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Toxics Feb 2022The use of pesticides presents a risk to terrestrial and aquatic ecosystems. For this reason, the development of strategies to prevent and restore pollution is of the...
The use of pesticides presents a risk to terrestrial and aquatic ecosystems. For this reason, the development of strategies to prevent and restore pollution is of the greatest interest, including the adsorption to organic matter. The aim of the present study was to investigate the sorption/desorption and kinetics of atrazine, chlorfenvinphos, endosulfan sulfate, and trifluralin onto several raw organic wastes by batch experiments. Three kinetic models were used to fit the obtained sorption kinetics data and two to fit the obtained adsorption isotherm data; both the Freundlich and pseudo-second-order kinetic models described the sorption isotherms well. The desorption study revealed hysteresis in all cases, showing strong, and not completely reversible, adsorption in most cases, with the exception of atrazine-sawdust and chlorfenvinphos-sawdust and chicken manure combinations, for which responses were weak and irreversible. The best kinetic, adsorption and desorption constants were achieved for the hydrophobic pesticides. With respect to sorption-desorption rates, orujillo was found to be the best adsorbent for atrazine, while composted urban solid waste was more suitable for trifluralin and endosulfan sulfate. Sorption constants and simple correlations indicated that, not only the organic matter content, but also the nature of the organic matter itself, and the pesticide and adsorbent properties, determine pesticide sorption-desorption. The use of wastes as efficient and cheap adsorbents for reducing the risk of pesticide pollution is proposed.
PubMed: 35202271
DOI: 10.3390/toxics10020085 -
Chemosphere Oct 2017A method for the determination of chlorfenvinphos, ethion and linuron in liver samples by LC-MS/MS is described. Sample treatment was performed by using Sola™...
A method for the determination of chlorfenvinphos, ethion and linuron in liver samples by LC-MS/MS is described. Sample treatment was performed by using Sola™ polymeric reverse phase SPE cartridges after protein precipitation. Gradient elution using 10 mM ammonium formate in methanol (A) and 10 mM ammonium formate in water (B) was used for chromatographic separation of analytes on a Hypersil™ end-capped Gold PFP reverse phase column (100 mm × 2.1 mm, 3 μm). All analytes were quantified without interference, in positive ionization mode using multiple reaction monitoring (MRM) with chlorfenvinphos-d10 as internal standard. The whole procedure was validated according to the FDA guidelines for bioanalytical methods. The calibration curves for chlorfenvinphos, linuron and ethion compounds were linear over the concentration range of 0.005-2 μM (i.e. 0.0018-0.720 μg/mL, 0.0019-0.770 μg/mL and 0.0012-0.500 μg/mL respectively) with coefficients of determination higher than 0.998. A Lower limit of quantification of 0.005 μM was achieved for all analytes, i.e. 5.76, 6.08 and 3.84 μg/kg of liver for chlorfenvinphos, ethion and linuron respectively. Compounds extraction recovery rates ranged from 92.9 to 99.5% with a RSD of 2.3%. Intra- and inter-day accuracies were within 90.9 and 100%, and imprecision varied from 0.8 to 8.2%. Stability tests proved all analytes were stable in liver extracts during instrumental analysis (+12 °C in autosampler tray for 72 h) at the end of three successive freeze-thaw cycles and at -20 °C for up to 9 months. This accurate and robust analytical method is therefore suitable for contamination or metabolism studies.
