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ACS Environmental Au Nov 2022Cell-based assays covering environmentally relevant modes of action are widely used for water quality monitoring. However, no high-throughput assays are available for...
Cell-based assays covering environmentally relevant modes of action are widely used for water quality monitoring. However, no high-throughput assays are available for testing developmental neurotoxicity of water samples. We implemented an assay that quantifies neurite outgrowth, which is one of the neurodevelopmental key events, and cell viability in human neuroblastoma SH-SY5Y cells using imaging techniques. We used this assay for testing of extracts of surface water collected in agricultural areas during rain events and effluents from wastewater treatment plants (WWTPs), where more than 200 chemicals had been quantified. Forty-one chemicals were tested individually that were suspected to contribute to the mixture effects among the detected chemicals in environmental samples. Sample sensitivity distributions indicated higher neurotoxicity for surface water samples than for effluents, and the endpoint of neurite outgrowth inhibition was six times more sensitive than cytotoxicity in the surface water samples and only three times more sensitive in the effluent samples. Eight environmental pollutants showed high specificity, and those ranged from pharmaceuticals (mebendazole and verapamil) to pesticides (methiocarb and clomazone), biocides (1,2-benzisothiazolin-3-one), and industrial chemicals (-methyl-2-pyrrolidone, 7-diethylamino-4-methylcoumarin, and 2-(4-morpholinyl)benzothiazole). Although neurotoxic effects were newly detected for some of our test chemicals, less than 1% of the measured effects were explained by the detected and toxicologically characterized chemicals. The neurotoxicity assay was benchmarked against other bioassays: activations of the aryl hydrocarbon receptor and the peroxisome proliferator-activated receptor were similar in sensitivity, highly sensitive and did not differ much between the two water types, with surface water having slightly higher effects than the WWTP effluent. Oxidative stress response mirrored neurotoxicity quite well but was caused by different chemicals in the two water types. Overall, the new cell-based neurotoxicity assay is a valuable complement to the existing battery of effect-based monitoring tools.
PubMed: 37101724
DOI: 10.1021/acsenvironau.2c00026 -
Scientific Reports Jul 2021Carbon xerogels (CXs) were synthesized by polycondensation of resorcinol and formaldehyde, followed by thermal annealing, and subjected to hydrothermal oxidation....
Carbon xerogels (CXs) were synthesized by polycondensation of resorcinol and formaldehyde, followed by thermal annealing, and subjected to hydrothermal oxidation. Solid-phase extraction (SPE) cartridges were filled with CXs and tested for extraction of metaflumizone and other seven environmental micropollutants (acetamiprid, atrazine, isoproturon, methiocarb, carbamazepine, diclofenac, and perfluorooctanesulfonic acid) before chromatographic analysis. The recoveries obtained with the pristine CX were low for most analytes, except for metaflumizone (69 ± 5%). Moreover, it was concluded that the adsorption/desorption process of the micropollutants performed better on CXs with a less acidic surface (i.e., pristine CX). Thus, cartridges were prepared with pristine CX and multi-walled carbon nanotubes (MWCNTs) in a multi-layer configuration. This reusable cartridge was able to simultaneously extract the eight micropollutants and was used to validate an analytical methodology based on SPE followed by ultra-high performance liquid chromatography-tandem mass spectrometry. A widespread occurrence of 6/8 target compounds was observed in surface water collected in rivers supplying three drinking water treatment plants and in the resulting drinking water at the endpoint of each distribution system. Therefore, the first study employing CXs and MWCNTs as sorbent in multi-layer SPE cartridges is herein reported as a proof of concept for determination of multi-class water micropollutants.
PubMed: 34226575
DOI: 10.1038/s41598-021-93163-2 -
The Science of the Total Environment Oct 2020The electrooxidation of methiocarb and bisphenol A was studied in complex matrices, namely, simulated and real sanitary landfill leachate samples, using a boron-doped...
The electrooxidation of methiocarb and bisphenol A was studied in complex matrices, namely, simulated and real sanitary landfill leachate samples, using a boron-doped diamond anode. With simulated sanitary landfill leachate samples, the influence of the type and ratio of carbon source (glucose/humic acid) and electrolyte (NaCl or NaSO) on the emerging contaminants removal was assessed. Using real sanitary landfill leachate, the influence of current density was evaluated. The experimental results showed that electrooxidation, using a boron-doped diamond anode, can be successfully utilized to degrade methiocarb and bisphenol A when present in complex matrices, such as sanitary landfill leachate, and that methiocarb is more easily oxidized than bisphenol A. Furthermore, it was found that the presence of chloride and high humic acid content increases emerging contaminants removal rate, showing that electrooxidation at boron-doped diamond is particularly adequate to solve the problems raised by sanitary landfill leachate, even when contaminated with emerging contaminants.
