeras. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Marinas y Costeras; ArgentinaFil: Calderon, Gabriela. Universidad Nacional de Mar del Plata; ArgentinaFil: Amé, María Valeria. Universidad Nacional de Córdoba; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; ArgentinaFil: Menone, Mirta Lujan. Universidad Nacional de Mar del Plata; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Marinas y Costeras. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Marinas y Costeras; Argentin

MTs in Palaemonetes argentinus as potential biomarkers of zinc contamination in freshwaters

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.Fil: Bertrand, Lidwina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; ArgentinaFil: Monferran, Magdalena Victoria. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas; Argentina. 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; ArgentinaFil: Métais, Isabelle. Université Catholique de l'Ouest; FranciaFil: Mouneyrac, Catherine. Université Catholique de l'Ouest; FranciaFil: Amé, María Valeria. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; Argentin

Tissue-specific bioconcentration and biotransformation of cypermethrin and chlorpyrifos in a native fish (<i>Jenynsia multidentata</i>) exposed to these insecticides singly and in mixtures

The aim of the present study was to evaluate the accumulation of cypermethrin and chlorpyrifos when the fish Jenynsia multidentata was exposed to these pesticides singly and in technical and commercial mixtures. Adult female fish were exposed over 96 h to 0.04 μg/L of cypermethrin; 0.4 μg/L of chlorpyrifos; 0.04 μg/L of cypermethrin + 0.4 μg/L of chlorpyrifos in a technical mixture; and 0.04 μg/L of cypermethrin + 0.4 μg/L of chlorpyrifos in a mixture of commercial products. Fish exposed to cypermethrin accumulated this compound only in muscle, probably because of the low biotransformation capacity of this organ and the induction of cytochrome P4501A1 (CYP1A1) expression in the liver. The accumulation of chlorpyrifos occurred in fish exposed to the insecticide (intestine > liver > gills) even when these fish had higher gluthatione-S-transferase (GST) activin gills and P-glycoprotein (P-gp) expression in the liver, compared with the control. Fish exposed to the technical mixture showed cypermethrin accumulation (liver > intestine > gills) with higher levels than those measured in fish after only cypermethrin exposure. Higher expression levels of CYP1A1 in the liver were also observed compared with the Control. Fish exposed to the commercial mixture accumulated both insecticides (cypermethrin: intestine > gills and chlorpyrifos: liver > intestine > gills > muscle). In the organs where accumulation occurred, biotransformation enzymes were inhibited. Consequently, the commercial formulation exposure provoked the highest accumulation of cypermethrin and chlorpyrifos in J. multidentata, possibly associated with the biotransformation system inhibition.Centro de Investigaciones del Medioambient

Evaluación de la calidad de agua del Río Tercero (Ctlamochita)

El Río Tercero, o Ctalamochita, es uno de los más caudalosos y utilizados de la Provincia de Córdoba. En su recorrido pasa por grandes ciudades, donde recibe descargas de industrias y efluentes cloacales. Se eligieron los sitios antes de las ciudades más importantes y aguas abajo de las mismas, incluyendo de esta forma las descargas cloacales y de las industrias ubicadas cerca del río. Los sitios seleccionados fueron: al comienzo del nacimiento del río, en la ciudad de Río Tercero, aguas debajo de esta ciudad, antes y después de Villa María, en el balneario de Bell Ville y al finalizar el recorrido del río en el Club Matienzo de la localidad de Saladillo En este trabajo se caracterizó la calidad del agua del Río Ctalamochita o Tercero, a través de diferentes herramientas estadísticas y mediante el uso del Índice de Calidad de Agua (ICA). Para ello se utilizaron los parámetros clásicos de monitoreo; físicos, químicos y bacteriológicos medidos en agua desde el año 2005 al 2009. Estos datos se analizaron utilizando estadística descriptiva, el Índice de Calidad de Agua (ICA), y análisis multivariado. Los resultados de estos análisis evidenciaron el deterioro que sufre el río al atravesar las grandes ciudades, como Villa María y Bell Ville. Estas diferencias son explicadas por algunas variables entre las que se destaca el aumento del contenido de fósforo total aguas abajo de las mencionadas ciudades.Fil: O'Mill, Patricia. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas; Argentina.Fil: O'Mill, Patricia. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas, Físicas y Naturales; Argentina.Fil: O'Mill, Patricia. Secretaría de Recursos Hídricos y Coordinación; Argentina.Fil: Amé, Valeria. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas; Argentina.Fil: Cossavella, Ana María. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas, Físicas y Naturales; Argentina.Fil: Cossavella, Ana María. Secretaría de Recursos Hídricos y Coordinación; Argentina.Fil: Larrosa, Nancy. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas, Físicas y Naturales; Argentina.Fil: Carranza, Patricia María. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas, Físicas y Naturales; Argentina.Otras Ciencias de la Tierra y relacionadas con el Medio Ambient

