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1.
Chemosphere ; 262: 127612, 2021 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-32750590

RESUMO

Widely used conazole fungicides (CFs) belong to the most frequently detected pesticides in Central European arable soils. However, data on their environmental behaviour and bioavailability to soil organisms are surprisingly scarce. In the present laboratory microcosm study prochloraz, tebuconazole, epoxiconazole and flusilazole were applied to 12 different agricultural soils at background levels. Bioaccumulation to earthworm E. andrei and lettuce L. sativa roots and leaves was evaluated in non-aged (biota exposure after addition of pesticides) and aged (exposure started three months later) systems. In contrast with expectations from ageing effect (decrease of bioavailability), bioaccumulation in E. andrei was both reduced and enhanced after ageing depending on soil properties. The reduction of bioaccumulation correlated positively to the percentage of clay but negatively to soil organic matter. The affinity of compost worm E. andrei towards organic matter where hydrophobic pesticide molecules are sorbed is discussed as a possible explanation. An apparent effect of ageing (reduction of bioavailability) was particularly observed in lettuce roots, where bioaccumulation was significantly reduced in time. However, bioaccumulation in leaves changed ambiguously in aged variants among CFs, possibly as a combined result of bioconcentration, dilution by plant growth and metabolism. This study brings first insights into how the bioaccumulation of conazole fungicides is affected by sequestration in agricultural soils. The results indicate that in complex systems, the ageing is not necessarily connected with decrease of bioaccumulation.


Assuntos
Fungicidas Industriais/metabolismo , Poluentes do Solo/metabolismo , Agricultura , Animais , Bioacumulação , Disponibilidade Biológica , Argila , Compostos de Epóxi , Fungicidas Industriais/análise , Alface/metabolismo , Oligoquetos/metabolismo , Praguicidas/análise , Silanos , Solo/química , Poluentes do Solo/análise , Triazóis
2.
Food Chem ; 339: 127843, 2021 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-32889134

RESUMO

Thiabendazole (TBZ) is extensively used in agriculture to control molds; residue of TBZ may pose a threat to humans. Herein, surface-enhanced Raman spectroscopy (SERS) coupled variable selected regression methods have been proposed as simple and rapid TBZ quantification technique. The nonlinear correlation between the TBZ and SERS data was first diagnosed by augmented partial residual plots method and calculated by runs test. Au@Ag NPs with strong enhancement factor (EF = 4.07 × 106) of Raman signal was used as SERS active material to collect spectra from TBZ. Subsequently, three nonlinear regression models were comparatively investigated and the competitive adaptive reweighted sampling-extreme learning machine (CARS-ELM) achieved a higher correlation coefficient (Rp2 = 0.9406) and the lower root-mean-square-error of prediction (RMSEP = 0.5233 mg/L). Finally, recoveries of TBZ in apple samples were 83.02-93.54% with relative standard deviation (RSD) value < 10%. Therefore, SERS coupled CARS-ELM could be employed as a rapid and sensitive approach for TBZ detection in Fuji apples.


Assuntos
Algoritmos , Análise de Alimentos/métodos , Malus/química , Análise Espectral Raman/métodos , Tiabendazol/análise , Análise de Alimentos/estatística & dados numéricos , Contaminação de Alimentos/análise , Fungicidas Industriais/análise , Humanos , Nanopartículas Metálicas/química
3.
Ecotoxicol Environ Saf ; 207: 111221, 2021 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-32911181

RESUMO

Pydiflumetofen is a novel and efficient broad-spectrum chiral fungicide consisting of a pair of enantiomers. A simple and sensitive chiral analytical method was established to determine the enantiomers of this chiral fungicide in food and environmental samples by ultra-high-performance liquid chromatography tandem triple quadrupole mass spectrometry (UHPLC-MS/MS) using QuEChERS method coupled with octadecylsilane-dispersive solid-phase extraction (C18-dSPE) as extraction procedure. The specific optical rotation and the absolute configuration of the enantiomers were identified by polarimetry and electronic circular dichroism (ECD). The elution order of the pydiflumetofen enantiomers on Lux Cellulose-2 was S-(-)-pydiflumetofen and R-(+)-pydiflumetofen. The average recoveries of eleven matrices ranged from 71.3% to 107.4%. The intraday relative standard deviations (RSDs) were less than 11.8%, and the interday RSDs were less than 12.6% for the two enantiomers. Stereoselective dissipation in pakchoi and soil were observed: S-(-)-pydiflumetofen was degraded faster than R-(+)-pydiflumetofen in pakchoi, causing the enantiomer fraction (EF) of the enantiomers to change from 0.50 to 0.42 in 7 days. However, R-(+)-pydiflumetofen was degraded faster than S-(-)-pydiflumetofen in soil, causing the EF of the enantiomers to change from 0.49 to 0.52 in 21 days. This study provides a method for monitoring pydiflumetofen enantiomer residues, which is crucial for improving risk assessments and the development of chiral pesticides.


