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Environmental Pollution (Barking, Essex... Jan 2022Scientific literature is full of works studying the removal of different pollutants from water through different Advanced Oxidation Processes (AOPs). Many of them only...
Scientific literature is full of works studying the removal of different pollutants from water through different Advanced Oxidation Processes (AOPs). Many of them only suggest it is reused for agricultural purposes or for small crops in pots. This study is based on the reuse of reclaimed agricultural wastewater contaminated with four insecticides (chlorantraniliprole, imidacloprid, pirimicarb and thiamethoxam) for growing lettuce in field conditions. First, solar photocatalysis with TiO/NaSO was used on a pilot plant in a sunny area (Murcia, SE of Spain) as an environmentally friendly technology to remove insecticide residues and their main reaction intermediates from contaminated water. The necessary fluence (H, kJ m) to accomplish 90% removal (H) ranged from 0.12 to 1212 kJ m for pirimicarb and chlorantraniliprole, respectively. Only six (derived from imidacloprid, pirimicarb and thiametoxam) of 18 transformation intermediate products studied were detected in reclaimed water during the photoperiod (2000 kJ m of accumulated UVA radiation) although all of them were totally photodegraded after a fluence of 1250 kJ m. Secondly, reclaimed agro-wastewater was used to irrigate two lettuce crops grown under greenhouse conditions and under agricultural field conditions. In no cases, insecticide residues nor their TIPs were noticed above their respective LOQs (limits of quantification) in soil and lettuce samples (between 0.03 and 0.04 μg kg for pirimicarb and 2.49 and 2.23 μg kg for thiamethoxam, respectively) when they were irrigated with reclaimed water, while residues of the four insecticides and some of their intermediates were found in soil and lettuce by the end of cultivation when they were irrigated with non-reclaimed contaminated water. According to the results, this technology can be applied in a sustainable way, mainly in areas with water scarcity and high solar radiation, contributing to water utilisation in drought areas and the use of renewable energy.
Topics: Agricultural Irrigation; Insecticides; Lactuca; Pesticide Residues; Technology; Wastewater
PubMed: 34655696
DOI: 10.1016/j.envpol.2021.118367 -
Journal of Food Science and Technology Jun 2022The indiscriminate utilization of agrochemicals causes environmental and animal life impacts. In this regard, methodologies have been developed to offer efficiency and...
UNLABELLED
The indiscriminate utilization of agrochemicals causes environmental and animal life impacts. In this regard, methodologies have been developed to offer efficiency and quickness for agrochemicals detection. Due to their selectivity and molecular recognition sites, Molecular Imprinted Polymer (MIPs) have been widely employed in some areas, including biotechnology, waste analyses, foodstuff, biological fluids, and others. This work proposed developing a method to determine aminocarb, pirimicarb, dimethoate, omethoate, pyridaphenthion, and fenitrothion pesticides using molecularly imprinted polymer combined with solid-phase extraction (MIP-SPE) for clean-up and paper spray ionization mass spectrometry for their analysis. Extractions analysis for Aminocarb, Pirimicarb, and Omethoate using MIP-SPE showed better performance when compared with MIP and NIP. The values were found with > 0.98 for all pesticides, and LODs and LOQs values were 50 and 100 µg kg, respectively. The precision and accuracy were assessed at three concentration levels-low, medium, and high. The precision values (interday and intraday) were below 10%, and the variation of recovery was between 80 and 120% for all pesticides. Therefore, it was possible to verify the presence of two carbamates and five organophosphorus without the necessity of preconcentration samples with precision and good recovery.
SUPPLEMENTARY INFORMATION
The online version contains supplementary material available at 10.1007/s13197-022-05464-7.
PubMed: 35602426
DOI: 10.1007/s13197-022-05464-7 -
Journal of Environmental Management Nov 2023An amount of works has reported the effect of wastewater matrix composition on pollutants removal by different AOPs. The biggest challenge is that each wastewater source...
