Remediation of endosulfan-contaminated water by hairy roots: removal and phytometabolization assessment.

Although many countries banned the insecticide endosulfan, it is still an environmental pollutant. Plants metabolize the two diastereomers of the formulations known as technical grade endosulfan (TGE) by two phase I pathways: hydrolysis leading to less toxic derivatives and oxidation giving endosulfan sulfate which is as toxic as endosulfan itself. We assessed the removal, bioaccumulation and phase I metabolization of TGE from water matrices using hairy root clones (HRs) of three edible species, Brassica napus, Raphanus sativus and Capsicum annuum. B. napus and C. annuum HRs removed 86% of TGE from the bioreaction media in 2 and 96 h, respectively, whereas R. sativus HRs removed 91% of TGE within 6 h of biotreatment. In the experiments with B. napus, only endosulfan sulfate was detected in both biomass and medium, whereas R. sativus and C. annuum accumulated endosulfan sulfate and endosulfan alcohol. Besides, endosulfan lactone was detected in C. annuum reaction medium. Acute ichthyotoxicity assays toward Poecilia reticulata showed that media contaminated with TGE lethal levels did not produce mortality after the phytotreatments. This research highlights the feasibility of using HRs to evaluate plant enzymatic abilities toward xenobiotics and their potential for the design of ex situ decontamination processes.

Validation of exposure indexes to pesticides through the analysis of exposure and effect biomarkers in ground pesticide applicators from Argentina.

The characterization of the population exposed to pesticides and the use of effective biomarkers to evaluate potential health effects are determinant to identify vulnerable groups, understanding the causality of diverse pathologies and propose prevention policies. This is particularly important in countries where intensive agricultural practices had an explosive expansion in last decades. The aim of this study was assessing the usefulness of two exposure indexes questionnaire-based: Intensity Level of the pesticide Exposure (ILE) and Cumulative Exposure Index (CEI) and their scales, in terrestrial applicators of pesticide from the Province of Córdoba (Argentina). The analysis was performed contrasting ILE and CEI results with perceived symptomatology, in addition to effect and exposure biomarkers. A cross-sectional study was designed to compare pesticides body burdens and effect biomarkers between subjects occupationally (OE) and non-occupationally exposed (NOE) to pesticides. Prevalence of perceived symptomatology and genotoxicity damage was higher in the OE group. The exposure condition was the only variable explaining these differences. Significant associations were found between CEI and neurologic symptomatology (p < 0.05) and between ILE and plasmatic cholinesterase (p < 0.1). However, residues of HCB, ß-HCH, α-endosulfan, pp'DDE, endrin, ß-endosulfan, pp'DDT, endosulfan sulfate and mirex were found in blood samples from both groups. To our knowledge, this is the first report on pesticides body burdens in occupational exposure settings in Argentina. So far, our current results indicate that the occupational condition affects the health of the workers. Significant associations found between symptomatology and biomarkers with scales of CEI and ILE suggest their usefulness to verify different levels of exposure. Further research is necessary to propose these indexes as an affordable tool for occupational health surveillance in areas with difficult access to health care centres.

Validación de un método para la determinación del ácido 3-fenoxibenzoico en orina por QuEChERS, microextracción líquido-líquido dispersiva y cromatografía líquida de alta resolución-arreglo de diodos / Validation of a method for the determination of 3-phenoxybenzoic acid in urine using QuEChERS, microextraction liquid-liquid dispersive and high-performance liquid chromatography-diode array

