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

Effects of water quality on aspects of reproductive biology of Cnesterodon decemmaculatus

The Suquía River basin (Córdoba, Argentina) is under a strong negative impact due to multiple sources of anthropic pollution. The main goal of our study was to evaluate if variations in the water quality of Suquía river basin affect the reproductive biology of Cnesterodon decemmaculatus and determine if the responses provided by the species can be considered as biomarkers of river quality. This assessment was performed through the measurement of morphological, histological and somatic parameters in adult males collected at four sampling sites during the beginning and the end of the breeding season. The water quality evaluation carried out through the estimation of a water quality index (WQI) and pesticides concentrations in water, revealed a pollution gradient along the studied basin. The same variation pattern was registered for the somatic index. In addition, the analysis of the morphology of the male copulatory organ (gonopodium) showed that individuals collected at Córdoba city had the lowest Gonopodium-Somatic Index (Gonop-SI) value, while those sampled at the most polluted site showed abnormalities in the small structures of the gonopodium. On the other hand, few histological alterations were found in the liver whereas no alterations were found in gonads along the river. The results obtained allowed us to characterize the environmental conditions of the studied basin and demonstrated the water quality deterioration along the Suquía River.Fil: Zambrano Schmidt Deussen, Micaela Jimena. 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; ArgentinaFil: Rautenberg, Gisela Evelín. 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; ArgentinaFil: Bonifacio, Alejo Fabian. 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; ArgentinaFil: Filippi, Iohanna. 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: Bonansea, Rocio Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Ciencias de la Salud. Universidad Nacional de Córdoba. Instituto de Investigaciones en Ciencias de la Salud; ArgentinaFil: Hued, Andrea Cecilia. 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; Argentin

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 Cordoba (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, β-HCH, α-endosulfan, pp'DDE, endrin, β-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.Fil: Filippi, Iohanna. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Ciencias de la Salud. Universidad Nacional de Córdoba. Instituto de Investigaciones en Ciencias de la Salud; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; ArgentinaFil: Lucero, Patricia. Centro de Excelencia En Productos y Procesos de Cordoba; ArgentinaFil: Bonansea, Rocio Ines. 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: Lerda, Daniel. Universidad Católica de Córdoba; ArgentinaFil: Butinof, Mariana. Universidad Nacional de Córdoba. Facultad de Medicina; ArgentinaFil: Fernandez, Ricardo. Universidad Católica de Córdoba; 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; ArgentinaFil: Amé, María Valeria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; ArgentinaFil: Muñoz, Sonia Edith. Universidad Nacional de Córdoba. Facultad de Medicina; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Ciencias de la Salud. Universidad Nacional de Córdoba. Instituto de Investigaciones en Ciencias de la Salud; Argentin

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

Valoración de la exposición a plaguicidas en cultivos extensivos de Argentina y su potencial impacto sobre la salud

