Assessment of the occurrence and interaction between pesticides and plastic litter from vineyard plots.

In this research, aged plastic fragments collected from vineyards were characterized in terms of composition, residues of pesticides, and their potential to exchange these compounds with the aquatic media. To this end, we employed the qualitative and quantitative information provided by complementary analytical techniques, including chromatography, organic and inorganic mass spectrometry, infrared spectroscopy and electronic microscopy. Debris of weathered plastics were identified as polypropylene and polyethylene, containing different types of additives, from organic UV stabilizers to inorganic fillers, such as calcium salts. Regardless of polymer type, plastic litter collected from vineyards contained residues of pesticides, and particularly of fungicides, with total concentrations in the range of values from 114 ng g-1 to 76.4 µg g-1. Data obtained under different extraction conditions suggested that a fraction of these compounds was absorbed in aged polymers, penetrating inside the material. The parallel analysis of plastic litter and vineyard soils reflected higher pesticide residues in the former matrix. Furthermore, several fungicides, considered as labile in vineyard soils (i.e. zoxamide and folpet), were those showing the highest levels in plastic litter. Simulated sorption-desorption studies, with plastic debris in contact with surface water, demonstrated the higher affinity of aged materials by moderately polar pesticides than their new counterparts. For the first time, the manuscript highlights the presence of plastic litter in vineyards soils, reflecting the accumulation of several fungicides in this matrix, in some cases, with a different stability pattern to that observed in the soil from same vineyards.

Occurrence and risk assessment of pesticides and pharmaceuticals in viticulture impacted watersheds from Northwest Spain.

An automated analytical methodology was developed, validated and applied to monitor 73 organic pollutants (pesticides and pharmaceuticals) in surface and groundwater samples obtained in watersheds from an intensive viticulture, rural region, in the Northwest of Spain. Filtered samples were concentrated using a reusable solid-phase extraction sorbent, on-line combined with liquid chromatography tandem mass spectrometry (LC-MS/MS). The analytical procedure achieved limits of quantification between 1 ng L-1 and 10 ng L-1, with a throughput of 2 samples hour-1, providing accurate recoveries for more than 90% of the 73 selected compounds, using calibration solutions prepared in ultrapure water (in presence of methanol and formic acid) as neat solvent. The distribution and the concentrations of pesticides in small streams impacted by discharges of treated municipal wastewaters were different in rural and residential areas. On the other hand, pharmaceuticals showed a similar distribution in both streams. In surface waters from viticulture impacted watersheds, with a limited influence of municipal wastewaters, pulses of pesticides were noticed, with values above 100 ng L-1 for several fungicides. Cardiovascular pharmaceuticals, psychiatric drugs and/or their transformation products were also ubiquitous in these samples, with low, but relatively stable concentrations among sampling campaigns. Within the suite of investigated compounds, maximum pesticide residues remained below their predicted-non effect concentration (PNEC) in all samples. On the other hand, the environmental concentrations of the cardiovascular drug olmesartan stayed systematically above its PNEC in fresh water samples.

Basic micro-pollutants in sludge from municipal wastewater treatment plants in the Northwest Spain: Occurrence and risk assessment of sludge disposal.

Sludge is one of the most problematic residues generated during wastewater treatment. Herein, we validate a single-step, sensitive procedure for the determination of a selection of 46 basic micro-pollutants, either used as pharmaceuticals or pesticides, in sludge from municipal sewage treatment plants (STPs), using liquid chromatography tandem mass spectrometry as determination technique. The proposed method permitted to achieve accurate recoveries (values from 70% to 120%, for samples spiked at different concentration levels) using solvent-based calibration standards. This feature, combined with limits of quantification lower than 5 ng g-1 (dry weight), allowed the rapid and sensitive quantification of target compounds in freeze-dried sludge samples. Out of 46 investigated pollutants, 33 species showed detection frequencies above 85% in a group of 48 sludge samples, obtained from 45 STPs located in the Northwest of Spain. The assessment of eco-toxicological risks associated to sludge disposal as fertilizer in agriculture and/or forestry, considering average concentrations found in sludge samples, highlighted eight pollutants (sertraline, venlafaxine, N-desethyl amiodarone, amiodarone, norsertraline, trazodone, amitriptyline and ketoconazole) representing an environmental hazard based on ratios between predicted soil levels and non-effect concentrations estimated using the equilibrium partition method.

Direct, automated and sensitive determination of glyphosate and related anionic pesticides in environmental water samples using solid-phase extraction on-line combined with liquid chromatography tandem mass spectrometry.