An amount of works has reported the effect of wastewater matrix composition on pollutants removal by different AOPs. The biggest challenge is that each wastewater source has a challenging composition (organic and inorganic compounds, pollutants, etc.) and not only the concentration of all these species but also the interaction between them may affect the effectiveness of the studied process. This work has been carried out to evaluate the photo-degradation kinetics of six different pesticides (flutriafol, imidacloprid, myclobutanil, pirimicarb, thiamethoxam and triadimenol) by solar photo-Fenton (SPF) process at acidic pH. First, oxidant concentration (HO) was optimized with an actual WWTP effluent. Then, the process was validated with two different secondary and tertiary WWTP effluents, in which main intermediate transformation by-products were identified. Finally, the effect of the inorganic water matrix components (bicarbonate, chloride, sulphate, nitrate and phosphate) was evaluated by a multivariate analysis. Once HO has been optimized at 30 mg L, the photo-degradation efficiency of pesticides in real wastewater samples was compared. DOC content of both secondary and tertiary WWTP effluents was dropped by 67%. The identification of the main intermediate transformation by-products (such as 1H-1,2,4-triazole, desmethyl-formamido pirimicarb, thiamethoxam urea, chloronicotinic acid and imidacloprid urea) was reviewed. Following, the multivariate analysis on pesticides photo-degradation, generally, predicted four significant effects in common for the studied pesticides: a positive effect (interaction bicarbonate/nitrate) and three negative ones (chloride, phosphate and the interaction chloride/sulphate); among others. In addition, optimum values of inorganic ion concentrations, to obtain an optimum desirability on studied pesticides removal by SPF at acidic pH, were also evaluated.
Topics: Wastewater; Pesticides; Hydrogen Peroxide; Iron; Thiamethoxam; Bicarbonates; Chlorides; Nitrates; Environmental Pollutants; Water Pollutants, Chemical; Oxidation-Reduction
PubMed: 37536137
DOI: 10.1016/j.jenvman.2023.118699 -
Environmental Health Insights 2022This study assessed concentrations of pesticide residues in fruits and vegetables from farm-to-fork in Kampala Metropolitan Area, Uganda. A total of 160 samples of fruit...
This study assessed concentrations of pesticide residues in fruits and vegetables from farm-to-fork in Kampala Metropolitan Area, Uganda. A total of 160 samples of fruit and vegetables collected from farms, markets, streets, restaurants and homes were analysed using liquid chromatography-tandem mass spectrometry; and Gas Chromatograph-Mass Spectrometer for dithiocarbamates. Multiple pesticide residues were detected in majority of the samples (95.6%). The proportions of the most frequently detected pesticides residue classes were organophosphates (91.3%), carbamates (67.5%), pyrethroids (60.0%) dithiocarbamates (48.1%) and neonicotinoids (42.5%). Among organophosphates, propotamophos, acephate, fonofos, monocrotophos and dichlorvos were the most detected active ingredients; aminocarb, methomyl and pirimicarb were the commonly detected carbamates; while imidacloprid, a neonicotinoid and lambda-cyhalothrin, pyrethroid were also highly detected. Twenty-seven pesticide were tested at all stages, of which the concentrations either decreased or increased along the chain. Multiple pesticide residues occurred in commonly consumed fruit and vegetables with decreasing or increasing concentrations from farm-to-fork.
PubMed: 35846167
DOI: 10.1177/11786302221111866 -
NanoImpact Jan 2022During emission, TiO nanoparticles (NPs) might meet various chemicals, including metal ions and organic compounds in aquatic environments (e.g., surface water,...
During emission, TiO nanoparticles (NPs) might meet various chemicals, including metal ions and organic compounds in aquatic environments (e.g., surface water, sediments). At environmentally safe concentrations, combinations of both TiO NPs and those chemicals might cause cocktail effects (i.e., mixture toxicity) to aquatic organisms. Previous models such as concentration addition and independent action require dose-response curves of single components in the mixtures to predict the mixture toxicity. Structure-activity relationship (QSAR) models might predict the toxicity of nano-mixtures without dose-response curves of single components in the mixtures. However, current quantitative structure-activity relationship (QSAR) models are mainly focused on predicting cytotoxicity (i.e., cell viability) of heterogeneous metallic TiO nanoparticles (NPs) or mixtures of TiO NPs and four metal ions (Cu, Cd, Ni and Zn). To minimize the experimental cost of nano-mixture risk assessment, in this study, we developed novel nano-mixture QSAR models to predict i) EC of 76 nano-mixtures containing TiO NPs and one of eight inorganic/organic compounds (i.e., AgNO, Cd(NO), Cu(NO), CuSO, NaHAsO, NaAsO, Benzylparaben and Benzophenone-3), to Daphnia magna(D. magna), and ii) immobilization of D. magna exposed to one of 98 mixtures containing TiO NPs and one of eleven inorganic/organic compounds (i.e., AgNO, Cd(NO), Cu(NO), CuSO, NaHAsO, NaAsO, Benzylparaben Benzophenone-3, Pirimicarb, Pentabromodiphenyl Ether and Triton X-100). The nano-mixture QSAR models were developed with mixture descriptors (D) combing quantum descriptors of mixture components (e.g., TiO NPs and its partners) by using different machine learning techniques (i.e., random forest, neural network, support vector machine, and multiple linear regression). Nano-mixture QSAR models built with the random forest algorithm and proposed mixture descriptors exhibited good performance for predicting logEC (Adj.R = 0.955 ± 0.003, RMSE = 0.016 ± 0.002, and MAE = 0.008 ± 0.001) and immobilization (Adj.R = 0.888 ± 0.011, RMSE = 11.327 ± 0.730, and MAE = 5.933 ± 0.442). The models developed in this study were implemented in a user-friendly application for assessing the aquatic toxicity of TiO based nano-mixtures.