Assuntos
Fungicidas Industriais/análise , Pirazóis/análise , Cromatografia Líquida de Alta Pressão/métodos , Cromatografia Líquida , Praguicidas/análise , Solo/química , Poluentes do Solo/análise , Extração em Fase Sólida/métodos , Estereoisomerismo , Espectrometria de Massas em Tandem/métodos
4.
Ecotoxicol Environ Saf ; 207: 111236, 2021 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-32911182

RESUMO

The fungicides epoxiconazole and pyraclostrobin have been widely used to control wheat fusarium head blight. This study was designed to investigate the dissipation behaviors in different climate regions and provide data for the modification of maximum residue limits of the two fungicides. Wheat samples were collected from field sites in twelve different regions, China and analyzed with an HPLC-MS/MS method for simultaneous detection of epoxiconazole and pyraclostrobin in wheat. The average recoveries of epoxiconazole and pyraclostrobin in wheat matrix were 87-112% and 85-102%, respectively, with the relative standard deviations ≤8.1%. The limits of quantification of epoxiconazole and pyraclostrobin in grain and straw were both 0.01 mg/kg. The dissipations of epoxiconazole and pyraclostrobin followed first-order kinetics, with the half-lives of 10.3 days and 7.6 days, respectively. The terminal residues of epoxiconazole and pyraclostrobin in grain were below 0.034 and 0.028 mg/kg, separately, both lower than the maximum residue limits recommended by China. Based on Chinese dietary pattern and terminal residue distributions, the risk quotients of epoxiconazole and pyraclostrobin were 13.9% and 65.9%, respectively, revealing the evaluated wheat exhibited an acceptably low dietary risk to consumers.


Assuntos
Compostos de Epóxi/análise , Fungicidas Industriais/análise , Resíduos de Praguicidas/análise , Estrobilurinas/análise , Triazóis/análise , Triticum/fisiologia , China , Cromatografia Líquida de Alta Pressão , Dieta , Exposição Dietética/estatística & dados numéricos , Compostos de Epóxi/toxicidade , Fungicidas Industriais/toxicidade , Resíduos de Praguicidas/toxicidade , Medição de Risco , Estrobilurinas/toxicidade , Espectrometria de Massas em Tandem/métodos , Triazóis/toxicidade , Triticum/efeitos dos fármacos
5.
Ecotoxicol Environ Saf ; 207: 111286, 2021 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-32931973

RESUMO

Azoxystrobin (AZX) is a broad-spectrum systemic fungicide massively used worldwide. Its mode of action consists in the inhibition of mitochondrial respiration decreasing the synthesis of ATP and leading to oxidative stress in the target fungus. However, whether this effect occurs in non target organisms has been scarcely studied. The objectives of this work were (1) to evaluate biomarkers of oxidative stress, hematological, physiological and of genotoxicity in the native cichlid fish Australoheros facetus exposed to environmentally relevant concentrations of AZX and (2) to compare these biomarkers in different developmental stages using juvenile and adult fish (n = 6) exposed during 48 h. The exposure concentrations were 0 (negative control, C (-)), 0.05, 0.5, 5 and 50 µg/L AZX of the commercial formulation AMISTAR®. Blood was drawn to evaluate hematology, and DNA damage through the comet assay (CA) and micronucleus test (MN). Genotoxicity was observed by mean of both biomarkers in juvenile and adult fish at 50 µg/L AZX. Samples of liver and gills were used to determine antioxidant enzymes activity, hydrogen peroxide (H2O2) and malondialdehyde (MDA) contents. In juvenile fish inhibition of superoxide dismutase (SOD) was observed in liver at 0.05, 5 and 50 µg/L AZX and in gills at 5 and 50 µg/L AZX. Glutathione- S- transferases (GST) activity increased in gills at all AZX concentrations tested. In adult fish, increase of hepatic catalase (CAT) activity at 0.5 and 50 µg/L AZX and MDA content at 50 µg/L AZX were observed. In gills only H2O2 content showed changes at 50 µg/L AZX. The sensitivity showed by gills constitutes the first report about AZX toxicity in this organ. All these negative effects were observed in the range of realistic AZX concentrations, which warns of the possible consequences that it may have on the health of aquatic biota. Differences between juvenile and adult fish demonstrate the relevance of considering the developmental stage on the evaluation of biomarkers.