Los piretroides son insecticidas ampliamente usados no sólo en el ámbito agropecuario y doméstico sino también en salud pública. Una vez absorbidos, son rápidamente metabolizados a compuestos polares eliminados por vía renal. Uno de los metabolitos común a un gran número de piretroides es el ácido 3-fenoxibenzoico (3-PBA) el cual es utilizado como marcador de exposición. Se presenta en este trabajo, la validación de una metodología analítica para la determinación del 3-PBA utilizando QuEChERS acoplado a microextracción líquido-líquido dispersiva con tricloroetileno como disolvente extractivo y cromatografía líquida de alta resolución con detector de foto-arreglo de diodos. La validación se realizó con muestras aisladas de orina de voluntarios adultos de ambos sexos sin exposición conocida y orina sintética. El método resultó lineal en el intervalo 9 μg L-1-79 μg L-1; los límites de detección y cuantificación fueron de 3 μg L-1 y 9 μg L-1, respectivamente. No se observaron señales de interferentes a los tiempos de retención del 3-PBA y del ácido 2-fenoxibenzoico (2-PBA), estándar interno, en las muestras de orina blanco. Las señales cromatográficas en las muestras enriquecidas fueron espectralmente homogéneas. Las precisiones intradiarias (RSDr%) (n= 5) para 9 μg L-1 estuvieron comprendidas entre 9,3%-9,9% y para 27 μg L-1 entre 5,9%-10,6%. Las precisiciones interdiarias (RSDint%) (n=15) para los mismos niveles de concentración fueron de 11,8% y 9,1%, respectivamente. El rango de porcentajes de recuperación para 9 μg L-1 fue de 87%-119% y para 27 μg L-1 de 70%-91%. Se evaluó la estabilidad del analito en la muestra y en el extracto. El analito resultó estable a -20 °C durante 7 días en la muestra y durante 1 día en el extracto. Los valores de incertidumbre relativa e incertidumbre expandida fueron evaluados mediante la ecuación de Horwitz, los resultados obtenidos fueron para el nivel 9 μg L-1 de 33% y 65% y para el nivel 27 μg L-1 de 28% y 55%. La aplicabilidad del método validado fue evaluada con muestras reales de personas sin exposición laboral conocida, quienes declararon haber usado insecticidas piretroides. El método resultó sensible y selectivo.

Pyrethroid insecticides are used not only in the agricultural and domestic environment, but also in public health. Once absorbed, they are rapidly metabolized into polar compounds eliminated by the kidneys. One of the metabolites common to many pyrethroids is 3-phenoxybenzoic acid (3-PBA) which are used to evaluate exposure. We present in this paper the validation of an analytical methodology for the determination of 3-PBA using QuEChERS coupled to dispersive liquid-liquid microextraction with trichloroethylene as an extractive solvent and high-performance liquid chromatography with a photodiode array detector. Validation was carried out with isolated samples of urine from adult volunteers of both sexes without exposure and synthetic urine. The method was linear in the interval 9 μg L-1-79 μg L-1; the limit of detection and quantitation were 3 μg L-1 and 9 μg L-1, respectively. Interfering signals were not observed in the blank urine samples and the chromatographic signals in the enriched samples were spectrally homogeneous. The within-run precision (RSDr%) (n = 5) for 9 μg L-1 were between 9.3%-9.9% and for 27 μg L-1 between 5.9%-10.6%. The between-run precision (RSDint%) (n = 15) for the same concentration levels were 11.8% and 9.1%, respectively. The recovery for 9 μg L-1 ranged from 87%-119% and for 27 μg L-1 from 70%-91 %. The stability of the analyte was evaluated in the sample and in the extract. The analyte in the sample was stable at -20 °C for 7 days and in the extract was stable for 1 day. The values of relative uncertainty and expanded uncertainty obtained by the Horwitz equation were 33% and 65% for 9 μg L-1, and 28% and 55% for 27 μg L-1. The applicability of the validated method was evaluated with real samples of people without known occupational exposure, who declared having used pyrethroid insecticides. The method was sensitive and selective.

Treatment of endosulfan contaminated water with in vitro plant cell cultures.

