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1.
Environ Pollut ; 343: 123186, 2024 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-38142029

RESUMO

The second-generation neonicotinoid thiamethoxam, is prevalent in soils because of its extensive application and persistence. However, the comprehensive effects of thiamethoxam residue in soils on cultivated plants are still poorly understood. This study examined variations of growth state, physiological parameters, antioxidant activity, and metabolites in lettuce after thiamethoxam exposure; the removal effects of different washing procedures were also investigated. The results indicated that thiamethoxam in soils significantly increased the fresh weight, seedling height and chlorophyll content in lettuce, and also altered its lipid, carbohydrate, nucleotide and amino acids composition based on untargeted metabolomics. KEGG pathway analysis uncovered a disruption of lipid pathways in lettuce exposed to both low and high concentrations of thiamethoxam treatments. In addition, the terminal residues of thiamethoxam in lettuce were below the corresponding maximum residue limits stipulated for China. The thiamethoxam removal rates achieved by common washing procedures in lettuce ranged from 26.9% to 42.6%. This study thus promotes the understanding of the potential food safety risk caused by residual thiamethoxam in soils.


Assuntos
Inseticidas , Lactuca , Tiametoxam , Inseticidas/análise , Tiazóis/análise , Neonicotinoides/toxicidade , Neonicotinoides/química , Solo/química , Lipídeos
2.
Fitoterapia ; 162: 105282, 2022 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-35988845

RESUMO

BACKGROUND: The roots of horseradish (Armoracia rusticana) are used for infections of respiratory airway and for urinary tract infections due to isothiocyanates (ITC), enzymatically formed during fermentation of glucosinolates by myrosinase. HYPOTHESIS/PURPOSE: The present study aims to present a comprehensive overview on the phytochemical composition of A. rusticana roots, especially concerning isothiocyanates and respective glucosinolates. The complex flavonoid spectrum of the herbal material is reviewed. Published data on in vitro activity of horseradish extracts and isolated compounds are summarized. These data indicate well-established use of horseradish as an antibacterial remedy against bacterial infections of the airway and urinary tract. STUDY DESIGN: To answer the question if other compounds from A. rusticana beside ITC contribute to the antibacterial activity, non-targeted LC-MS studies were performed with fermented and non-fermented horseradish extracts, and detailed phytochemical profiles were established. RESULTS: Comparative investigations on the antibacterial activity indicated that only ITC-containing extracts and fractions exert antibacterial activity. The huge variety of non-ITC compounds do not significantly contribute to the antibacterial activity, but can be used for analytical characterisation and quality control of the herbal material. Detailed phytochemical analysis additionally revealed a variety of compounds, not described until now for horseradish roots: the flavonol glycosides kaempferol-3-O-ß-d-xylopyranosyl-(1''' â†’ 2'')-ß-d-galactopyranoside, kaempferol-3-O-α-l-rhamnopyranosyl-(1''' â†’ 6'')-ß-d-glucopyranoside, kaempferol-3-O-ß-d-glucopyranoside, Kaempferol-3-O-ß-d-xylopyranosyl-7-O-ß-d-glucopyranoside, Kaempferol-3-O-ß-d-xylopyranosyl-(1'''' â†’ 2''')-ß-d-galactopyranoside-7-O-ß-d-glucopyranoside, the oxo-indole derivative spirobrassinin, the phenylthiazole 2-methylsulfanyl-4-phenyl-4,5-dihydro-1,3-thiazole, a series of lysophophatidylethanolamine and 13 different N-phenylpropenoyl-L-amino acids. CONCLUSION: The antibacterial effects of horseradish are only due to the presence of glucosinolates resp. the corresponding ITC, and the detailed overall composition of horseradish extracts has been reported.


Assuntos
Armoracia , Glucosinolatos , Aminoácidos , Antibacterianos/farmacologia , Armoracia/química , Galactose/análise , Glucosinolatos/análise , Glucosinolatos/química , Glucosinolatos/farmacologia , Glicosídeos/análise , Indóis , Isotiocianatos/farmacologia , Quempferóis , Estrutura Molecular , Compostos Fitoquímicos/análise , Compostos Fitoquímicos/farmacologia , Extratos Vegetais/análise , Extratos Vegetais/farmacologia , Raízes de Plantas/química , Tiazóis/análise
3.
Anal Bioanal Chem ; 413(7): 1955-1966, 2021 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-33481048