Assuntos
Ciclídeos/sangue , Dano ao DNA , Fungicidas Industriais/toxicidade , Estresse Oxidativo/efeitos dos fármacos , Pirimidinas/toxicidade , Estrobilurinas/toxicidade , Poluentes Químicos da Água/toxicidade , Animais , Biomarcadores/sangue , Catalase/metabolismo , Ciclídeos/genética , Ensaio Cometa , Fungicidas Industriais/análise , Brânquias/efeitos dos fármacos , Brânquias/metabolismo , Hematologia , Peróxido de Hidrogênio/metabolismo , Fígado/efeitos dos fármacos , Fígado/metabolismo , Pirimidinas/análise , Estrobilurinas/análise , Superóxido Dismutase/metabolismo , Poluentes Químicos da Água/análise
6.
Food Chem ; 338: 127975, 2021 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-32950865

RESUMO

A completely new electroanalytical method for the determination of fenhexamid (FNX) residues in fruit samples has been developed. This method is based on anodic oxidation of fungicide in Britton-Robinson buffer (pH 4) containing 10% (v/v) methanol using square-wave voltammetry when five different carbon-based electrodes were tested. An electrochemical behaviour of FNX was studied on a glassy carbon electrode using cyclic voltammetry, while glassy carbon paste electrode was selected for analytical purposes. Linear range for FNX from 3.96 to 49.50 µmol L-1 characterized by coefficient of determination of 0.9964, sensitivity of 0.176 µA L µmol-1, and detection limit of 1.32 µmol L-1 were calculated. Results acquired from analyses of blueberries and wine grapes were compared to those obtained by a reference chromatographic method, and a satisfactory agreement has been reached. Finally, it seems that the present voltammetric approach could find its application in food quality control as screening assay.


Assuntos
Amidas/análise , Carbono/química , Eletroquímica/instrumentação , Análise de Alimentos/instrumentação , Frutas/química , Vitis/química , Vinho/análise , Eletrodos , Fungicidas Industriais/análise , Oxirredução , Resíduos de Praguicidas/análise , Fatores de Tempo
7.
Sci Total Environ ; 754: 142098, 2021 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-32911151

RESUMO

Despite the high usage of pesticides in current agricultural practices, its effects to humans and to the environment (non-target species) are a continuous concern. Soil dwelling organisms are among the first in line of exposure to pesticides, however their risks are often based on the pure active ingredient (a.i.) and not on the commercial formulated products (FPs) actually applied in the fields. In the present study, we investigated the effects of two fungicide FPs versus its a.i. (s): Amistar® XTRA and the respective a.i. (s) azoxystrobin and cyproconazole, and Prosaro® 250 EC and the respective a.i. (s) prothioconazole and tebuconazole, to the non-target soil oligochaete Enchytraeus crypticus. The standard Enchytraeid Reproduction Test was used to assess effects on survival and reproduction. Results showed that Amistar was more toxic than Prosaro, particularly for reproduction (EC50 = 161 mg Amistar/kg soil, EC50 = 350 mg Prosaro/kg soil). For both FPs, reproductive effects were mainly related to one of its a.i. (s) (azoxystrobin [EC50 = 37 mg azosxystrobin/kg soil] for Amistar, and tebuconazole [EC50 = 41 mg tebuconazole/kg soil] for Prosaro), while lethal effects were not predicted by the toxicity of its a.i. (s) (particularly in the case of Prosaro, which was more toxic than its a.i. (s)). These findings highlight the need to further explore the toxicity data of the FPs compared to the a.i. (s), aiming to predict a more realistic environmental hazard of pesticides.


Assuntos
Fungicidas Industriais , Oligoquetos , Poluentes do Solo , Animais , Fungicidas Industriais/análise , Fungicidas Industriais/toxicidade , Pirimidinas , Reprodução , Solo , Poluentes do Solo/análise , Poluentes do Solo/toxicidade , Estrobilurinas , Triazóis
8.
Sci Total Environ ; 758: 144067, 2021 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-33321360