Topics: Chlorfenvinphos; Chromatography, Liquid; Linuron; Liver; Organothiophosphorus Compounds; Pesticides; Reproducibility of Results; Tandem Mass Spectrometry
PubMed: 28577486
DOI: 10.1016/j.chemosphere.2017.05.157 -
Water, Air, and Soil Pollution 2022The scientific data review shows that advanced oxidation processes based on the hydroxyl or sulfate radicals are of great interest among the currently conventional water... (Review)
Review
The scientific data review shows that advanced oxidation processes based on the hydroxyl or sulfate radicals are of great interest among the currently conventional water and wastewater treatment methods. Different advanced treatment processes such as photocatalysis, Fenton's reagent, ozonation, and persulfate-based processes were investigated to degrade contaminants of emerging concern (CECs) such as pesticides, personal care products, pharmaceuticals, disinfectants, dyes, and estrogenic substances. This article presents a general overview of visible light-driven advanced oxidation processes for the removal of chlorfenvinphos (organophosphorus insecticide), methylene blue (azo dye), and diclofenac (non-steroidal anti-inflammatory drug). The following visible light-driven treatment methods were reviewed: photocatalysis, sulfate radical oxidation, and photoelectrocatalysis. Visible light, among other sources of energy, is a renewable energy source and an excellent substitute for ultraviolet radiation used in advanced oxidation processes. It creates a high application potential for solar-assisted advanced oxidation processes in water and wastewater technology. Despite numerous publications of advanced oxidation processes (AOPs), more extensive research is needed to investigate the mechanisms of contaminant degradation in the presence of visible light. Therefore, this paper provides an important source of information on the degradation mechanism of emerging contaminants. An important aspect in the work is the analysis of process parameters affecting the degradation process. The initial concentration of CECs, pH, reaction time, and catalyst dosage are discussed and analyzed. Based on a comprehensive survey of previous studies, opportunities for applications of AOPs are presented, highlighting the need for further efforts to address dominant barriers to knowledge acquisition.
PubMed: 36090740
DOI: 10.1007/s11270-022-05831-2 -
The Science of the Total Environment Jul 2019A photoelectrocatalyst consisting of WO nanosheets or nanorods has been synthesized by electrochemical anodization under hydrodynamic conditions, and has been used for...
A photoelectrocatalyst consisting of WO nanosheets or nanorods has been synthesized by electrochemical anodization under hydrodynamic conditions, and has been used for the degradation of two toxic pesticides: chlorfenvinphos and bromacil. Nanostructures have been characterized by FESEM and Raman spectroscopy. Photoelectrochemical degradation tests have been carried out both for individual pesticide solutions and for a mixture solution, and the concentration evolution with time has been followed by UV-Vis spectrophotometry. For individual pesticides, pseudo-first order kinetic coefficients of 0.402h and 0.324h have been obtained for chlorfenvinphos and bromacil, respectively, while for the mixture solution, these kinetic coefficients have been 0.162h and 0.408h. The change in behavior towards pesticide degradation depending on whether individual or mixture solutions were used might be indicative of a competitive process between the two pesticide molecules when interacting with the WO nanostructures surface or when approaching the semiconductor/electrolyte interface.
PubMed: 31004907
DOI: 10.1016/j.scitotenv.2019.04.150 -
Environmental Monitoring and Assessment Mar 2023For beekeeping to be sustainable, the management of colonies for the production of bee products must be economically viable without endangering the lives of bees, and...
For beekeeping to be sustainable, the management of colonies for the production of bee products must be economically viable without endangering the lives of bees, and must include acceptable practices such as the treatment of hives with appropriate products. Occasionally, the use of acaricides to treat the hives against varroosis is uncontrolled and can accumulate in the hives, putting the colonies at risk. In this work, a screening of seven acaricides was carried out in different apiaries in Andalusia (Spain). Their distribution in beeswax, brood, honey, and bees from colonies in different surroundings was evaluated at different times. It was found that beeswax was highly contaminated but honey, brood and bees had acceptable levels, below their respective MRL or LD50, after a certain period following varrocide treatments. Acaricides banned for their use against Varroa, such as chlorfenvinphos, cypermethrin and especially acrinathrin, were found in the hives analysed.
Topics: Bees; Animals; Honey; Acaricides; Environmental Monitoring; Waxes
PubMed: 36892612
DOI: 10.1007/s10661-023-11047-6 -
Environmental Science and Pollution... May 2022The aim of this study was to determine residue levels of pesticides in Swiss commercial beeswax. Foundation samples were collected in 2019 from nine commercial...