RESUMO

The selective detection of salicylaldehyde skeleton is of great significance in phytochemistry and biological research but rarely reported. In this research, a simple and highly selective "turn-on" fluorescence sensor (CDB-Am) for salicylaldehyde skeleton was developed based on switch of photoinduced electron transfer (PET) and aggregation-induced emission (AIE). CDB-Am bearing amino-cyanodistyrene structure responded to salicylaldehyde in the range of 3.1 to 40 µM with a detection limit of 0.94 µM. The sensing process of formation of Schiff-base adduct CDB-SA was confirmed by 1H NMR, MS, and FT-IR spectra, revealing that a recovered AIE property accounted for the turn-on fluorescence response of CDB-Am and the intramolecular hydrogen bonding played a crucial role in the disruption of PET process. This sensing ability was successfully applied for both fluorescence qualitative test of salicylaldehyde skeleton on TLC analysis and quantitative detection of salicylaldehyde skeleton with good accuracy in the root bark of Periploca sepium, suggesting the extensive applications in phytochemistry and traditional Chinese herbal medicine. Furthermore, CDB-Am exhibited the first excellent fluorescence imaging ability in detecting salicylaldehyde skeleton in a living system. This work supplied a new strategy of preparing a novel "turn-on" fluorescence probe for detecting salicylaldehyde skeleton in complex environments and living bodies.


Assuntos
Aldeídos/análise , Corantes Fluorescentes/análise , Bases de Schiff/análise , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Cromatografia em Camada Fina , Fluorescência , Humanos , Ligação de Hidrogênio , Radical Hidroxila , Iminas/química , Limite de Detecção , Células MCF-7 , Espectroscopia de Ressonância Magnética , Espectrometria de Massas , Medicina Tradicional Chinesa , Microscopia de Fluorescência , Imagem Óptica , Casca de Planta , Raízes de Plantas , Espectrofotometria Ultravioleta , Sais de Tetrazólio/análise , Tiazóis/análise
4.
Environ Pollut ; 250: 397-406, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31022645

RESUMO

Recent studies have shown that neonicotinoids in pollen and honey (collected by honeybees) are likely to pose risks to honeybees. However, data on the integrated residue and spatial-temporal variation of neonicotinoids from noncrop plants, the principle sources of pollen for honey bees, are very limited, especially in China. In this study, we employed a novel assessment method based on the relative potency factor to calculate the integrated residue of seven neonicotinoids in pollen and honey samples collected from noncrop plants in 12 stations of Zhejiang province in three consecutive months. The integrated concentration of neonicotinoids (IMIRPF) ranged from no detected (ND) to 34.93 ng/g in pollen and ND to 8.51 ng/g in honey. Acetamiprid showed the highest detection frequency of 41.7%, followed by clothianidin (33.3%) and dinotefuran (22.2%). The highest IMIRPF occurred in April for stations in the fringe areas of Zhejiang province, whereas for stations in the central areas of Zhejiang province, the IMIRPF in May was relatively higher than the other two months. In terms of spatial change, the pollution variation of pollen samples in Lin'an-Tonglu-Pujiang was relative highly polluted-lightly polluted-highly polluted. For honey samples, spatial variation showed a single trend, and peak values were found in Wenzhou, which may be attributed to the local climate and farming practices. This fundamental information will be helpful to understand the effects of neonicotinoids on honeybees foraging habits.


Assuntos
Poluentes Ambientais/análise , Mel/análise , Neonicotinoides/análise , Pólen/química , Agricultura , Animais , Abelhas , China , Monitoramento Ambiental , Guanidinas/análise , Nitrocompostos/análise , Plantas , Análise Espaço-Temporal , Tiazóis/análise
5.
Crit Care ; 23(1): 62, 2019 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-30795779

RESUMO

There is a high degree of uncertainty regarding optimum care of patients with potential or known intake of oral anticoagulants and traumatic brain injury (TBI). Anticoagulation therapy aggravates the risk of intracerebral hemorrhage but, on the other hand, patients take anticoagulants because of an underlying prothrombotic risk, and this could be increased following trauma. Treatment decisions must be taken with due consideration of both these risks. An interdisciplinary group of Austrian experts was convened to develop recommendations for best clinical practice. The aim was to provide pragmatic, clear, and easy-to-follow clinical guidance for coagulation management in adult patients with TBI and potential or known intake of platelet inhibitors, vitamin K antagonists, or non-vitamin K antagonist oral anticoagulants. Diagnosis, coagulation testing, and reversal of anticoagulation were considered as key steps upon presentation. Post-trauma management (prophylaxis for thromboembolism and resumption of long-term anticoagulation therapy) was also explored. The lack of robust evidence on which to base treatment recommendations highlights the need for randomized controlled trials in this setting.