RESUMO

Repeated spraying of fungicides is a common phenomenon in greenhouse strawberry cultivation, and the continuous harvest of strawberries makes them prone to contamination by accumulated fungicides. Despite this, very few residue safety assessments of fungicides on greenhouse strawberries are conducted after repeated spraying of fungicides, and no research exists on fungicide dissipation and accumulation mechanism. Therefore, the present study investigated the dissipation and accumulation of four fungicides (pyraclostrobin, pyrimethanil, procymidone, and cyprodinil) after two typical repeated sprayings (a single fungicide repeated spraying and two fungicides sprayed using an alternate repeated technique). The half-life of pyraclostrobin after three single repeated sprayings was 18 d; however, its average half-life decreased to 9 d after alternate repeated spraying with cyprodinil. The shortened half-life may be attributed to cyprodinil water solution washing during alternate repeated spraying. The other three fungicides showed similar half-lives after single and alternate repeated spraying, following the order of cyprodinil (12 d and 10 d) > procymidone (11 d and 10 d) > pyrimethanil (6 d and 7 d). The octanol-water partition coefficient was a more efficient indicator of the half-life order of the fungicides than vapor pressure and water solubility. Pyraclostrobin showed the highest deposition efficiency but negligible residue accumulation; further, the residue accumulation of the four fungicides followed the order of procymidone > cyprodinil > pyrimethanil > pyraclostrobin after both single and alternate repeated spraying. A safety assessment demonstrated that the maximum number of times cyprodinil could be sprayed after single spraying was one; however, this number doubled after alternate spraying. The risk of exceeding the maximum residue limits of the fungicides on greenhouse strawberries decreased; however, the combined dietary risks of fungicides after alternate spraying might be high. Alternate repeated spraying of procymidone and pyrimethanil may be the optimal repeated spraying combination for greenhouse strawberries.


Assuntos
Fragaria , Fungicidas Industriais , Resíduos de Praguicidas , Fungicidas Industriais/análise , Resíduos de Praguicidas/análise , Medição de Risco
9.
Environ Sci Pollut Res Int ; 28(1): 1029-1039, 2021 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-32827299

RESUMO

Thiophanate methyl is a broad-spectrum benzimidazole fungicide extensively applied in pre- and post-harvest, for the control of a wide range of fruit and vegetable pathogens. In the current work, the residue behavior of thiophanate methyl after application on strawberries and an estimation of the consumer dietary exposure was performed. Supervised field trials were conducted in Egypt (Qaluobiya Governorate) as to investigate the residue dynamics and terminal residues at different PHIs of thiophanate methyl and its metabolite carbendazim in strawberries under Egyptian conditions. For the measurement of residues in fruits, a QuEChERS-based protocol coupled with LC-MS/MS was optimized and successfully validated at 0.01 mg kg-1. The half-life (t1/2) of thiophanate methyl in strawberries was estimated, and a dietary risk assessment was performed employing both FAO/WHO and EFSA approaches.


Assuntos
Fragaria , Fungicidas Industriais , Resíduos de Praguicidas , Cromatografia Líquida , Egito , Fungicidas Industriais/análise , Meia-Vida , Resíduos de Praguicidas/análise , Medição de Risco , Espectrometria de Massas em Tandem , Tiofanato/análise
10.
Food Chem ; 343: 128504, 2021 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-33158677

RESUMO

Thiabendazole (TBZ), has been extensively employed as a pesticide and/or a fungicide in agriculture, while its residues would threaten to public health and safety. Simple, rapid and sensitive probes for detection of TBZ in real food samples is significantly desirable. In present work, a highly selective and sensitive luminescent sensor for monitoring TBZ in oranges has been constructed based on a Tb3+-functionalized Zr-MOF (Tb3+@1). Tb3+@1 exhibited many attractive sensing properties toward TBZ, including broad linear range (0-80 µM), high selectivity, low LOD (0.271 µM) and rapid response time (less than1 min). Moreover, the probe was employed to determine TBZ in real orange samples, in which good recoveries from 98.41 to 104.48% were obtained. It only takes 35 min for the whole process of detection TBZ in real orange samples combined with QuEChERS method. Therefore, this work provided a reliable and rapid method for monitoring the TBZ in real orange samples.


Assuntos
Citrus sinensis/química , Limite de Detecção , Substâncias Luminescentes/química , Estruturas Metalorgânicas/química , Resíduos de Praguicidas/análise , Térbio/química , Tiabendazol/análise , Fungicidas Industriais/análise , Resíduos de Praguicidas/química , Tiabendazol/química , Fatores de Tempo
11.
Chemosphere ; 263: 128023, 2021 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-33297046