Los plaguicidas configuran un aspecto central de las prácticas agrícolas. El área pampeana agrupa un IEP mayor al promedio nacional y los IIAT superiores, correspondientes al 2,4-D y clorpirifos. El aumento en ambos índices de exposición se asoció a incrementos en las tasas de mortalidad por cáncer a nivel departamental. El daño genotóxico en aplicadores no se asoció a los niveles de exposición; sí la disminución de la actividad de butirilcolinesterasa. Los instrumentos "índices" y resultados alcanzados brindan valiosos elementos para vigilar la exposición a plaguicidas en Argentina.http://ref.scielo.org/tfp3m2publishedVersionFil: Butinof, Mariana. Universidad Nacional de Córdoba; Argentina.Fil: Fernández, Ricardo. Universidad Católica de Córdoba; Argentina.Fil: Muñoz, Sonia. Consejo Nacional de Investigaciones Científicas y Técnicas Instituto Nacional de Investigaciones en Ciencias de la Salud; Argentina.Fil: Lerda, Daniel. Universidad Católica de Córdoba; Argentina.Fil: Blanco, Marcelo. Universidad Nacional de Córdoba; Argentina.Fil: Lantieri, María Josefina. Consejo Nacional de Investigaciones Científicas y Técnicas Instituto Nacional de Investigaciones en Ciencias de la Salud; Argentina.Fil: Antolini, Luciana. Universidad Nacional de Córdoba; Argentina.Fil: Gieco, Marbela. Consejo Nacional de Investigaciones Científicas y Técnicas Instituto Nacional de Investigaciones en Ciencias de la Salud; Argentina.Fil: Ortiz, Pablo. Universidad Nacional de córdoba; Argentina.Fil: Filippi, Iohanna. Universidad Nacional de Córdoba; Argentina.Fil: Franchini, Germán. Consejo Nacional de Investigaciones Científicas y Técnicas Instituto Nacional de Investigaciones en Ciencias de la Salud; Argentina.Fil: Eandi, Mariana. Universidad Nacional de Córdoba; Argentina.Fil: Montedoro, Franco. Universidad Nacional de Córdoba; Argentina.Fil: María del Pilar Díaz. Consejo Nacional de Investigaciones Científicas y Técnicas Instituto Nacional de Investigaciones en Ciencias de la Salud; Argentina.Salud Pública y Medioambienta

Evaluación de biomarcadores de efecto y exposición a plaguicidas en trabajadores de cultivos extensivos de la provincia de Córdoba para la validación de escalas de exposición