Assuntos
Anticoagulantes/uso terapêutico , Lesões Encefálicas Traumáticas/tratamento farmacológico , Administração Oral , Anticoagulantes/efeitos adversos , Áustria , Lesões Encefálicas Traumáticas/fisiopatologia , Consenso , Dabigatrana/efeitos adversos , Dabigatrana/uso terapêutico , Desamino Arginina Vasopressina/farmacologia , Humanos , Comunicação Interdisciplinar , Tempo de Tromboplastina Parcial/métodos , Pirazóis/análise , Pirazóis/sangue , Pirazóis/uso terapêutico , Piridinas/análise , Piridinas/sangue , Piridinas/uso terapêutico , Piridonas/análise , Piridonas/sangue , Piridonas/uso terapêutico , Rivaroxabana/análise , Rivaroxabana/sangue , Rivaroxabana/uso terapêutico , Tiazóis/análise , Tiazóis/sangue , Tiazóis/uso terapêutico , Tromboembolia/prevenção & controle , Tomografia Computadorizada por Raios X/métodos , Ácido Tranexâmico/uso terapêutico , Resultado do Tratamento , Vitamina K/antagonistas & inibidores , Vitamina K/uso terapêutico
6.
Environ Entomol ; 48(2): 351-362, 2019 04 03.
Artigo em Inglês | MEDLINE | ID: mdl-30753426

RESUMO

Worldwide studies have used the technique of pollen trapping, collecting pollen loads from returning honey bee (Apis mellifera L.) (Hymenoptera: Apidae) foragers, to evaluate the exposure of honey bees to pesticides through pollen and as a biomonitoring tool. Typically, these surveys have found frequent contamination of pollen with multiple pesticides, with most of the estimated risk of acute oral toxicity to honey bees coming from insecticides. In our survey of pesticides in trapped pollen from three commercial ornamental plant nurseries in Connecticut, we found most samples within the range of acute toxicity in a previous state pollen survey, but a few samples at one nursery with unusually high acute oral toxicity. Using visual sorting by color of the pollen pellets collected in two samples from this nursery, followed by pesticide analysis of the sorted pollen and palynology to identify the plant sources of the pollen with the greatest acute toxicity of pesticide residues, we were able to associate pollen from the plant genus Spiraea L. (Rosales: Rosaceae) with extraordinarily high concentrations of thiamethoxam and clothianidin, and also with high concentrations of acephate and its metabolite methamidophos. This study is the first to trace highly toxic pollen collected by honey bees to a single plant genus. This method of tracking high toxicity pollen samples back to potential source plants could identify additional high-risk combinations of pesticide application methods and timing, movement into pollen, and attractiveness to bees that would be difficult to identify through modeling each of the contributing factors.


Assuntos
Abelhas , Resíduos de Praguicidas/análise , Pólen/química , Spiraea , Animais , Jardinagem , Guanidinas/análise , Inseticidas/análise , Neonicotinoides/análise , Tiametoxam/análise , Tiazóis/análise
7.
Environ Toxicol Chem ; 38(2): 423-435, 2019 02.
Artigo em Inglês | MEDLINE | ID: mdl-30575066

RESUMO

Discerning potential effects of insecticides on honey bee colonies in field studies conducted under realistic conditions can be challenging because of concurrent interactions with other environmental conditions. Honey bee colony models can control exposures and other environmental factors, as well as assess links among pollen and nectar residues in the landscape, their influx into the colony, and the resulting exposures and effects on bees at different developmental stages. We extended the colony model BEEHAVE to represent exposure to the insecticide clothianidin via residues in pollen from treated cornfields set in real agricultural landscapes in the US Midwest. We assessed their potential risks to honey bee colonies over a 1-yr cycle. Clothianidin effects on colony strength were only observed if unrealistically high residue levels in the pollen were simulated. The landscape composition significantly impacted the collection of pollen (residue exposure) from the cornfields, resulting in higher colony-level effects in landscapes with lower proportions of semi-natural land. The application of the extended BEEHAVE model with a pollen exposure-effects module provides a case study for the application of a mechanistic honey bee colony model in pesticide risk assessment integrating the impact of a range of landscape compositions. Environ Toxicol Chem 2019;38:423-435. © 2018 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.