RESUMO

Formation of bound residues (BR) has generally been considered as a detoxification process for organic contaminants. BR is an indispensable component for risk assessment of pesticides. In this study, BR of 14C-pyraoxystrobin in three soils cultivated for 100 days were characterized in light fraction (LF), loosely combined humus (LCH), stably combined humus (SCH), humic acid (HA), fulvic acid (FA), and humin. Isotope labeling technique was used to detect the distribution of BR of 14C-pyraoxystrobin in the six fractions of soil organic matter (SOM). The results showed that the amount of total BR was positively correlated with the SOM content (p < 0.05). The BR of 14C-pyraoxystrobin in cambisol soil was largest at 31.26 ± 0.04% of the induced radioactivity. During the whole incubation period, the BR of pyraoxystrobin in LCH of the three soils were consistently higher than that in SCH, and the amount of BR in FA was consistently greater than that in HA. The BR of 14C-pyraoxystrobin bound with humin increased over time. In addition, a degradation product 3-(4-chlorophenyl)-1-methyl-1H-pyrazol-5-ol (M1) from the hydrolysis of pyraoxystrobin was detected in cambisol soil, indicating the bonding of M1 with the HA separated from LCH (HALCH) via ester or ether linkages. The results provide new insights into the fate of BR of pyraoxystrobin in soils and may help to develop an understanding for the risk assessment of pyraoxystrobin and other strobilurin fungicides.


Assuntos
Fungicidas Industriais , Poluentes do Solo , Acrilatos , Fungicidas Industriais/análise , Substâncias Húmicas/análise , Pirazóis , Solo , Poluentes do Solo/análise
12.
Shokuhin Eiseigaku Zasshi ; 61(4): 143-147, 2020.
Artigo em Japonês | MEDLINE | ID: mdl-33012769

RESUMO

In this study, we developed an LC-MS/MS-based rapid and simple analytical method for six fungicides; imazalil, o-phenylphenol, thiabendazole, fludioxonil, azoxystrobin and pyrimethanil, the latter three were newly approved for use after 2011. For expediting and simplification, we merged the extraction method with that of the pesticide analysis. For purification step, loading of 1 mL of sample extracts to 500 mg Oasis HLB column and elution with 8 mL of acetonitrile gave satisfactory results. The performance of the present method was confirmed for orange, grapefruit, and lemon samples fortified with the six fungicides. The results showed that the average recovery ranged from 89.7 to 100.0%, intra- and inter-assay CV% ranged from 1.5 to 5.0% and from 0.5 to 4.9%, respectively, achieving the target values of the Japanese official guideline for residual pesticide analysis. The limits of quantification of this method were determined to be 1 mg/kg for o-phenylphenol, and 0.2 mg/kg for the other five fungicides. These values were lower than their corresponding regulation values. In addition, we confirmed the usability of the present method for fungicide inspection of commercially available citrus fruits. During 2017-2019, there was no conflict between the food labeling and the fungicides detected and no fungicide with the concentration exceeding maximum residue level was detected.


Assuntos
Cromatografia Líquida , Citrus , Análise de Alimentos , Fungicidas Industriais , Espectrometria de Massas em Tandem , Citrus/química , Análise de Alimentos/métodos , Contaminação de Alimentos/análise , Fungicidas Industriais/análise
13.
J Chromatogr A ; 1633: 461628, 2020 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-33128975

RESUMO

In this work, a hydroxyl-containing porous organic framework (HC-POF) was prepared by a simple solvothermal reaction with 1,4-phthalaldehyde and phloroglucinol as monomers. Sol-gel method was used to coat HC-POF on the glass stir bar. The prepared HC-POF coated stir bar shows better extraction performance for six triazole fungicides (TFs) compared to commercial polydimethylsiloxane and ethylene glycol-silicone coated stir bars. Fourier transform infrared Spectrometry and X-ray photoelectron Spectrometry were used to explore interactions between HC-POF coating and TFs. It is assumed that the coating mainly adsorbs TFs through π-π interactions, hydrogen bonding and hydrophobic interactions. Based on this fact, a new method of HC-POF coated stir bar sorptive extraction combined with high performance liquid chromatography-diode array detector was developed for the determination of six TFs in grape and cabbage samples. A series of extraction and desorption conditions were carefully optimized, including salt concentration, sample solution pH, stirring rate and desorption solvent. Under the optimized experimental conditions, the proposed method displayed limits of detection in the range of 0.022 -0.071 µg L-1, which is the lowest among the reported SBSE methods for target TFs analysis. The linear range for six TFs was 0.1/0.2-500 µg L-1 and the recoveries for the spiked grape and cabbage were 81.0-109% and 80.7-111%, respectively.