PubMed: 32563882
DOI: 10.1016/j.scitotenv.2020.140153 -
Talanta Jul 2019This paper describes the synthesis of a silica based MSU-1 mesoporous solid and its application as sorbent in solid-phase extraction to pre-concentrate thirteen...
This paper describes the synthesis of a silica based MSU-1 mesoporous solid and its application as sorbent in solid-phase extraction to pre-concentrate thirteen pesticides of low-high polarity (methomyl, cymoxanil, carbofuran, monolinuron, isoproturon, methidathion, methiocarb, malathion, phosalone, diazinon, penconazole, neburon and chlorotoluron) in ground and river water. The synthesis was based in an H-bonding interaction assembling (IN) between two non-ionic components (the inorganic silica surface, I and the polyethylene oxide template, N) by adding tetraethoxysilane to the non-ionic surfactant Brij®100, the latter previously dissolved in HCl 1 M. 50 mL water samples adjusted at pH= 3.5 were passed, at a flow rate of 5 mL/min, through a home-made cartridge containing 50 mg of MSU-1 sorbent, pre-conditioned with 5 mL of ultrapure water; then, the cartridge was washed with 5 mL of ultrapure water. Following elution with 5 mL of acetonitrile, the pesticides were determined by ultra performance liquid chromatography coupled to triple quadrupole-mass spectrometry. Two selected reaction monitoring transitions were monitored per compound, the most intense one being used for quantification and the second one for confirmation. Three points were used for identification, as established in the Directive 96/23/EC for LC-MS/MS analysis, which deals with confirmatory methods for organic residues and contaminants listed in the Group B (veterinary drugs and contaminants). Medium matrix effect (|20%|
methiocarb and malathion, whereas diazinon and phosalone showed strong matrix effect (ME≥>|50%|). Therefore, the standard addition methodology was applied by adding an adequate amount of the pesticide standard mixture to the final sample extract. All pesticides were quantified using this approach for practical reasons, thus avoiding two different calibrations. The method quantification limit (MQL) of pesticides was 0.01 μg/L for all of them, except for diazinon (0.1 μg/L). Recoveries of the target pesticides at MQL and 0.25 µg/L concentration levels in blank river water were in the range 70.1-113.5% and 86.7-107.3%, respectively, with RSDs lower than 16.3% and 15.7%, respectively. Four ground water samples and three river water samples, taken from Almería (Spain), were analyzed by the proposed method and only phosalone at a concentration level of 0.05 µg/L was found in one river water sample. PubMed: 30952305
DOI: 10.1016/j.talanta.2019.02.092 -
Scientific Reports Dec 2020Pristine and functionalized multi-walled carbon nanotubes (MWCNTs) were investigated as adsorbent materials inside solid-phase extraction (SPE) cartridges for extraction...
Pristine and functionalized multi-walled carbon nanotubes (MWCNTs) were investigated as adsorbent materials inside solid-phase extraction (SPE) cartridges for extraction and preconcentration of 8 EU-relevant organic micropollutants (with different pKa and polarity) before chromatographic analysis of surface water. The recoveries obtained were > 60% for 5/8 target pollutants (acetamiprid, atrazine, carbamazepine, diclofenac, and isoproturon) using a low amount of this reusable adsorbent (50 mg) and an eco-friendly solvent (ethanol) for both conditioning and elution steps. The introduction of oxygenated surface groups in the carbon nanotubes by using a controlled HNO hydrothermal oxidation method, considerably improved the recoveries obtained for PFOS (perfluorooctanesulfonic acid) and methiocarb, which was ascribed to the hydrogen bond adsorption mechanism, but decreased those observed for the pesticide acetamiprid and for two pharmaceuticals (carbamazepine and diclofenac), suggesting π-π dispersive interactions. Moreover, a good correlation was found between the recovery obtained for methiocarb and the amount of oxygenated surface groups on functionalized MWCNTs, which was mainly attributed to the increase of phenols and carbonyl and quinone groups. Thus, the HNO hydrothermal oxidation method can be used to finely tune the surface chemistry (and texture) of MWCNTs according to the specific micropollutants to be extracted and quantified in real water samples.
PubMed: 33339850
DOI: 10.1038/s41598-020-79244-8 -
The Science of the Total Environment Nov 2020Water is an essential resource for all living organisms. The continuous and increasing use of pesticides in agricultural and urban activities results in the pollution of...
Improved fully automated method for the determination of medium to highly polar pesticides in surface and groundwater and application in two distinct agriculture-impacted areas.