An automated procedure for the simultaneous determination of six anionic pesticides, including glyphosate (GLY) and its transformation product aminomethylphosphonic acid (AMPA), was developed and applied to the analysis of environmental water samples. The proposed method combines on-line concentration of water samples (0.160 mL), with compounds separation in an anion-exchange liquid chromatography (LC) column, followed by their selective determination by tandem mass spectrometry (MS/MS). The global procedure was completed in 25 min, providing limits of quantification (LOQs) between 5 ng L-1 and 20 ng L-1, with reduced effect of the surface water matrix in the efficiency of process (SPE and ionization yields). The method was applied to the analysis of grab samples obtained from three watersheds, in two rural and one residential area, in Galicia (Northwest Spain). Out of six investigated compounds, Fosetyl, AMPA and GLY were noticed in the set of processed samples. Their detection frequencies increased from 12% (Fosetyl) to 88% (AMPA). Median concentrations followed the same trend varying from 9 ng L-1 (Fosetyl) to 44 ng L-1 (AMPA). The higher levels and the large seasonal variations in the residues of the latter species were noticed in small rivers affected by discharges of municipal sewage treatment plants (STPs).

Solid-phase extraction and fractionation of multiclass pollutants from wastewater followed by liquid chromatography tandem-mass spectrometry analysis.

Herein, we describe a modular solid-phase extraction (SPE) setup, combining three sorbents, for the effective extraction of neutrals, acidic, and basic micropollutants from wastewater, followed by their further elution in three independent extracts. The performance of this approach was demonstrated for a suite of 64 compounds, corresponding to different chemical families, using liquid chromatography tandem-mass spectrometry (LC-MS/MS). Target compounds were effectively extracted from wastewater samples; moreover, 62 out of 64 species were isolated in just one of the three fractions (neutrals, acids, and bases) obtained from the combination of sorbents. Globally, the efficiency and the selectivity of the SPE methodology improved the features obtained using generic SPE polymers, displaying just reversed-phase interactions. The overall recoveries of the analytical method, calculated against solvent-based calibration standards, stayed between 80 and 120% for 57 and 60 compounds, in raw and treated wastewater, respectively. Procedural limits of quantification (LOQs) varied from 1 to 20 ng L-1. Analysis of urban wastewater samples identified a group of 19 pollutants showing either negligible median removal efficiencies (± 20%) during wastewater treatment, or even a noticeable enhancement (case of the biodegradation product of the drug valsartan), which might be useful as markers of wastewater discharges in the aquatic environment.

Resultados preliminares del impacto de la COVID-19 en niños/as y adolescentes expuestos a maltrato intrafamiliar / Preliminary results of the impact of COVID-19 on children and adolescents exposed to intrafamily abuse

Resumen: Los datos preliminares confirman el impacto psicológico que la crisis por COVID-19 está provocando en niños y adolescentes de población comunitaria. Se desconoce cómo afecta a la población infantil que sufre maltrato intrafamiliar. El objetivo del estudio fue examinar el impacto emocional adicional que supone la medida de confinamiento en menores de edad expuestos a violencia de pareja hacia la mujer que recibían atención psicológica en la Región de Murcia. Ciento ochenta y cinco madres informaron vía telefónica cómo el confinamiento afectó a 269 niños/as de entre 0 y 18 años. También los 108 menores que tenían 6 años o más, cumplimentaron el listado sobre su propio estado emocional. El incremento en la incidencia de alteraciones psicológicas en esta población ha sido baja (1.1-4.8%), si bien entre aquellos que aumentó la sintomatología predominaron la desorganización comportamental y la alteración emocional. Asimismo, se comprobó que algunas variables (sexo, edad, días de confinamiento, conflicto familiar) contribuyeron al incremento de desorganización comportamental y estrés traumático/depresión. Es preciso desarrollar más trabajos en esta línea por las implicaciones que se pueden derivar tanto a nivel de diagnóstico como de tratamiento.

Abstract: Preliminary data confirm the psychological impact that the COVID-19 crisis is causing in children and adolescents in the community population. It is unknown how it affects the child population who suffer intrafamilial abuse. The objective of the study was to examine the additional emotional impact of the measure of confinement in minors exposed to intimate partner violence towards women who received psychological attention in the Region of Murcia. One hundred and eighty-five mothers reported, by telephone comunication, how the confinement affected to 269 children between the ages of 0 and 18. Also the 108 minors who were 6 years old or older completed the list on their own emotional state. The incidence increasement of psychological disorders within this population has been low (1.1-4.8%), although among those with increased symptoms, behavioral disorganization and emotional disturbance was predominant. Likewise, it was found that some variables (sex, age, days of confinement, family conflict) contributed to increase the behavioral disorganization and traumatic stress/depression. It is necessary to develop more research in this line due to the derived implications both at diagnosis and treatment levels.

Disseminated cutaneous histoplasmosis in acquired immunodeficiency syndrome: report of 23 cases.

Disseminated cutaneous histoplasmosis is an opportunistic infection in patients with acquired immunodeficiency syndrome. We report a series of 23 cases (21 men, two women; median age 29 years) with disseminated cutaneous histoplasmosis seen at two hospital centres. Most of the patients (21/23) were classified as stage C3. The most common dermatological findings were papules, crusting plaques, nodules and ulcers, mainly located on the face and chest. Of the 23 cases, 15 (65%) had pulmonary involvement. Amphotericin B and itraconazole were the main drugs used for treatment. Treatment response was variable: four of the patients were cured, six improved and remain stable, nine patients died, and four patients were lost to follow-up.