Assuntos
Abelhas , Guanidinas/análise , Inseticidas/análise , Modelos Teóricos , Neonicotinoides/análise , Resíduos de Praguicidas/análise , Pólen/química , Tiazóis/análise , Zea mays/crescimento & desenvolvimento , Animais , Abelhas/fisiologia , Monitoramento Ambiental , Minnesota , Néctar de Plantas/química , Medição de Risco , South Dakota , Wisconsin
8.
Braz. J. Pharm. Sci. (Online) ; 55: e18218, 2019. tab, graf
Artigo em Inglês | LILACS | ID: biblio-1011650

RESUMO

Diabetes mellitus is a chronic disease resulting in oxidative stress that promotes tissue damage. The appearance of this disease is highly related to lifestyle and food of the population, being of great interest to search for a dietary supplement that can also act by reducing oxidative alterations. Based on the broad range of biological activity of thiazole derivatives, this work aimed to evaluate the in vitro antioxidant activity of a novel hydrazine-thiazole derivative and studies in vivo. In in vivo experiments, the liver extracts of healthy and diabetic Wistar rats were used, with analysis to determine the enzymatic activity of SOD, CAT, GPx, and GR, and determination of lipid peroxidation. Finally, in the blood of these animals, biochemical parameters were evaluated. Statistical evidence of changes caused in liver enzymes and liquid peroxidation was not detected; however, these parameters were also not changed between control groups with and without diabetes. On the other hand, concerning biochemical parameters, significant differences were detected in uric acid, alkaline phosphatase, ALT, and urea, indicating a possible antioxidant protective role of such substances in the liver and kidney of diabetic animals that could be acting by means other than that commonly reported in the literature.


Assuntos
Animais , Masculino , Ratos , Tiazóis/análise , Técnicas In Vitro/métodos , Hidrazinas/análise , Estresse Oxidativo/fisiologia , Suplementos Nutricionais , Diabetes Mellitus/tratamento farmacológico , Antioxidantes/análise
9.
Chemosphere ; 201: 159-167, 2018 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-29524816

RESUMO

Neonicotinoid insecticides (NIs) have recently been recognized as co-factors in the decline of honeybee colonies because most neonicotinoids are systemic and can transfer into the pollen and nectar of many pollinated crops. In this study, we collected pollen, nectar and leaves from a cotton crop treated with imidacloprid and thiamethoxam to measure the residue levels of these two NIs at different application doses during the flowering period. Then, the residual data were used to assess the risk posed by the systemic insecticides to honeybees following mandated methods published by the European Food Safety Authority (EFSA), and a highly toxic risk to honeybees was highlighted. Imidacloprid was found in both pollen and nectar samples, whereas thiamethoxam was found in 90% of pollen samples and over 60% of nectar samples. Analysis of the pollen and nectar revealed residual amounts of imidacloprid ranging from 1.61 to 64.58 ng g-1 in the pollen and from not detected (ND) to 1.769 ng g-1 in the nectar. By comparison, the thiamethoxam concentrations in pollen and nectar ranged from ND to 14.521 ng g-1 and from ND to 4.285 ng g-1, respectively. The results of this study provide information on the transfer of two NIs from seed treatment to areas of the plant and provides an understanding of the potential exposure of the bee and other pollinators to systemic insecticides.


Assuntos
Abelhas/efeitos dos fármacos , Produtos Agrícolas/química , Gossypium/química , Neonicotinoides/análise , Nitrocompostos/análise , Oxazinas/análise , Resíduos de Praguicidas/análise , Tiazóis/análise , Animais , China , Neonicotinoides/toxicidade , Nitrocompostos/toxicidade , Oxazinas/toxicidade , Resíduos de Praguicidas/toxicidade , Folhas de Planta/química , Néctar de Plantas/química , Pólen/química , Polinização , Medição de Risco , Sementes/química , Tiametoxam , Tiazóis/toxicidade
10.
ACS Chem Neurosci ; 8(11): 2558-2567, 2017 11 15.
Artigo em Inglês | MEDLINE | ID: mdl-28759721