Assuntos
Brassica/química , Cromatografia Líquida de Alta Pressão , Análise de Alimentos/métodos , Fungicidas Industriais/análise , Extração Líquido-Líquido/métodos , Estruturas Metalorgânicas/química , Triazóis/análise , Vitis/química , Adsorção , Dimetilpolisiloxanos/química , Fungicidas Industriais/isolamento & purificação , Limite de Detecção , Porosidade , Reprodutibilidade dos Testes , Triazóis/isolamento & purificação
14.
Environ Pollut ; 267: 115481, 2020 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-32892012

RESUMO

Fungicides have been extensively used around the world in agriculture due to their effectiveness of sterilization. Recent evidences have shown that fungicides would exert a negative effect on gut microbiota and result in gut microbiota dysbiosis and metabolism disorder on non-target organisms and even humans. However, research on residues and potential health risks of fungicides in daily consumed vegetables has received less attention compared to insecticides. In this study, we studied three widely applied fungicides, procymidone, dimethomorph, and azoxystrobin, in China. We collected 551 samples of 10 different vegetables in 11 cities from Zhejiang province during 2015-2017. Three fungicides were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The average apparent recoveries of three fungicides ranged from 84.2% to 110% with the relative standard deviations lower than 10%. The LOD values of procymidone, dimethomorph, and azoxystrobin was 2, 0.09, and 1 µg/kg, respectively. The levels of procymidone, dimethomorph, and azoxystrobin in those vegetables ranged from ND-875, ND-238, and ND-76 µg/kg, respectively. The highest mean concentrations of procymidone, dimethomorph, and azoxystrobin were found in eggplant (68 µg/kg), spinach (16.4 µg/kg), and kidney bean (4 µg/kg), respectively. Tomato (62.6% of samples), eggplant (44.3% of samples), and cucumber (41.6% of samples) were most frequently detected with fungicides. Solanaceous fruit vegetables have the highest detection rate than other vegetables, and fungicides were most frequently detected in winter. The mean concentrations of three fungicides in different vegetables were all below the maximum residue limits for the national food safety standards of China, and the health risks resulting from consuming those vegetables in adults and children were all within the safe ranges. The data provided here clarify the distributions of fungicides in commonly consumed vegetables and their potential health risks.


Assuntos
Fungicidas Industriais , Resíduos de Praguicidas , Adulto , Criança , China , Cromatografia Líquida , Frutas/química , Fungicidas Industriais/análise , Humanos , Resíduos de Praguicidas/análise , Espectrometria de Massas em Tandem , Verduras
15.
Ecotoxicol Environ Saf ; 206: 111182, 2020 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-32911370

RESUMO

As a lipophilic fungicide, pyraclostrobin is highly toxic to aquatic organisms, especially to fish. In recent years, research has mainly focused on the pyraclostrobin residue in fish tissues under chronic toxicity, but less is known about its distribution in fish tissues under acute toxicity conditions. In this study, the distribution of pyraclostrobin in fish tissues (blood, liver, muscle and gill) was determined by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The purification effects of different purification materials [1) mixtures of PSA, C18 and MgSO4; 2) QuEChERS-PC; and 3) Oasis HLB SPE] were compared for the detection of pyraclostrobin in fish tissues. Finally, the quick and easy clean-up tool of the Oasis HLB SPE procedure was selected. Under optimum conditions, the linearities had a good relationship (determination coefficient R2 > 0.999). The mean recoveries of the analyte for all tested concentrations ranged from 86.94% to 108.81% with RSDs of 0.7%-4.9%. The pyraclostrobin residue amount was much different in fish tissues. Furthermore, the pyraclostrobin residue in different fish tissues increased initially and then decreased gradually. The concentrations in each tissue were initially ranked before 120 min in the following order: gill > liver > blood > muscle. These phenomena may be attributed to the stress response of fish under acute poisoning. This is the first study to document the distribution of pyraclostrobin in fish tissues under acute toxicity conditions, and it provides reference for the management of agrochemicals in terms of aquatic ecological risks.


Assuntos
Fungicidas Industriais/análise , Resíduos de Praguicidas/análise , Estrobilurinas/análise , Tilápia/metabolismo , Poluentes Químicos da Água/análise , Animais , Cromatografia Líquida de Alta Pressão , Fungicidas Industriais/toxicidade , Músculos/química , Especificidade de Órgãos , Resíduos de Praguicidas/toxicidade , Estrobilurinas/farmacocinética , Estrobilurinas/toxicidade , Espectrometria de Massas em Tandem , Distribuição Tecidual , Testes de Toxicidade Aguda , Poluentes Químicos da Água/toxicidade
16.
Environ Sci Pollut Res Int ; 27(35): 43958-43969, 2020 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-32748361