Tesis - Doctorado en Ciencias de la Salud - Universidad nacional de Córdoba. Facultad de Ciencias Médicas. Secretaria de Graduados en Ciencias de la Salud, 2022Antecedentes: el riesgo cardiometabólico implica una compleja desregulación de procesos inflamatorios y oxidativos con la modulación del sistema nervioso autonómico. La actividad física (AF) podría estar relacionada con un menor estatus inflamatorio y oxidativo mientras que el tiempo sedentario (SEDT) podría tener un efecto desfavorable, incrementando la inflamación, el estrés oxidativo y alterando la regulación autonómica aumentando el riesgo de enfermedad cardiometabólica. A la vez, potenciales factores, tal como la aptitud cardiorrespiratoria (CRF), la edad y la composición corporal podrían afectar la asociación entre AF, SEDT y los marcadores de inflamación y estrés oxidativo. Objetivos: el objetivo general del presente estudio fue analizar relaciones entre patrones de actividad física, el nivel de aptitud aeróbica y biomarcadores de estrés oxidativo e inflamación en individuos con riesgo de enfermedades crónicas no transmisibles. Como objetivos específicos se incluyeron: determinar las asociaciones entre AF, SEDT, CRF y los niveles de marcadores inflamatorios y de estrés oxidativo; analizar la asociación entre la AF, SEDT, CRF y los índices de control autonómico [variabilidad de la frecuencia cardíaca (VFC) y recuperación de la frecuencia cardíaca post ejercicio (RFC)]; establecer las asociaciones entre los índices de VFC y RFC y los marcadores de inflamación y estrés oxidativo; y establecer si existen diferencias en la asociación entre AF, SEDT y marcadores inflamatorios utilizando métodos de medición objetivos y subjetivos de AF y SEDT. Métodos: la muestra total constó de 111 voluntarios (70 mujeres y 41 hombres, edad = 52,8 8,2 años; IMC = 29,1 6,4 kg•m-2) de entre 39-70 años pertenecientes al Estudio sobre Estilos de Vida y Marcadores de Estrés Oxidativo en Individuos con Riesgo Cardiometabólico desarrollado en el Hospital Nacional de Clínicas. Una submuestra de 44 individuos (29 mujeres y 15 hombres, edad = 49,5 6,4 años; IMC = 28,1 6,2 kg•m-2) participaron del estudio sobre evaluación objetiva de la AF y su relación con marcadores de inflamación, estrés oxidativo y control autonómico. Los datos fueron recolectados entre las 7.00 y las 10.30 A.M. en ayunas y en el siguiente orden: frecuencia cardíaca de reposo para el análisis de la VFC; muestra de sangre para la medición de marcadores bioquímico-clínicos [glucosa, triglicéridos totales, colesterol total, HDL-C, LDL-C y hemoglobina glicosilada (HbA1C) y fibrinógeno], inflamatorios [proteína C reactiva (PCR) y citoquinas (IL-1β, INF-γ, TNF, MCP-1, IL-6, IL-8, IL-10, IL-18, IL-23)] y de estrés oxidativo [actividad de la catalasa (CAT) y de la glutatión peroxidasa (GPX)]. Medidas de la presión sanguínea [sistólica (PAS) y diastólica (PAD)], antropométricas [talla, masa corporal y circunferencia de la cintura (CC)]. Además, se realizó una prueba submáxima en cicloergómetro para estimar el consumo máximo de oxígeno (VO2max) como medida de la CRF y con recuperación activa para valorar la RFC absoluta (FC a los 30 s, 1 min, 2 min, 3 min, 4 min y 5 min post ejercicio) y la RFC relativa (Δ30, Δ1, Δ2, Δ3, Δ4, Δ5) así como la cinética de la RFC [constante temporal (τ) y amplitud (FCamp)]. Posteriormente, los participantes completaron un cuestionario sobre sus hábitos de AF [Cuestionario Internacional de AF (IPAQ), versión corta] y siete días de monitoreo objetivo de AF mediante acelerometría [tiempo sedentario (SEDT), tiempo de AF ligera (AFL), tiempo de AF moderada (AFM), tiempo de AF vigorosa (AFV) y la suma de AF moderada a vigorosa (AFMV)]. Los análisis de VFC, RFC, la prueba de ejercicio y el monitoreo objetivo de la AF solo fue realizado en una submuestra de 44 participantes. Para los análisis se establecieron conglomerados de edad (adultos jóvenes, adultos de mediana edad y adultos mayores), de CRF (baja, moderada y alta) y un conglomerado compuesto de riesgo cardiometabólico (bajo riesgo y alto riesgo). Resultados: en la muestra total los diferentes modelos univariados (ajustados por las covariables de confusión) mostraron que el SEDT no se asoció significativamente con ninguno de los marcadores inflamatorios y lo mismo ocurrió con la AFMV. Sin embargo, se observaron asociaciones significativas entre la AFL e IL-1β (B = -0,004; P = 0,021) y entre la AFV y TNF-α (B = -0,017; P = 0,017) e IL-6 (B = -0,018; P = 0,04). Asimismo, se halló un efecto de interacción entre la AF y el SEDT con diferentes covariables, particularmente el sexo, la edad y la CC. El análisis de la AF y SEDT mediante el IPAQ mostró diferencias significativas entre hombres y mujeres respecto de los minutos diarios de AFMV, AFV y AF total (P < 0,05). En contraposición, no hubo diferencias significativas respecto del SEDT entre ambos sexos. Cuando se compararon los niveles de AF por conglomerados de edad, se observó que los participantes pertenecientes al grupo de adultos jóvenes exhibieron mayores niveles de AFV en comparación con el grupo de adultos de mediana edad (P < 0,05), pero no con respecto al grupo de adultos mayores. En los conglomerados de riesgo cardiometabólico tanto la AFV como la AFMV exhibieron una asociación inversa con la PAS y PAD. Adicionalmente, se observó un efecto de interacción entre el SEDT y la edad sobre la concentración de HDL-C (B = -0,003; P = 0,016). El conglomerado con mayor riesgo cardiometabólico exhibió mayores niveles de PCR y Fibrinógeno (P < 0,01). Por otra parte, en la submuestra de 44 participantes se observó que, en comparación con los hombres, las mujeres exhibieron mayor SEDT (P = 0,035), con menores frecuencias en la interrupción del sedentarismo (P = 0,014) mientras que exhibieron mayores niveles de IL-6 (P = 0,02) y TNF-α (P = 0,01) con menores índices de VFC (P < 0,05). Se observaron asociaciones ajustadas significativas entre el SEDT y los niveles de CPR (B = 0,006; P = 0,001) y MCP-1 (B = 0,003; P = 0,038) y entre ciertos índices de la VFC y marcadores de inflamación/estrés oxidativo mientras que los índices de la RFC estuvieron inversamente asociados con Ln CAT [Δ3 (B = -54,7; P = 0,042), Δ4 (B = -54,1; P = 0,021] and Δ5 vs. Ln PCR [B = -19,8; P = 0,033]. El conglomerado de mayor CRF mostró menores valores de TNF-α (P = 0,02) e IL-10 (P = 0,003) y mejores índices de VFC (P < 0,05). El análisis de concordancia entre las medidas objetivas y subjetivas del SEDT resultó en un sesgo de 42 66 min con límites de acuerdo de -88 a 172 min en tanto que para las medidas de AF los resultados mostraron un sesgo de 2,2 148,0 min con límites de acuerdo de -288 a 293 min. Conclusiones: tomados conjuntamente, los resultados del presente estudio sugieren que prolongados tiempos de sedentarismo combinados con bajos niveles de AF de intensidad moderada a vigorosa pueden incrementar el ambiente inflamatorio y el estrés oxidativo. El aumento del estado proinflamatorio, a su vez, podría estar relacionado con una desmejora del control autonómico (i.e., equilibrio simpático-vagal) incrementando así el riesgo de enfermedad cardiovascular. Los resultados también muestran que la CRF es un potente modulador, no solo de la respuesta inflamatoria ante factores de riesgo cardiometabólicos sino también de la regulación autonómica de dicha respuesta. La baja concordancia observada entre las medidas de AF y SEDT obtenidas con el método subjetivo y el objetivo indican que las diferencias entre las asociaciones de la muestra completa y la submuestra se deban en parte al instrumento de evaluación utilizado.The increased use of pesticides has augmented the chances of contact between populations and these compounds, increasing consequently accident chances and expositions held over time. The aims of the present thesis were: a- To evaluate the exposure to pesticides in occupationally exposed subjects (OE; terrestrial applicators of pesticides) of the province of Córdoba, using two indexes of pesticide exposure, one indicative of the intensity level of the exposure (IIE) and another of the cumulative exposure level (IEA) and its scales, and validate their usefulness using health conditions, as well as effect and exposure biomarkers; and b- To estimate the exposure to pesticides through a dietary risk analysis in OE subjects and their controls (subjects not occupationally exposed to pesticides; NOE). Cross-sectional studies were designed to evaluate the exposure to pesticides and the health conditions of the participants, with the due approval of the Ethics Committee for Health Research. Enrolled subjects provided information on perceived symptomatology and biological samples for the determination of effect biomarkers (cholinesterase activity in plasma and erythrocytes, and markers of genotoxic damage (micronuclei (MN), sister chromatid exchange (ICH), chromosomal aberrations (AC) and comet assay (EC)), and exposure biomarkers (concentration of pesticides in plasma and urine). The perceived symptomatology and all the genotoxic damage biomarkers evaluated were significantly higher in the OE group. These resutls show that the occupational exposure to pesticides would negatively affect the health of workers. Cholinesterase activity was within the reference range for both groups of subjects, but with higher levels of activity within the OE group. In plasma, organochlorine pesticide residues of hexachlorobenzene (HCB), β- hexachlorohexane (β-HCH), α-endosulfan, dichlorodiphenyl dichloroethylene (pp ́DDE), endrin, β-endosulfan, dichloro diphenyl trichloroethane (pp ́DDT) endosulfan sulfate and mirex were found, without significant differences between groups, but with higher detection frequencies (FD) in the OE group. Within the OE group, the associations found between the IEA with neurological symptomatology and the IIE with the activity of plasmatic cholinesterases show the usefulness of the questionnaires used, to be propose as surveillance tools, and of the cholinesterase biomarkers to differentiate levels of exposure and to identify vulnerable groups. In urine, specific metabolites of the organophosphate (OP) pesticides pirimiphos, parathion and chlorpyrifos (2-diethylamino-6-methyl-4-pyrimidinol (DEAMPY), p- nitrophenol (PNP) and 3,5,6-trichloropyridinol (TCPY), respectively) were found, with a FD> 85%. With lower FD, malathion and diazinon metabolites (malathion dicarboxylic acid (MDA) and 2-isopropyl-4-methyl-6-hydroxypyrimidine (IMPY)) were found. Concentration levels of DEAMPY found in this population were at least two times higher than those reported in other countries. The PNP FD (100%) suggests that the population was recently exposed to the banned pesticide. Regarding pyrethroid metabolites (PYR), the common degradation metabolite of cypermethrin, deltamethrin and permethrin, 3-phenoxybenzoic acid (3-PBA) was found in 100% of the population. With a lower FD, the specific cyfluthrin metabolite, 4-fluoro-3-phenoxybenzoic acid (4-F-3-PBA) was found, with statistical higher concentration in the OE group. The dietary risk analysis showed that the daily intakes of OP and PYR pesticides are within food safe values. However, the negative correlations found between cholinesterase activity, and the metabolites DEAMPY, IMPY and PNP, indicate a possible risk to human health, even at environmental levels of exposure. This thesis is the first biomonitoring integrating the study of health conditions, levels of pesticides in biological matrices and levels of exposure in terrestrial pesticide applicators in the country. It is also the first report of concentrations of OC, OP and PYR pesticides and/or their metabolites in biological matrices of an occupationally exposed population in the country and of the control population in the study areas. On the other hand, and from the health point of view, the knowledge of the health effects, in relation to the magnitude of the use of these compounds and the regular practices in the territory, provides essential elements to improve the knowledge of the conditions of occupational and environmental exposure to pesticides, identify shortcomings that allow reinforcing good agricultural practices and generate preventive proposals. These elements become of political relevance for decision-making in health and effective and timely health intervention, for the care of vulnerable groups and the protection of the entire population.2024-03-16Fil: Filippi, Iohanna. Universidad Nacional de Córdoba. Facultad de Ciencias Médicas; Argentina