RESUMO

The amyloid aggregation process of amyloid ß1-42 peptide is responsible for Alzheimer's disease, affecting millions of elderly people worldwide. Although there has been a great deal of attention directed toward tackling this disease, still no medicine has been found for this fatal disorder. To address this challenge, it is vital to thoroughly understand the molecular mechanism underlying the amyloid peptide aggregation process, as well as seek substances that could hamper this aggregation. In order to shed light on mechanisms leading to amyloidogenesis, we employed a microfluidic system to determine the possible influence of in vivo-like flow in the microchip channel itself on feline Aß1-42 peptide amyloidogenesis. We have shown that shear forces occurring during such flow immensely accelerated peptide aggregation. We also tested the inhibitory influence of 3,3'-[1,6-(2,5-dioxahexane)]bis(1-dodecylimidazolium) dichloride gemini surfactant on peptide amyloidogenesis. Our results suggest that this surfactant may inhibit amyloid ß1-42 fibril formation.


Assuntos
Peptídeos beta-Amiloides/química , Amiloide/química , Dispositivos Lab-On-A-Chip , Fragmentos de Peptídeos/química , Agregados Proteicos , Amiloide/efeitos dos fármacos , Amiloide/ultraestrutura , Animais , Benzotiazóis , Gatos , Dicroísmo Circular , Avaliação Pré-Clínica de Medicamentos , Fluorometria , Microscopia de Força Atômica , Microscopia Eletrônica de Transmissão , Agregação Patológica de Proteínas/prevenção & controle , Dobramento de Proteína/efeitos dos fármacos , Reologia , Espalhamento a Baixo Ângulo , Resistência ao Cisalhamento , Tensoativos/farmacologia , Tiazóis/análise , Difração de Raios X
11.
Actas Dermosifiliogr ; 108(8): 758-770, 2017 Oct.
Artigo em Inglês, Espanhol | MEDLINE | ID: mdl-28673419

RESUMO

INTRODUCTION: Preservatives are added to cosmetic, household cleaning, and other industrial products to prevent the growth of microorganisms. Unfortunately, exposure to these substances can cause sensitization. MATERIAL AND METHODS: Between January and June 2015, we analyzed the ingredients of 2300 products commercially available in Spain to identify the frequency of a wide variety of preservatives in different product categories. We analyzed 1093 skin care and cosmetic products sold exclusively in pharmacies (dermocosmetics), 458 household cleaning and personal hygiene and cosmetic products sold in supermarkets, 636 topical medications, and 113 cosmetic products sold in a herbal shop. RESULTS: Phenoxyethanol, citric acid, sodium benzoate, and potassium sorbate were very common in all the cosmetic product categories. Parabens were present in 16.1% of dermocosmetic products, 14.45% of cosmetic products available in supermarkets, 0.88% of cosmetic products available in the herbal shop, 5.18% of topical medications, and in none of the cleaning products. Isothiazolinones were identified in 2.56% of dermocosmetic products, 18% of cosmetic products in supermarkets, 7.9% of cosmetic products in the herbal shop, 63.63% of household cleaners, and in none of the topical medications. Formaldehyde releasers were detected in 5.76% of dermocosmetic products, 6.42% of cosmetic products sold in supermarkets, 7.96% of cosmetic products sold in the herbal shop, 3.93% of topical medications, and 16.74% of household cleaners. CONCLUSIONS: Evaluation of the presence of preservatives in everyday products allows us to indirectly estimate exposure levels to each one. Measures restricting the use of the most problematic preservatives need to be strengthened.


Assuntos
Produtos Domésticos/análise , Preparações Farmacêuticas/química , Conservantes Farmacêuticos/análise , Comércio , Cosméticos/química , Formaldeído/análise , Parabenos/análise , Preparações de Plantas/química , Sabões/química , Tiazóis/análise
12.
Environ Pollut ; 228: 297-304, 2017 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-28551560