RESUMO

The effect of fungicides, commonly used in vine cultures, on the health of terrestrial and aquatic ecosystems has been poorly studied. The objective of this study was to evaluate the toxicity of three viticulture fungicides (myclobutanil, cymoxanil, and azoxystrobin) on non-target organisms, the bacteria Rhodopirellula rubra, Escherichia coli, Pseudomonas putida, and Arthrobacter sp., the microalgae Raphidocelis subcapitata, and the macrophyte Lemna minor. Fungicide toxicity was performed in acute cell viability assay for bacteria; 72-h and 7-day growth inhibition tests for R. subcapitata and L. minor, respectively. Contents of photosynthetic pigments and lipid peroxidation in L. minor were evaluated. Arthrobacter sp. and P. putida showed resistance to these fungicides. Even though azoxystrobin affected R. rubra and E. coli cell viability, this effect was due to the solvent used, acetone. Cell viability decrease was obtained for R. rubra exposed to cymoxanil and E. coli exposed to myclobutanil (30 min of exposure at 10 mg/L and 240 min of exposure at 46 mg/L, respectively). R. subcapitata showed about 10-fold higher sensitivity to azoxystrobin (EC50-72h = 0.25 mg/L) and cymoxanil (EC50-72h = 0.36 mg/L) than L. minor to azoxystrobin and myclobutanil (EC50-72h = 1.53 mg/L and EC50-72h = 1.89 mg/L, respectively). No lipid peroxidation was observed in L. minor after fungicide exposure, while changes of total chlorophyll were induced by azoxystrobin and myclobutanil. Our results showed that non-target aquatic organisms of different trophic levels are affected by fungicides used in viticulture.


Assuntos
Fungicidas Industriais , Ecossistema , Ecotoxicologia , Escherichia coli , Fungicidas Industriais/análise , Fungicidas Industriais/toxicidade , Planctomycetales
17.
J Chromatogr A ; 1628: 461437, 2020 Sep 27.
Artigo em Inglês | MEDLINE | ID: mdl-32822977

RESUMO

During stoppers production, large amounts of cork by-products (CBPs) are generated, being used as low-value material. This project aims to turn CBPs into smart, natural and sustainable materials (sorbent) for solid-phase extraction (SPE) of pesticides from water. The study describes the use of CBPs for the extraction of 17 fungicides (metalaxyl, cyprodinil, tolylfluanid, procymidone, folpet, fludioxonil, myclobutanil, kresoxim methyl, iprovalicarb, benalaxyl, trifloxystrobin, fenhexamid, tebuconazole, iprodione, pyraclostrobin, azoxystrobin and dimethomorph) followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) analysis. The most critical parameters affecting SPE were optimized by experimental design methodology. Under the optimal conditions, the method was successfully validated in terms of linearity, repeatability, and intermediate precision. Fungicide recovery was assessed in different real water samples including river, fountain, rainwater and spring water at 3 concentration levels (0.1, 0.5 and 10 µg L-1). Recoveries ranged between 70-118% with RSD values lower than 20%, and matrix effects were not observed. Finally, the method was applied to samples from irrigation, rain, and river water, all collected in vineyards areas, revealing the presence of 10 of the 17 fungicides, at concentration up to hundreds of µg L-1. The use of CBPs seems to be a promising low-cost and ecofriendly alternative to be employed as sorbent in SPE techniques to extract fungicides from the aquatic environment.


Assuntos
Fungicidas Industriais/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Extração em Fase Sólida/métodos , Poluentes Químicos da Água/análise , Adsorção , Análise de Variância , Tamanho da Partícula , Chuva , Rios/química , Espectrometria de Massas em Tandem/métodos , Água/química
18.
Sci Total Environ ; 742: 140436, 2020 Nov 10.
Artigo em Inglês | MEDLINE | ID: mdl-32623160

RESUMO

Pesticide exposure is a growing global concern for pollinator conservation. While most current pesticide studies have specifically focused on the impacts of neonicotinoid insecticides toward honeybees and some native bee species, wild pollinators may be exposed to a broader range of agrochemicals. In 2016 and 2017 we collected a total of 637 wild bees and butterflies from the margins of cultivated agricultural fields situated on five Conservation Areas in mid-northern Missouri. Pollinators were composited by individual genera (90 samples) and whole tissues were then analyzed for the presence of 168 pesticides and degradation products. At least one pesticide was detected (% frequency) in the following wild bee genera: Bombus (96%), Eucera (75%), Melissodes (73%), Ptilothrix (50%), Xylocopa (50%), and Megachile (17%). Similarly, at least one pesticide was detected in the following lepidopteran genera: Hemaris (100%), Hylephila (75%), Danaus (60%), and Colias (50%). Active ingredients detected in >2% of overall pollinator samples were as follows: metolachlor (24%), tebuconazole (22%), atrazine (18%), imidacloprid desnitro (13%), bifenthrin (9%), flumetralin (9%), p, p'-DDD (6%), tebupirimfos (4%), fludioxonil (4%), flutriafol (3%), cyproconazole (2%), and oxadiazon (2%). Concentrations of individual pesticides ranged from 2 to 174 ng/g. Results of this pilot field study indicate that wild pollinators are exposed to and are potentially bioaccumulating a wide variety of pesticides in addition to neonicotinoids. Here, we provide evidence that wild bee and butterfly genera may face exposure to a wide range of insecticides, fungicides, and herbicides despite being collected from areas managed for conservation. Therefore, even with the presence of extensive habitat, minimal agricultural activity on Conservation Areas may expose pollinators to a range of pesticides.