Evaluación de la calidad de agua del Río Tercero (Ctalamochita)

El Río Tercero, o Ctalamochita, es uno de los más caudalosos y utilizados de la Provincia de Córdoba. En su recorrido pasa por grandes ciudades, donde recibe descargas de industrias y efluentes cloacales. Se eligieron los sitios antes de las ciudades más importantes y aguas abajo de las mismas, incluyendo de esta forma las descargas cloacales y de las industrias ubicadas cerca del río. Los sitios seleccionados fueron: al comienzo del nacimiento del río, en la ciudad de Río Tercero, aguas debajo de esta ciudad, antes y después de Villa María, en el balneario de Bell Ville y al finalizar el recorrido del río en el Club Matienzo de la localidad de Saladillo En este trabajo se caracterizó la calidad del agua del Río Ctalamochita o Tercero, a través de diferentes herramientas estadísticas y mediante el uso del Índice de Calidad de Agua (ICA). Para ello se utilizaron los parámetros clásicos de monitoreo; físicos, químicos y bacteriológicos medidos en agua desde el año 2005 al 2009. Estos datos se analizaron utilizando estadística descriptiva, el Índice de Calidad de Agua (ICA), y análisis multivariado. Los resultados de estos análisis evidenciaron el deterioro que sufre el río al atravesar las grandes ciudades, como Villa María y Bell Ville. Estas diferencias son explicadas por algunas variables entre las que se destaca el aumento del contenido de fósforo total aguas abajo de las mencionadas ciudades.Fil: O’Mill, Patricia. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas; Argentina.Fil: O’Mill, Patricia. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas, Físicas y Naturales; Argentina.Fil: O’Mill, Patricia. Secretaría de Recursos Hídricos y Coordinación; Argentina.Fil: Amé, María Valeria. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas; Argentina.Fil: Cosavella, Ana María. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas, Físicas y Naturales; Argentina.Fil: Cosavella, Ana María. Secretaría de Recursos Hídricos y Coordinación; Argentina.Fil: Larrosa, Nancy. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas, Físicas y Naturales; Argentina.Fil: Carranza, Patricia. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas, Físicas y Naturales; Argentina.Otras Ingeniería del Medio Ambient

The fate of glyphosate and AMPA in a freshwater endorheic basin: An ecotoxicological risk assessment

Glyphosate is themostwidely used herbicideworldwide. However, there are some uncertain aspects with respect to its environmental fate. To evaluate the existence and distribution of this pesticide and its metabolite, aminomethylphosphonic acid (AMPA), their presence in fresh water, sediment, and suspended particulate matter (SPM) was measured in samples collected in a river running across a large city and through areas with intensive and extensive agriculture. The aquatic risk associated to the occurrence of these compounds was estimated using the hazard quotient (HQ) calculation for water and sediment. From the analyzed samples, overall 35% contained glyphosate, AMPA, or both compounds. Concentrations of the analytes were spread in different percentages depending on the environmentalmatrices considered,with levels ranging from12 to 20 times higher for glyphosate and AMPA in sediment and SPM, as compared with the levels found in water. The most polluted area was situated within a green belt zone of the city; while in second place were sites located in areas of extensive agriculture. Aquatic organisms inhabiting areas both inside and outside agricultural areas are threatened by water glyphosate concentrations. Benthic organisms inside the greenbelt zone and inside the lower basin are threatened by the concentrations of glyphosate in sediment. Even when the concentrations measured in water were below the levels of concern for wildlife, results showed the risk of agricultural practices to aquatic biota. An update of the limits established for freshwater biota protection is needed.Facultad de Ciencias ExactasCentro de Investigaciones del Medio Ambient