Determination of glyphosate and its derivative, aminomethylphosphonic acid, in human urine by gas chromatography coupled to tandem mass spectrometry and isotope pattern deconvolution

An analytical method for the simultaneous determination of glyphosate (GLY) and its main derivative, aminomethyl-phosphonic acid (AMPA), in human urine has been developed using gas chromatography coupled to tandem mass spectrometry (MS/MS) operated in multiple reaction monitoring mode (MRM). Sample preparation involved dilution of urine with water and derivatization with a mixture of trifluoroacetic acid anhydride and trifluoroethanol. Derivatization conditions such as reaction time and temperature, derivative stability, injection solvent, MS ionization mode and MS-MS transitions, among others, were studied to obtain the highest method sensitivity. The target compounds were initially quantified by the isotope dilution method using isotopically labelled analogs of GLY and AMPA as internal standards. However, due to spectral overlap between GLY and labelled GLY in the selected quantitative transition, a quantification method based on isotope pattern deconvolution (IPD) has been developed. The instrumental limits of detection were 0.05 ng mL−1 for both compounds, while the method detection limits were 0.39 and 0.25 ng mL−1, for AMPA and GLY, respectively. The mean recoveries from urine and water spiked at different concentrations were 77 and 69% for AMPA and 90 and 102% for GLY, respectively, with mean relative standard deviations of 8–10% (urine samples, n = 12) and 3.6–4% (water samples, n = 6). Once validated, the feasibility of the method was tested by determination of AMPA and GLY in human urine samples from people living close to agricultural areas. The developed method affords the determination of these compounds at trace concentrations in complex matrices such as urine, avoiding elaborate handling and cleanup steps. Isotope pattern deconvolution has proven to be a successful alternative to calibration curve for GLY overriding the method uncertainties associated to spectral overlapping.Fil: Junqué, Eva. Consejo Superior de Investigaciones Científicas; EspañaFil: Fernández, Pilar. Consejo Superior de Investigaciones Científicas; EspañaFil: Filippi, Iohanna. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; ArgentinaFil: Grimalt, Joan O.. Consejo Superior de Investigaciones Científicas; Españ