Topics: Animals; Cadmium; Daphnia; Organic Chemicals; Quantitative Structure-Activity Relationship; Titanium; Water Pollutants, Chemical
PubMed: 35559889
DOI: 10.1016/j.impact.2022.100383 -
Chemosphere Jul 2021This work assesses the behavior (adsorption, degradation and leaching) of four insecticides (chlorantraniliprole, thiametoxam, imidacloprid and pirimicarb) and their...
This work assesses the behavior (adsorption, degradation and leaching) of four insecticides (chlorantraniliprole, thiametoxam, imidacloprid and pirimicarb) and their main reaction intermediates in a clay-loam textured soil (1.6% OM). Following the batch equilibrium method, the K (as log values) ranged from 1.2 to 3.9 (thiametoxam and pirimicarb, respectively). All the insecticides were moderately persistent (t = 39-100 days) in the following order: thiametoxam > imidacloprid > pirimicarb > chlorantraniliprole. Two major transformation products, desmethyl-formamido pirimicarb and desmethyl pirimicarb, were formed as consequence of dealkylation of the parent compound. Using disturbed soil columns only thiametoxam (93% of the initial amount) and imidacloprid (42% of the initial amount) were recovered from leachates. In the case of pirimicarb and chlorantraniliprole, 74% and 30%, respectively, were recovered from the soil. Thiametoxam and imidacloprid can be catalogued as mobile compounds, while pirimicarb and chlorantraniliprole are classified as immobile according to the screening indices used (GUS and ELI). Leachates containing thiametoxam and imidacloprid were subjected to photocatalytic treatment for 240 min using TiO/NaSO with the help of a photochemical reactor equipped with LED lamp. Both compounds had a very fast degradation rate (half-lives ≤ 0.5 min) in deionized water, while their half-lives were 112 min and 178 min, respectively, in leaching water. This implies a strong effect of the water matrix composition, mainly due to organic matter dissolved (quenching). Only traces of thiametoxam urea and hydroxy imidacloprid were detected during the photocatalytic experiment.
Topics: Adsorption; Clay; Insecticides; Soil; Soil Pollutants
PubMed: 33979936
DOI: 10.1016/j.chemosphere.2021.129965 -
Chemosphere Mar 2023Due to their extensive use and high biological activity, insecticides largely contribute to loss of biodiversity and environmental pollution. The regulation of...
Due to their extensive use and high biological activity, insecticides largely contribute to loss of biodiversity and environmental pollution. The regulation of insecticides by authorities is mainly focused on lethal concentrations. However, sub-lethal effects such as alterations in behavior and neurodevelopment can significantly affect the fitness of individual fish and their population dynamics and therefore deserve consideration. Moreover, it is important to understand the impact of exposure timing during development, about which there is currently a lack of relevant knowledge. Here, we investigated whether there are periods during neurodevelopment of fish, which are particularly vulnerable to insecticide exposure. Therefore, we exposed zebrafish embryos to six different insecticides with cholinergic mode of action for 24 h during different periods of neurodevelopment and measured locomotor output using an age-matched behavior assay. We used the organophosphates diazinon and dimethoate, the carbamates pirimicarb and methomyl as well as the neonicotinoids thiacloprid and imidacloprid because they are abundant in the environment and cholinergic signaling plays a major role during key processes of neurodevelopment. We found that early embryonic motor behaviors, as measured by spontaneous tail coiling, increased upon exposure to most insecticides, while later movements, measured through touch-evoked response and a light-dark transition assay, rather decreased for the same insecticides and exposure duration. Moreover, the observed effects were more pronounced when exposure windows were temporally closer to the performing of the respective behavioral assay. However, the measured behavioral effects recovered after a short period, indicating that none of the exposure windows chosen here are particularly critical, but rather that insecticides acutely interfere with neuronal function at all stages as long as they are present. Overall, our results contribute to a better understanding of risks posed by cholinergic insecticides to fish and provide an important basis for the development of safe regulations to improve environmental health.
Topics: Animals; Insecticides; Zebrafish; Diazinon; Cholinergic Agents; Phenotype
PubMed: 36646183
DOI: 10.1016/j.chemosphere.2023.137874 -
Analytical Methods : Advancing Methods... Oct 2022Carbamate (CB) pesticides possess potential carcinogenic and mutagenic activities towards humans even at very low dosages. Thus, broad-specificity probes with high...