The aim of this study was to determine residue levels of pesticides in Swiss commercial beeswax. Foundation samples were collected in 2019 from nine commercial manufacturers for analysis of 21 pesticides using ultra-high performance liquid chromatography. Individual samples showed the variability and residue ranges and pooled samples represented the average annual residue values of the Swiss production. In total, 17 pesticides were identified and 13 pesticides were quantified. They included 13 acaricides and/or insecticides, two fungicides as well as a synergist and a repellent. The means calculated from individual samples were similar to the average annual residue values for most tested pesticides. Mean values of 401, 236, 106 and 3 μg·kg were obtained for the beekeeping-associated contaminants coumaphos, tau-fluvalinate, bromopropylate and N-(2,4-Dimethylphenyl)-formamide (DMF; breakdown product of amitraz), respectively. For the other pesticides, the mean values were 203 μg·kg (synergist piperonyl butoxide), 120 μg·kg (repellent N,N-Diethyl-3-methylbenzamide, DEET), 19 μg·kg (chlorfenvinphos) and 4 μg·kg ((E)-fenpyroximate), while the means for acrinathrin, azoxystrobin, bendiocarb, boscalid, chlorpyrifos, flumethrin, permethrin, propoxur and thiacloprid were below the limit of quantification (< LOQ). Individual samples contained from seven to 14 pesticides. The ranges of values for coumaphos and piperonyl butoxide (from 14 to 4270 μg·kg; from 6 to 1555 μg·kg, respectively) were larger as compared to the ranges of values for DEET and tau-fluvalinate (from < LOQ to 585 μg·kg; from 16 to 572 μg·kg, respectively). In conclusion, the most prominent contaminants were the pesticides coumaphos and tau-fluvalinate, which are both acaricides with previous authorization for beekeeping in Switzerland, followed by piperonyl butoxide, a synergist to enhance the effect of insecticides.
Topics: Acaricides; Bees; Chromatography, High Pressure Liquid; Coumaphos; DEET; Insecticides; Pesticide Residues; Pesticides; Piperonyl Butoxide; Switzerland; Waxes
PubMed: 35018599
DOI: 10.1007/s11356-021-18363-9 -
Food Chemistry Mar 2024We propose a new analytical methodology to determine seven pesticides (atrazine, chlorpyrifos, chlorfenvinphos, α-endosulfan, bromopropylate, coumaphos, and...
We propose a new analytical methodology to determine seven pesticides (atrazine, chlorpyrifos, chlorfenvinphos, α-endosulfan, bromopropylate, coumaphos, and τ-fluvalinate) in royal jelly and propolis products using gas chromatography-mass spectrometry. Sample treatment, with minor modifications for propolis, consisted of a solvent extraction with a hexane and isopropanol mixture, and a further clean-up step. Meanwhile, chromatographic analysis (<25 min) was performed in a DB-5MS column under programmed temperature conditions. In all cases we validated the method in terms of selectivity, limits of detection (0.1-2.8 μg kg) and quantification (0.3-9.2 μg kg), linearity, matrix effect (<±20 %), trueness (recoveries between 93 % and 118 %), and precision (relative standard deviation < 11 %). All royal jelly liquid dietary supplements were positive for chlorfenvinphos and, in the case of one of them, for α-endosulfan; chlorfenvinphos was determined in some fresh royal jelly samples, and no pesticide residues were detected in the propolis samples analysed.
Topics: Pesticides; Propolis; Gas Chromatography-Mass Spectrometry; Chlorfenvinphos; Endosulfan; Solvents
PubMed: 37948804
DOI: 10.1016/j.foodchem.2023.137911 -
International Journal For Parasitology.... May 2024Through a collaborative effort across six Sub-Saharan African countries, using recognized international assessment techniques, 23 stocks of three tick species...
Through a collaborative effort across six Sub-Saharan African countries, using recognized international assessment techniques, 23 stocks of three tick species (Rhipicephalus microplus, Rhipicephalus appendiculatus and Amblyomma variegatum) of economic importance for rural small holder farming communities from East and West Africa were collected from cattle, and evaluated in in vitro larval packet tests (LPT). The results demonstrated medium to high resistance to chlorfenvinphos and amitraz across species. Rhipicephalus microplus demonstrated high level alpha-cypermethrin and cypermethrin resistance. Stocks of A. variegatum (West Africa) and R. appendiculatus (Uganda) demonstrated medium level ivermectin resistance. The four least susceptible stocks (East and West African R. microplus, A. variegatum and R. appendiculatus) were taken into in vivo controlled cattle studies where fipronil was found effective against West and East African R. microplus isolates although persistent efficacy failed to reach 90%. Cymiazole and cypermethrin, and ivermectin based acaricides were partially effective against R. microplus without persistent efficacy. Flumethrin spray-on killed A. variegatum within 72 h for up to 10 days posttreatment, however product application was directly to tick attachment sites, which may be impractical under field conditions. A flumethrin pour-on formulation on goats provided persistent efficacy against A. variegatum for up to one-month. Therapeutic control was achieved against R. appendiculatus through weekly spraying cattle with flumethrin, amitraz or combined cymiazole and cypermethrin. A fipronil pour-on product offered four-week residual control against R. appendiculatus (with slow onset of action). Few studies have assessed and directly compared acaricidal activity in vitro and in vivo. There was some discordance between efficacy indicated by LPT and in vivo results. This observation calls for more research into accurate and affordable assessment methods for acaricide resistance. No single active or product was effective against all three tick species, emphasising the need for the development of alternative integrated tick management solutions.