Water is an essential resource for all living organisms. The continuous and increasing use of pesticides in agricultural and urban activities results in the pollution of water resources and represents an environmental risk. To control and reduce pesticide pollution, reliable multi-residue methods for the detection of these compounds in water are needed. In this context, the present work aimed at providing an analytical method for the simultaneous determination of trace levels of 51 target pesticides in water and applying it to the investigation of the target pesticides in two agriculture-impacted areas of interest. The method developed, based on an isotopic dilution approach and on-line solid-phase extraction-liquid chromatography-tandem mass spectrometry, is fast, simple, and to a large extent automated, and allows the analysis of most of the target compounds in compliance with European regulations. Application of the method to the analysis of selected water samples collected at the lowest stretches of the two largest river basins of Catalonia (NE Spain), Llobregat and Ter, revealed the presence of a wide suite of pesticides in the Llobregat basin, some of them at concentrations above the water quality standards (irgarol and dichlorvos) or the acceptable method detection limits (methiocarb, imidacloprid, and thiacloprid), and much cleaner waters in the Ter River basin. Risk assessment of the pesticide concentrations measured in the Llobregat River indicated high risk due to the presence of irgarol, dichlorvos, methiocarb, azinphos ethyl, imidacloprid, and diflufenican (hazard quotient (HQ) values>10), and moderate potential risk in the Ter River, associated to the occurrence of bentazone and irgarol (HQ > 1).
PubMed: 32736100
DOI: 10.1016/j.scitotenv.2020.140650 -
International Journal of Environmental... Sep 2016In order to assess the prevalence of pesticide contamination and the risk of florists' exposure when handling cut flowers, sampling and analysis of 90 bouquets of the...
In order to assess the prevalence of pesticide contamination and the risk of florists' exposure when handling cut flowers, sampling and analysis of 90 bouquets of the most commonly sold cut flowers in Belgium (50 bouquets of roses; 20 of gerberas, and 20 of chrysanthemums) were carried out. The bouquets were collected from 50 florists located in the seven largest cities of Belgium (Antwerp, Brussels, Charleroi, Ghent, Leuven, Liege, and Namur) and from five supermarkets located in the different regions. To have a better understanding of the route of exposure and professional practices a questionnaire was also addressed to a group of 25 florists who volunteered to take part in the survey. All florists were interviewed individually when collecting the questionnaire. The residual pesticide deposit values on cut flowers were determined in an accredited laboratory using a multi-residue (QuEChERS Quick Easy Cheap Effective Rugged Safe) method and a combination of gas chromatography (GC) and liquid chormatograhphy (LC) analysis. A total of 107 active substances were detected from all samples; i.e., an average of about 10 active substances per bouquet. The most severely contaminated bouquet accumulated a total concentration of residues up to 97 mg/kg. Results show that roses are the most contaminated cut flowers; with an average of 14 substances detected per sample and a total concentration per rose sample of 26 mg/kg. Some active substances present an acute toxicity (acephate, methiocarb, monocrotophos, methomyl, deltamethrin, etc.) and exposure can generate a direct effect on the nervous system of florists. Nevertheless, fungicides (dodemorph, propamocarb, and procymidone) were the most frequently detected in samples and had the highest maximum concentrations out of all the active substances analysed. Dodemorph was the most frequently detected substance with the highest maximum concentration (41.9 mg/kg) measured in the rose samples. It appears from the survey that, despite being exposed to high deposits of residues, florists usually do not protect themselves from contact with residues even if they spend several hours handling cut flowers and preparing bouquets (from 2 to 6 h/day, depending on the time of year and/or selling periods) daily. Bad habits (eating, drinking, or smoking at work) and absence of personal protective equipment of most florists also increase the risk of contact with pesticide residues.
Topics: Adult; Belgium; Chromatography, Gas; Commerce; Female; Flowers; Humans; Male; Occupational Exposure; Pesticide Residues; Surveys and Questionnaires; Young Adult
PubMed: 27669276
DOI: 10.3390/ijerph13100943 -
International Journal of Environmental... May 2017Flowers are frequently treated with pesticides and, as a result, florists handling daily a large number of flowers can be exposed to pesticide residues. A study was...