Endosulfan is a Persistent Organic Pollutant insecticide still used in many countries. It is commercially available as mixtures of two diastereomers, α- and ß-endosulfan, known as technical grade endosulfan (TGE). A laboratory model based on the use of axenic plant cell cultures to study the removal and metabolization of both isomers from contaminated water matrixes was established. No differences were recorded in the removal of the two individual isomers with the two tested endemic plants, Grindelia pulchella and Tessaria absinthioides. Undifferentiated cultures of both plant species were very efficient to lower endosulfan concentration in spiked solutions. Metabolic fate of TGE was evaluated by analyzing the time course of endosulfan metabolites accumulation in both plant biomass and bioremediation media. While in G. pulchella we only detected endosulfan sulfate, in T. absinthioides the non-toxic endosulfan alcohol was the main metabolite at 48h, giving the possibility of designing phytoremediation approaches.

Calidad de vida urbana en la Argentina de la posconvertibilidad. Procesos sociales y territoriales en el período 2003-2012 / Quality of urban life in Argentina at post-convertibility: Social and territorial processes in the period 2003-2012

El objetivo del presente trabajo consiste en indagar los niveles de calidad de vida de la población urbana en la Argentina entre 2003 y 2012, período signado por la implementación de un modelo de crecimiento denominado posconvertibilidad, neodesarrollismo o posneoliberalismo, para reconocer sus efectos en la evaluación del bienestar de sus habitantes. Con tal fin, se elabora un Índice de Calidad de Vida de implantación puntual aplicado a las ciudades donde se releva la Encuesta Permanente de Hogares (EPH-INDEC), cuyas bases de datos corresponden a 32 aglomerados urbanos. El análisis se complementa con la búsqueda de la asociación estadística entre niveles de calidad de vida y distribución del ingreso en las ciudades incorporadas a la consulta de la EPH. Por tanto, el análisis pretende contribuir al conocimiento de las disparidades socioterritoriales entre las aglomeraciones urbanas, en el marco de procesos sociales, económicos, políticos y culturales que prefigurarían cambios importantes en el bienestar de los hogares argentinos a lo largo de los últimos diez años. (AU)

Evaluación de la exposición ambiental a plaguicidas orgánicos persistentes en dos barrios de la provincia de Córdoba / Assessment of environmental exposure to persistent organic pesticides in two neighborhoods of the province of Corodba

Se determinó la concentración de plaguicidas organoclorados en 167 muestras de sangre entera de habitantes de dos barrios (Sitio Nº 1 y Sitio Nº 2) de la provincia de Córdoba ubicados en los alrededores de depósitos de plaguicidas obsoletos. La presencia de plaguicidas se determinó por cromatografía gaseosa con detector de captura electrónica utilizando columnas capilares de distinta polaridad. Los plaguicidas más frecuentemente encontrados fueron p,p’-DDE, β-HCH y HCB. La máxima concentración detectada fue 7,31 μg/l y correspondió a p,p’-DDE. El β-HCH mostró valores más altos que los otros isómeros en la familia de los hexaclorociclohexanos (HCH). Se observó buena correlación entre la concentración de p,p’-DDE yla edad tal como se esperaba para un contaminante persistente y bioacumulable. El trabajo aporta información sobre los niveles de plaguicidas organoclorados en sangre en una población con exposición ambiental estudiada frente a denuncias periodísticas y de los mismos habitantes del lugar.

Organochlorine pesticides were analyzed in 167 samples of whole blood colleted from people from two different sites in the province of Córdoba (Site Nº 1 and Site Nº 2). These sites were close to unused pesticides store. The presence of pesticides was determined by gas-chromatography with electron-capture detection using capillary columns. p,p’-DDE, β-HCH and HCB were the most frequently pesticide detected. The highest concentration found was 7,31 μg/l of p,p’-DDE. β-HCH showed highest values than its two isomers. As expected, significant relationship was found between the level of p,p’-DDE andthe age, since the former is a persistent and bioacumulative compound. This paper shows the organochlorine pesticides levels in a population with environmental exposure.