PubMed: 38761529
DOI: 10.1016/j.ijpddr.2024.100541 -
Pathogens (Basel, Switzerland) Oct 2023is a relevant tick species from a One Health perspective, playing an important role as a vector of , the main agent of spotted fever rickettsiosis in Brazil. In this...
is a relevant tick species from a One Health perspective, playing an important role as a vector of , the main agent of spotted fever rickettsiosis in Brazil. In this study, we evaluated the susceptibility of two populations from Goiás state (midwestern Brazil) to different acaricides. The first tick population (GYN strain) originated from an experimental farm, where the ticks are annually exposed to acaricides. The second (PNE strain) was collected in a national park (Emas National Park), where the ticks had not been exposed to acaricides. Immersion tests were conducted with 21-day-old laboratory-reared larvae and nymphs originating from adult ticks collected in the areas mentioned above. The chosen acaricides were two synthetic pyrethroids (cypermethrin and deltamethrin), one organophosphate (chlorfenvinphos), one formamidine (amitraz), and two combinations of pyrethroids and organophosphates (cypermethrin, chlorpyrifos and citronellal; cypermethrin, fenthion and chlorpyrifos). Mortality data were used to determine the lethal concentration (LC) values at which 50%, 90%, and 99% of the ticks died (LC, LC, and LC, respectively), and resistance ratios (RR) were calculated based on the LC values. The RR revealed differences between the acaricide-exposed (GYN) and unexposed (PNE) tick strains. The PNE strain larvae and nymphs were susceptible to all the tested acaricides. The GYN strain larvae were tolerant to cypermethrin, whereas the nymphs were tolerant to deltamethrin, chlorfenvinphos, and the combination of cypermethrin, chlorpyrifos, and citronellal (2 < RR ≤ 10). The GYN strain nymphs were resistant to amitraz (RR > 10). This is the first report of nymphs with resistance to amitraz and tolerance to deltamethrin, chlorfenvinphos, and the combination of cypermethrin, chlorpyrifos, and citronellal.
PubMed: 38003769
DOI: 10.3390/pathogens12111304 -
Molecules (Basel, Switzerland) Mar 2023Pesticides can be found in beehives for several reasons, including contamination from surrounding crops or for their use by beekeepers, which poses a risk to bee...
Pesticides can be found in beehives for several reasons, including contamination from surrounding crops or for their use by beekeepers, which poses a risk to bee ecosystems and consumers. Therefore, efficient and sensitive methods are needed for determining pesticide residues in bee products. In this study, a new analytical method has been developed and validated to determine seven acaricides (atrazine, chlorpyrifos, chlorfenvinphos, α-endosulfan, bromopropylate, coumaphos, and τ-fluvalinate) in bee pollen using gas chromatography coupled to mass spectrometry. After an optimization study, the best sample treatment was obtained when using a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) method employing an ethyl acetate and cyclohexane as the extractant mixture, and a mixture of salts for the clean-up step. A chromatographic analysis (<21 min) was performed in an Agilent DB-5MS column, and it was operated under programmed temperature conditions. The method was fully validated in terms of selectivity, limits of detection (0.2-3.1 µg kg) and quantification (0.6-9.7 µg kg), linearity, matrix effect (<20% in all cases), trueness (recoveries between 80% and 108%), and precision. Finally, the proposed method was applied to analyze commercial bee pollen samples, and some of the target pesticides (chlorfenvinphos, α-endosulfan, coumaphos, and τ-fluvalinate) were detected.
Topics: Bees; Animals; Gas Chromatography-Mass Spectrometry; Acaricides; Coumaphos; Chlorfenvinphos; Endosulfan; Ecosystem; Pesticides; Pesticide Residues; Pollen
PubMed: 36985469
DOI: 10.3390/molecules28062497