RESUMO

Garden centres frequently market nectar- and pollen-rich ornamental plants as "pollinator-friendly", however these plants are often treated with pesticides during their production. There is little information on the nature of pesticide residues present at the point of purchase and whether these plants may actually pose a threat to, rather than benefit, the health of pollinating insects. Using mass spectrometry analyses, this study screened leaves from 29 different 'bee-friendly' plants for 8 insecticides and 16 fungicides commonly used in ornamental production. Only two plants (a Narcissus and a Salvia variety) did not contain any pesticide and 23 plants contained more than one pesticide, with some species containing mixtures of 7 (Ageratum houstonianum) and 10 (Erica carnea) different agrochemicals. Neonicotinoid insecticides were detected in more than 70% of the analysed plants, and chlorpyrifos and pyrethroid insecticides were found in 10% and 7% of plants respectively. Boscalid, spiroxamine and DMI-fungicides were detected in 40% of plants. Pollen samples collected from 18 different plants contained a total of 13 different pesticides. Systemic compounds were detected in pollen samples at similar concentrations to those in leaves. However, some contact (chlorpyrifos) and localised penetrant pesticides (iprodione, pyroclastrobin and prochloraz) were also detected in pollen, likely arising from direct contamination during spraying. The neonicotinoids thiamethoxam, clothianidin and imidacloprid and the organophosphate chlorpyrifos were present in pollen at concentrations between 6.9 and 81 ng/g and at levels that overlap with those known to cause harm to bees. The net effect on pollinators of buying plants that are a rich source of forage for them but simultaneously risk exposing them to a cocktail of pesticides is not clear. Gardeners who wish to gain the benefits without the risks should seek uncontaminated plants by growing their own from seed, plant-swapping or by buying plants from an organic nursery.


Assuntos
Monitoramento Ambiental , Insetos/efeitos dos fármacos , Resíduos de Praguicidas/análise , Agroquímicos/análise , Animais , Abelhas , Fungicidas Industriais/análise , Jardinagem , Guanidinas/análise , Imidazóis/análise , Inseticidas/análise , Neonicotinoides , Nitrocompostos/análise , Oxazinas/análise , Praguicidas/análise , Néctar de Plantas/química , Pólen/química , Polinização/efeitos dos fármacos , Sementes/química , Tiametoxam , Tiazóis/análise
13.
Ecotoxicology ; 25(9): 1617-1629, 2016 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-27709399

RESUMO

The nitro-substituted neonicotinoid insecticides, which include imidacloprid, thiamethoxam and clothianidin, are widely used to control a range of important agricultural pests both by foliar applications and also as seed dressings and by soil application. Since they exhibit systemic properties, exposure of bees may occur as a result of residues present in the nectar and/or pollen of seed- or soil-treated crop plants and so they have been the subject of much debate about whether they cause adverse effects in pollinating insects under field conditions. Due to these perceived concerns, the use of the three neonicotinoids imidacloprid, clothianidin and thiamethoxam has been temporarily suspended in the European Union for seed treatment, soil application and foliar treatment in crops attractive to bees. Monitoring data from a number of countries are available to assess the presence of neonicotinoid residues in honey bee samples and possible impacts at the colony level and these are reviewed here together with a number of field studies which have looked at the impact of clothiandin on honey bees in relation to specific crop use and in particular with oilseed rape. Currently there is considerable uncertainty with regards to the regulatory testing requirements for field studies. Accordingly, a testing protocol was developed to address any acute and chronic risks from oilseed rape seeds containing a coating with 10 g clothianidin and 2 g beta-cyfluthrin per kg seeds (Elado®) for managed honey bee (Apis mellifera) colonies, commercially bred bumble bee (Bombus terrestris) colonies and red mason bees (Osmia bicornis) as a representative solitary bee species. This is described here together with a summary of the results obtained as an introduction to the study details given in the following papers in this issue.


Assuntos
Monitoramento Ambiental , Poluentes Ambientais/toxicidade , Inseticidas/toxicidade , Animais , Abelhas , Produtos Agrícolas , Poluentes Ambientais/análise , Guanidinas , Imidazóis/análise , Imidazóis/toxicidade , Inseticidas/análise , Neonicotinoides , Nitrocompostos/análise , Nitrocompostos/toxicidade , Oxazinas/análise , Oxazinas/toxicidade , Néctar de Plantas , Pólen , Polinização , Tiametoxam , Tiazóis/análise , Tiazóis/toxicidade
14.
Ecotoxicology ; 25(9): 1691-1701, 2016 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-27650369