Determination of glyphosate and its derivative, aminomethylphosphonic acid, in human urine by gas chromatography coupled to tandem mass spectrometry and isotope pattern deconvolution

An analytical method for the simultaneous determination of glyphosate (GLY) and its main derivative, aminomethyl-phosphonic acid (AMPA), in human urine has been developed using gas chromatography coupled to tandem mass spectrometry (MS/MS) operated in multiple reaction monitoring mode (MRM). Sample preparation involved dilution of urine with water and derivatization with a mixture of trifluoroacetic acid anhydride and trifluoroethanol. Derivatization conditions such as reaction time and temperature, derivative stability, injection solvent, MS ionization mode and MS-MS transitions, among others, were studied to obtain the highest method sensitivity. The target compounds were initially quantified by the isotope dilution method using isotopically labelled analogs of GLY and AMPA as internal standards. However, due to spectral overlap between GLY and labelled GLY in the selected quantitative transition, a quantification method based on isotope pattern deconvolution (IPD) has been developed. The instrumental limits of detection were 0.05 ng mL−1 for both compounds, while the method detection limits were 0.39 and 0.25 ng mL−1, for AMPA and GLY, respectively. The mean recoveries from urine and water spiked at different concentrations were 77 and 69% for AMPA and 90 and 102% for GLY, respectively, with mean relative standard deviations of 8–10% (urine samples, n = 12) and 3.6–4% (water samples, n = 6). Once validated, the feasibility of the method was tested by determination of AMPA and GLY in human urine samples from people living close to agricultural areas. The developed method affords the determination of these compounds at trace concentrations in complex matrices such as urine, avoiding elaborate handling and cleanup steps. Isotope pattern deconvolution has proven to be a successful alternative to calibration curve for GLY overriding the method uncertainties associated to spectral overlapping

Assessment of atmospheric levels of carbonyls in an urban environment of Argentina

It is well-documented that carbonyl compounds have adverse effects on human health. On the other hand, these oxygenated volatile organic compounds (OVOCs) are precursors of secondary pollutants such as tropospheric ozone or peroxy acetyl nitrate (PAN). In particular, formaldehyde, the simplest carbonyl, is the most abundant carbonyl in the air generated from the degradation of most volatile organic compounds (VOCs). This work presents for the first time the characterization and determination of levels of carbonyl compounds by passive monitoring performed from April–December 2021 in the city of Córdoba, Argentina, the second most populated Mediterranean city located in the center of the country. Annual concentrations, considering the 11 carbonyls measured, were in the range of 0.13–8.75 μgm−3. Formaldehyde and acetaldehyde were the carbonyls detected in the highest annual average concentrations of 4.44 ± 1.75 μgm−3 and 3.85 ± 1.44 μgm−3, respectively. These carbonyls represent a contribution of around 40–57% on total carbonyls measured. Statistical analysis to determine significant differences and Pearson correlations with the meteorological parameters were performed. Spring and summer were found to be the seasons with the highest carbonyl concentration linked to forest fire episodes, especially in springtime. The values for the C1/C2 and C2/C3 ratios showed that sources of carbonyl formation are anthropogenic. In addition, the prop-Equiv concentration was determined, where formaldehyde and acetaldehyde were the main producers of tropospheric ozone. The ozone formation potential (OFP) showed that spring and summer are the seasons where carbonyls contribute to the formation of tropospheric ozone.This study represents a first approach of the carbonyl concentration in the city and of the influence of meteorological parameters on the behavior of carbonyls.Fil: Baptista Ruiz, Andrea Carolina. 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: Villanueva, Florentina. Universidad de Castilla-La Mancha; EspañaFil: Filippi, Iohanna. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; ArgentinaFil: Cabañas, Beatriz. Universidad de Castilla-La Mancha; EspañaFil: Teruel, Mariano Andres. 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; Argentin