Carbamate (CB) pesticides possess potential carcinogenic and mutagenic activities towards humans even at very low dosages. Thus, broad-specificity probes with high sensitivity and speed are needed for multiple CB determination. This study is the first to focus on Dy ions-coordinated self-assembly on a silica core using a surface imprinting procedure, for the simultaneous fluorometric detection of residues of metolcarb (MC) and pirimicarb (PC) insecticides. A simple and mild solvothermal method was applied for the preparation of fluorescent imprinted microspheres starting from 1,10-phenanthroline (Phen)-ligated Dy ions to guide imprinted self-assembly of chitosan (CTS), glutaraldehyde (GA), and two carbamate pesticides (MC and PC) on the silica surface by means of coordinate bonds and hydrogen bonds. The as-prepared microspheres displayed strong fluorescence emissions the antenna effect derived from the Phen ligand and the Schiff base oligomers for sensitizing the Dy ions. An expanded in-depth mechanism study was performed on the fluorescence enhancement involving Förster resonance energy transfer (FRET) from the pesticides (donor) to the acceptor. A linear increase in fluorescence at 483 nm for MC and 574 nm for PC upon the imprinted microspheres was observed under the same 350 nm excitation wavelength. Moreover, the quantitative recognition process could be carried out simultaneously and tolerate strong distractions both from five other similar carbamate insecticides and from complicated matrices (, an extract of Ramat). The detection limit was 4 ng mL with a range of 10-60 ng mL for MC and 0.4 ng mL with a range of 1-30 ng mL for PC. Further characterization of the material, including TEM, SEM, XPS, and FTIR, Raman, and fluorescence spectra, verified that the Dy ions play a decisive role in promoting imprinted self-assembly around the silica core. Hence, a novel polynuclear Ln-organic imprinted probe having high selectivity, stability, and sensitivity for the detection of two carbamate insecticides is presented in this study.
Topics: Humans; Silicon Dioxide; Microspheres; Molecular Imprinting; Insecticides; Pesticides; Carbamates
PubMed: 36197096
DOI: 10.1039/d2ay01269c -
Journal of Hazardous Materials May 2022Peanut oil, edible vegetable oil largely consumed in China, may be polluted with pesticides during both peanut cultivation and processing. In this study, we analyzed...
Peanut oil, edible vegetable oil largely consumed in China, may be polluted with pesticides during both peanut cultivation and processing. In this study, we analyzed organochlorine pesticides, five currently used pesticides and two degradation products, in soils, seeds, peanuts, oil and dregs and systematically tracked variations of their levels in field soils and during the pressing process. The results showed that the application of metolachlor, pirimicarb and quizalofop-p-ethyl pesticides during peanut cultivation caused their concentrations in peanuts to increase. In most samples, the concentration of 3-phenoxybenzoic acid was higher than that of λ-cyhalothrin, and the variation trends of λ-cyhalothrin and 3-phenoxybenzoic acid in soil samples were similar, which indicate that after application, most λ-cyhalothrin may rapidly be degraded to 3-phenoxybenzoic acid. Regarding the pressing process of peanut oil, the sum of mass of oil and shells was less than the mass of the corresponding raw peanut. Compared with that in peanuts, the total mass of most pesticides in oil and shells was lower, while that of two degradation products was higher, an indication that the degradation products were still generated during the pressing process. Finally, the assessment of health risk of different age groups consuming the studied peanuts and peanut oil showed that the risk was very low.
Topics: Hydrocarbons, Chlorinated; Peanut Oil; Pesticides; Risk Assessment; Soil
PubMed: 35066221
DOI: 10.1016/j.jhazmat.2022.128272 -
Journal of Chromatography. A Oct 2021The low-cost set-up is based on the flexible microfluidic breadboard approach. To avoid the use of electrically driven devices at the high voltage injection end of the...
The low-cost set-up is based on the flexible microfluidic breadboard approach. To avoid the use of electrically driven devices at the high voltage injection end of the capillary pneumatically actuated pumps and valves are employed. It is coupled to the mass spectrometer with a sheathless electrospray obtained in an electrodeless interface configuration. This simplification is achieved by carrying out the analysis in two distinct steps, firstly the separation without the formation of an electrospray, and secondly detection in which the electrospray is created while pumping out the content of the capillary. The performance of the instrument was tested by analysing three benzalkonium ions and the four pesticides pyrifenox, pirimicarb, cyprodinil and pyrimethanil. Detection limits between 0.36 and 0.76 µM and peak reproducibilities between 5.2% and 6.6% (50 µM standards) were obtained for the latter.
Topics: Electrophoresis, Capillary; Pesticides; Reference Standards; Spectrometry, Mass, Electrospray Ionization
PubMed: 34537661
DOI: 10.1016/j.chroma.2021.462533