Flowers are frequently treated with pesticides and, as a result, florists handling daily a large number of flowers can be exposed to pesticide residues. A study was conducted among twenty volunteer florists located in Namur Province and in the Brussels Capital Region of Belgium in order to assess their potential dermal exposure to dislodgeable pesticide residues transferred from flowers to hands. Two pairs of cotton gloves were worn during two consecutive half days while handling flowers and preparing bouquets (from min 2 h to max 3 h/day). The residual pesticide deposits on the glove samples were extracted with a multi-residue Quick Easy Cheap Effective Rugged Safe (QuEChERS) method and analyzed by a combination of gas and liquid chromatography tandem mass spectrometry (GC-MS/MS and LC-MS/MS) by an accredited laboratory. A total of 111 active substances (mainly insecticides and fungicides) were detected, with an average of 37 active substances per sample and a total concentration per glove sample of 22.22 mg/kg. Several predictive levels of contamination were considered to assess the risk. The potential dermal exposures (PDE) of florists were estimated at the average, for different percentiles, and at the maximum concentration of residues in samples. At the PDE P90 and at the PDE (or worst case) values, three and five active substances respectively exceed the Acceptable Operator Exposure Level (AOEL), indicating risk situations. For the systemic exposure (SE), one active substance (clofentezine) exceeds the AOEL at the P90 predictive level. In the worst case, SE (at the maximum concentrations), four active substances (clofentezine, famoxadone, methiocarb, and pyridaben) exceed their respective AOEL values. Among the 14 most frequently detected active substances, two have SE values exceeding the AOEL. Exposure could be particularly critical for clofentezine with an SE value four times higher than the AOEL (393%). The exposure of florists appeared to be an example of a unique professional situation in which workers are exposed regularly to both a very high number of toxic chemicals and rather high concentration levels. Therefore the priority should be to raise the level of awareness among the florists who must change their habits and practices if they want to minimize their exposure.
Topics: Adult; Belgium; Chromatography, Liquid; Environmental Monitoring; Flowers; Gas Chromatography-Mass Spectrometry; Humans; Occupational Exposure; Pesticide Residues; Risk Assessment; Tandem Mass Spectrometry
PubMed: 28505067
DOI: 10.3390/ijerph14050526 -
Analytical and Bioanalytical Chemistry Sep 2015Distribution of pesticides both on the surface of leaves and in cross sections of plant stem and leaves was investigated using desorption electrospray ionization mass...
Distribution of pesticides both on the surface of leaves and in cross sections of plant stem and leaves was investigated using desorption electrospray ionization mass spectrometry imaging (DESI-MSI) with a spatial resolution of 50-100 μm. Two commercially available insecticide sprays containing different contact pesticides were applied onto leaves of Cotoneaster horizontalis, and the distributions of all active ingredients were directly analyzed. The first spray contained pyrethrins and rapeseed oil, both known as natural insecticides. Each component showed an inhomogeneous spreading throughout the leaf, based on substance polarity and solubility. The second spray contained the synthetic insecticides imidacloprid and methiocarb. Imidacloprid accumulated on the border of the leaf, while methiocarb was distributed more homogenously. In order to investigate the incorporation of a systemically acting pesticide into Kalanchoe blossfeldiana, a commercially available insecticide tablet containing dimethoate was spiked to the soil of the plant. Cross sections of the stem and leaf were obtained 25 and 60 days after application. Dimethoate was mainly detected in the transport system of the plant after 25 days, while it was found to be homogenously distributed in a leaf section after 60 days.
Topics: Mass Spectrometry; Pesticides; Plant Leaves
PubMed: 26229027
DOI: 10.1007/s00216-015-8900-2 -
The Science of the Total Environment Mar 2024The presence of pesticides in aquatic ecosystems poses significant risks to non-target organisms, necessitating monitoring and environmental risk assessment. This study...
The presence of pesticides in aquatic ecosystems poses significant risks to non-target organisms, necessitating monitoring and environmental risk assessment. This study aimed to evaluate the dynamics and environmental risk of pesticides in a hydro-agricultural area with intensive agricultural practices, in the Mediterranean region (South of Portugal). Seasonality and location influenced pesticide numbers and concentrations, with the highest levels observed during the dry season. Triazines, phenylureas, and organophosphates were the predominant pesticide classes, with terbuthylazine, bentazone, terbutryn, diazinon, and metolachlor exhibiting the highest detection frequencies (68 % to 72 %). Notably, 44 % of the quantified pesticides are no longer authorized in Portugal, with 33 % posing a high environmental risk. Some insecticides, including imidacloprid, methiocarb, and malathion, were occasionally detected at concentrations that posed high risks to the aquatic ecosystem (RQ ≥ 1). Irgarol, an algicide used in irrigation canals, presented a high risk in 91 % of the analysed samples. The study's distribution profile of pesticides revealed a significant transportation of these compounds from reservoirs to irrigation hydrants, establishing them as a secondary source of crop and environmental contamination. Additionally, the assessment of spatial distribution and environmental risk allowed for the identification of specific pollutants in different locations, prioritizing them based on their ecotoxicological risk to aquatic ecosystems. These findings reinforce the importance of implementing management measures at the level of hydro-agricultural areas, helping to stop the cycle of pesticide contamination. Only this type of strategy will make it possible to protect water quality, biodiversity and the health of citizens, contributing to the European Union's objectives of improving the condition of freshwater bodies and promoting the sustainable use of pesticides.
Topics: Pesticides; Ecosystem; Environmental Monitoring; Water Pollutants, Chemical; Agriculture; Water Supply
PubMed: 38278229
DOI: 10.1016/j.scitotenv.2024.170304