Can a low concentration of an organophosphate insecticide cause negative effects on an aquatic macrophyte? : Exposure of <i>Potamogeton pusillus</i> at environmentally relevant chlorpyrifos concentrations

The contamination of the aquatic environments with organophosphorus pesticides may affect non-target organisms. The aim of this study was to evaluate the toxic effects of the insecticide chlorpyrifos (CPF) at environmental concentrations on the freshwater macrophyte Potamogeton pusillus belonging to a genus of worldwide distribution. For this purpose, individuals were exposed from 3.5 to 94.5 ng of CPF L-1 for 96 h. A battery of biochemical responses including bioaccumulation, defense and damage biomarkers were measured in leaf, stem and root. Even when CPF was not detected in the macrophyte tissues, our results showed that this insecticide promotes oxidative stress and biomolecule damages in P. pusillus after acute exposure. Significant response of biomarkers was observed from the lowest tested concentration (3.5 ng CPF L-1). Oxidative stress was evidenced by increased lipid peroxidation and antioxidant enzymatic activation, including changes in superoxide dismutase, guaiacol peroxidase and glutathione peroxidase activities, especially in leaf. Also, a significant decrease in chlorophyll a and b contents was observed mainly in leaf. Finally, with some selected biomarkers, an Integrated Biomarker Response index was calculated showing a dose–response relationship with CPF exposure. Previous studies reported that herbicides and organophosphorus pesticides are responsible for several effects on photosynthetic systems but at higher exposure concentrations than the tested in this study. These results draw attention to the need for more studies in toxic effects of insecticides on aquatic macrophytes, at low concentrations and different biological levels, since the protection guidelines would not be preserving these species.Facultad de Ciencias ExactasCentro de Investigaciones del Medioambient

Antioxidant, phase II and III responses induced by lipoic acid in the fish Jenynsia multidentata (Anablapidae) and its influence on endolsulfan accumulation and toxicity

Antioxidants like lipoic acid (LA) are known to trigger augmented antioxidant and phase II and III responses. This study aimed to evaluate the effect of LA in P-glycoprotein (Pgp) expression, glutathione-S-transferase (GST) activity, total antioxidant competence, levels of lipid peroxides (TBARS) and accumulation of the organochlorine insecticide endosulfan (Endo: α-, β-isomers and sulfate metabolite) in different organs of the fish Jenynsia multidentata. One hundred and twenty females (1.55 ± 0.07 g) were fed during 8 days with (n = 60) or without (n = 60) a LA enriched ration (6000 mg/kg). Four experimental groups were defined: −LA/−Endo; +LA/−Endo; −LA/+Endo; and +LA/+Endo. Endo groups were exposed during 24 h to 1.4 μg of insecticide/L. Results showed that only LA induced a significant increment in liver Pgp expression. GST activity was augmented in liver after exposure to LA or Endo. TBARS levels were lowered in liver and gills after LA pre-treatment. Total antioxidant capacity was lowered in liver of Endo exposed fish, a result that was reversed by LA pre-treatment. It is concluded that LA induced the expected effects in terms of Pgp expression, GST activity and reduced TBARS levels although favored α-Endo accumulation in brain. However, the Endo metabolism to the more persistent endosulfan sulfate was not facilitated by LA pre-treatment.Fil: Monserrat, José María. Universidade Federal do Rio Grande do Norte; Brasil. Instituto de Ciências Biológicas; BrasilFil: Garcia, M. L.. Universidade Federal do Rio Grande do Norte; Brasil. Instituto de Ciências Biológicas; BrasilFil: Ventura Lima, J.. Universidade Federal do Rio Grande do Norte; Brasil. Instituto de Ciências Biológicas; BrasilFil: Gonzalez, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Mar del Plata. Instituto de Investigaciones Marinas y Costeras; ArgentinaFil: Ballesteros, Maria Laura. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Mar del Plata. Instituto de Investigaciones Marinas y Costeras; ArgentinaFil: Miglioranza, Karina Silvia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Mar del Plata. Instituto de Investigaciones Marinas y Costeras; ArgentinaFil: Amé, María Valeria. Universidad Nacional de Córdoba; ArgentinaFil: Wunderlin, Daniel Alberto. Universidad Nacional de Córdoba; Argentin