RESUMO

This study was part of a large-scale monitoring project to assess the possible effects of Elado® (10 g clothianidin & 2 g ß-cyfluthrin/kg seed)-dressed oilseed rape seeds on different pollinators in Northern Germany. Firstly, residues of clothianidin and its active metabolites thiazolylnitroguanidine and thiazolylmethylurea were measured in nectar and pollen from Elado®-dressed (test site, T) and undressed (reference site, R) oilseed rape collected by honey bees confined within tunnel tents. Clothianidin and its metabolites could not be detected or quantified in samples from R fields. Clothianidin concentrations in samples from T fields were 1.3 ± 0.9 µg/kg and 1.7 ± 0.9 µg/kg in nectar and pollen, respectively. Secondly, pollen and nectar for residue analyses were sampled from free flying honey bees, bumble bees and mason bees, placed at six study locations each in the R and T sites at the start of oilseed rape flowering. Honey samples were analysed from all honey bee colonies at the end of oilseed rape flowering. Neither clothianidin nor its metabolites were detectable or quantifiable in R site samples. Clothianidin concentrations in samples from the T site were below the limit of quantification (LOQ, 1.0 µg/kg) in most pollen and nectar samples collected by bees and 1.4 ± 0.5 µg/kg in honey taken from honey bee colonies. In summary, the study provides reliable semi-field and field data of clothianidin residues in nectar and pollen collected by different bee species in oilseed rape fields under common agricultural conditions.


Assuntos
Abelhas/fisiologia , Brassica napus/química , Monitoramento Ambiental , Guanidinas/análise , Mel/análise , Inseticidas/análise , Resíduos de Praguicidas/análise , Polinização/efeitos dos fármacos , Sementes/química , Tiazóis/análise , Animais , Alemanha , Inseticidas/toxicidade , Neonicotinoides , Resíduos de Praguicidas/toxicidade , Néctar de Plantas/química , Pólen/química , Sementes/toxicidade
15.
J Agric Food Chem ; 64(33): 6407-15, 2016 Aug 24.
Artigo em Inglês | MEDLINE | ID: mdl-27529118

RESUMO

Pesticide transport from seed dressings toward subsurface tile drains is still poorly understood. We monitored the neonicotinoid insecticides imidacloprid and thiamethoxam from sugar beet seed dressings in flow-proportional drainage water samples, together with spray applications of bromide and the herbicide S-metolachlor in spring and the fungicides epoxiconazole and kresoxim-methyl in summer. Event-driven, high first concentration maxima up to 2830 and 1290 ng/L for thiamethoxam and imidacloprid, respectively, were followed by an extended period of tailing and suggested preferential flow. Nevertheless, mass recoveries declined in agreement with the degradation and sorption properties collated in the groundwater ubiquity score, following the order bromide (4.9%), thiamethoxam (1.2%), imidacloprid (0.48%), kresoxim-methyl acid (0.17%), S-metolachlor (0.032%), epoxiconazole (0.013%), and kresoxim-methyl (0.003%), and indicated increased leaching from seed dressings compared to spray applications. Measured concentrations and mass recoveries indicate that subsurface tile drains contribute to surface water contamination with neonicotinoids from seed dressings.


Assuntos
Monitoramento Ambiental , Água Subterrânea/química , Imidazóis/análise , Inseticidas/análise , Nitrocompostos/análise , Oxazinas/análise , Solo/química , Tiazóis/análise , Poluentes Químicos da Água/análise , Agricultura , Beta vulgaris , Brometos/análise , Cromatografia Líquida de Alta Pressão , Compostos de Epóxi/análise , Herbicidas/análise , Metacrilatos/análise , Neonicotinoides , Fenilacetatos/análise , Sementes , Poluentes do Solo , Espectrometria de Massas por Ionização por Electrospray , Estrobilurinas , Tiametoxam , Triazóis/análise
16.
Food Chem ; 210: 26-34, 2016 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-27211616

RESUMO

Liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) is a primary tool for analysis of low volatility compounds in complex matrices. However, complex matrices, such as different types of tea, complicate analysis through ionization suppression or enhancement. In this study, sample preparation by a refined QuEChERS method combined with a dilution strategy removed almost all matrix effects caused by six types of tea. Tea samples were soaked with water and extracted with acetonitrile, cleaned up with a combination of PVPP (160mg) and GCB (20mg), and dried. Dried extracts were diluted with 20mL acetonitrile/water (15:85, v/v) before analysis by UPLC-MS/MS. The average recoveries of eight neonicotinoid insecticides (dinotefuran, nitenpyram, thiamethoxam, imidacloprid, clothianidin, imidaclothiz, acetamiprid, and thiacloprid) ranged from 66.3 to 108.0% from tea samples spiked at 0.01-0.5mgkg(-1). Relative standard deviations were below 16% for all recovery tests. The limit of quantification ranged from 0.01 to 0.05mgkg(-1).