Assuntos
Fungicidas Industriais/análise , Inseticidas/análise , Praguicidas/análise , Animais , Abelhas , Missouri , Neonicotinoides , Nitrocompostos
19.
Sci Total Environ ; 743: 140821, 2020 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-32679504

RESUMO

Five conazole fungicides (CFs) (epoxiconazole, tebuconazole, myclobutanil, uniconazole (P), rac-uniconazole, and diniconazole) were tested in order to provide additional information on i) the effects of CFs on the nematode Caenorhabditis elegans and on the aquatic insect Chironomus riparius under acute exposure scenarios and in multi-generation exposure studies, taking advantage of the short life cycle of nematodes and ii) on the bioaccumulation (earthworm Eisenia andrei) profiles of CFs including also the enantiomer-specific assessment of degradation in soils and uptake/elimination by earthworms. Acute toxicity was considered low following the exposure of up to 2.5 mg of CFs per liter of the test medium. In a multigeneration study on nematodes, all five generations exposed to epoxiconazole were significantly negatively affected in terms of reproductive efficiency, and the severity of effects increased from F0 to F1 generation and was sustained thereafter. Adverse effects were also observed in the case of uniconazole (P) and diniconazole, and similarly to epoxiconazole, the effects occurred within the active life of the pesticides and were assumed to be based on their half-lives in soil (e.g., 53.3 to 691 days for uniconazole and diniconazole in our study) and in sediment/water. Bioaccumulation of diniconazole and uniconazole by earthworms varied between soils (Lufa 2.1 ≥ Lufa 2.4 > sandy soil > Lufa 2.2) and compounds (diniconazole > uniconazole) and was enantioselective. Earthworms preferentially accumulated R-uniconazole as a result of faster elimination of the S-form, which was evidenced from the enantiomer-specific uptake/elimination rate constants derived from the bioaccumulation profiles. Our results suggest that multigeneration exposure studies can advantageously be used for assessing the long-term and trans-general effects of pesticides. Also, the enantioselectivity in bioaccumulation observed for both uniconazole and diniconazole suggests that enantioselectivity in the fate and effects should be considered when exploring ways for safer and sustainable use of chiral pesticides.


Assuntos
Fungicidas Industriais/análise , Oligoquetos , Poluentes do Solo/análise , Animais , Bioacumulação , Solo , Estereoisomerismo
20.
Chemosphere ; 261: 127696, 2020 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-32711239

RESUMO

The presence of fungicide and insecticide residues in wine has been largely investigated. However, few studies have addressed the persistence of these compounds in vineyard soils. In this research, we investigate the residues of a relevant number of fungicides and insecticides in vineyard soils, obtained in the Northwest of Spain, at the beginning of each agriculture campaign. Moreover, the dissipation of species showing high concentrations were monitored during the non-vegetative period of vines, in order to understand their soil evolution between application campaigns. To this end, a multiresidue analytical procedure based on pressurized liquid extraction (PLE) followed by liquid chromatography tandem mass spectrometry (LC-MS/MS) determination was first optimized. Under final working conditions, absolute recoveries in the range from 70 to 130% were achieved for 44 out of 51 selected compounds. The method LOQs remained at the low ng g-1 level (0.2-13 ng g-1) with a linear response range up to 500 ng g-1. Analysis of vineyard soils, collected during a 2-year period, from a geographic area with a high incidence of fungal diseases, demonstrated the presence of relevant concentrations of several fungicides and the insecticide imidacloprid (IMI) in this compartment. Most compounds detected at the end of the application season remained in soil at the beginning of the next year campaign. Among them, six fungicides (dimethomorph, boscalid, myclobutanil, penconazole, pyraclostrobin and pyrimethanil) and IMI showed average dissipation efficiencies below 50%, so they pose a potential to accumulate in this kind of soils.


Assuntos
Fungicidas Industriais/análise , Inseticidas/análise , Resíduos de Praguicidas/análise , Poluentes do Solo/análise , Agricultura , Cromatografia Líquida , Monitoramento Ambiental , Fazendas , Neonicotinoides , Nitrocompostos , Solo/química , Espanha , Espectrometria de Massas em Tandem/métodos , Triazóis , Vinho/análise
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