Biomonitoreo en exposición a plaguicidas y su aporte en vigilancia epidemiológica en agroaplicadores en Córdoba, Argentina

Resumen: Objetivo: Evaluar el nivel de exposición a plaguicidas y su correlación con indicadores de salud percibida y biomarcadores de daño (alteraciones genotóxicas y de actividad enzimática de la butirilcolinesterasa), en la población de agroaplicadores de cultivos extensivos (ACE) de la Provincia de Córdoba, Argentina. Método: Estudio transversal, en ACE (n = 47) seleccionados aleatoriamente de una muestra de 2000, y sujetos no expuestos controles (n = 52). Se relevaron variables sociodemográficas, condicionantes de exposición y de salud percibida, mediante cuestionario autoadministrado; indicadores biológicos de genotoxicidad: micronúcleos, aberraciones cromosómicas y ensayo cometa, y actividad de butirilcolinesterasa. Resultados: El 40% de los ACE tiene una antigüedad mayor de 10 años y casi el 50% reside a menos de 500 m de campos asperjados; reportan bajas tasas de uso de equipo de protección personal durante la mezcla, aplicación o reparación de equipos. Los síntomas generales, cardiorrespiratorios y dermatológicos fueron mayores entre los ACE (p <0,05), así como los indicadores de daño genotóxico (p <0,001). La actividad butirilcolinesterasa se asoció negativamente a niveles de exposición a plaguicidas. Conclusiones: Los ACE presentan un importante impacto negativo en la salud vinculado a la exposición a plaguicidas. Las escalas de exposición asociadas al uso de biomarcadores resultaron una herramienta útil para la vigilancia de la salud de los agroaplicadores. Abstract: Objective: To assess the level of exposure to pesticides and its correlation with perceived health indicators and injury biomarkers (genotoxic alterations and those caused by butyrylcholinesterase enzyme activity) in the population of pesticide applicators in extensive crops (PAEC) in Córdoba, Argentina. Methods: Transversal study, in PAEC (n = 47) randomly selected from a sample of 2000, and non-exposed subject controls (n = 52). The sociodemographic variables, exposure conditioning, and perceived health were surveyed by means of a self-administered questionnaire; biological indicators of genotoxicity: micronuclei, chromosomal aberrations and kite assay, and butyrylcholinesterase activity. Results: 40% of PAEC have over 10 years’ length of service and almost 50% of them reside less than 500 m from the sprinkled fields; they report low rates of personal protective equipment use while mixing, applying, or repairing the equipment. General, cardio-respiratory, and dermatological symptoms were greater among PAEC (p <0.05) as well as indicators of genotoxic injury (p <0.001). The butyrylcholinesterase activity was negatively associated with levels of exposure to pesticides. Conclusions: The PAEC show an important negative impact on health linked to exposure to pesticides. The exposure scales associated to the use of biomarkers were a useful tool for monitoring pesticide applicators’ health. Palabras clave: Biomonitoreo, Vigilancia epidemiológica, Exposición a plaguicidas, Agroaplicadores, Argentina, Keywords: Biomonitoring, Pesticide exposure, Epidemiological surveillance, Pesticide applicators, Argentin