Assuntos
Inseticidas/análise , Chá/química , Cromatografia Líquida , Guanidinas/análise , Imidazóis/análise , Neonicotinoides , Nitrocompostos/análise , Oxazinas/análise , Piridinas/análise , Espectrometria de Massas em Tandem/métodos , Tiametoxam , Tiazinas/análise , Tiazóis/análise
17.
Environ Toxicol Chem ; 35(2): 311-21, 2016 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-26467536

RESUMO

Limited data are available on the fate of clothianidin under realistic agricultural production conditions. The present study is the first large-scale assessment of clothianidin residues in soil and bee-relevant matrices from corn and canola fields after multiple years of seed-treatment use. The average soil concentration from 50 Midwest US corn fields with 2 yr to 11 yr of planting clothianidin-treated seeds was 7.0 ng/g, similar to predicted concentrations from a single planting of Poncho 250-treated corn seeds (6.3 ng/g). The water-extractable (i.e., plant-bioavailable) clothianidin residues in soil were only 10% of total residues. Clothianidin concentrations in soil reached a plateau concentration (amount applied equals amount dissipated) in fields with 4 or more application years. Concentrations in corn pollen from these fields were low (mean: 1.8 ng/g) with no correlation to total years of use or soil concentrations. For canola, soil concentrations from 27 Canadian fields with 2 yr to 4 yr of seed treatment use (mean = 5.7 ng/g) were not correlated with use history, and plant bioavailability was 6% of clothianidin soil residues. Average canola nectar concentrations were 0.6 ng/g and not correlated to use history or soil concentrations. Under typical cropping practices, therefore, clothianidin residues are not accumulating significantly in soil, plant bioavailability of residues in soil is limited, and exposure to pollinators will not increase over time in fields receiving multiple applications of clothianidin.


Assuntos
Abelhas/efeitos dos fármacos , Brassica rapa/química , Guanidinas/análise , Inseticidas/análise , Pólen/química , Poluentes do Solo/análise , Solo/química , Tiazóis/análise , Zea mays/química , Adsorção , Agricultura , Animais , Canadá , Europa (Continente) , Guanidinas/farmacocinética , Inseticidas/farmacocinética , Meio-Oeste dos Estados Unidos , Neonicotinoides , Resíduos de Praguicidas/análise , Néctar de Plantas/química , Tiazóis/farmacocinética
18.
J Chromatogr A ; 1428: 220-7, 2016 Jan 08.
Artigo em Inglês | MEDLINE | ID: mdl-26545338

RESUMO

A study was carried out to evaluate the possible presence of thiamethoxam, clothianidin and imidacloprid, as well as the metabolic breakdown products of these three neonicotinoids in pollen and honey obtained from brood chamber combs of honeybee colonies located next to sunflower and maize crops from coated seeds. Samples were analyzed by liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry detector, in combination with accurate mass tools such as diagnostic ions by exact mass, chlorine mass filters, and MS/MS experiments. The presence of thiamethoxam and clothianidin was confirmed in some of the pollen samples analyzed. Moreover, different metabolites of neonicotinoids were tentatively detected in the pollen and honey samples collected. The results suggested that four metabolites were found in the honey samples, while for pollen samples eleven metabolites were identified; among these, five were considered for the first time as metabolic breakdown products in sunflower and maize plants.


Assuntos
Técnicas de Química Analítica/métodos , Produtos Agrícolas/química , Guanidinas/análise , Mel/análise , Imidazóis/análise , Nitrocompostos/análise , Oxazinas/análise , Pólen/química , Tiazóis/análise , Animais , Cromatografia Líquida , Guanidinas/metabolismo , Helianthus/química , Imidazóis/metabolismo , Neonicotinoides , Nitrocompostos/metabolismo , Oxazinas/metabolismo , Reprodutibilidade dos Testes , Sementes/química , Espectrometria de Massas em Tandem , Tiametoxam , Tiazóis/metabolismo , Zea mays/química
19.
Environ Toxicol Chem ; 35(2): 295-302, 2016 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-26332416

RESUMO

Neonicotinoid insecticides, especially as seed treatments, have raised concerns about environmental loading and impacts on pollinators, biodiversity, and ecosystems. The authors measured concentrations of neonicotinoid residues in the top 5 cm of soil before planting of maize (corn) in 18 commercial fields with a history of neonicotinoid seed treatment use in southwestern Ontario in 2013 and 2014 using liquid chromatography-tandem mass spectrometry with electrospray ionization. A simple calculator based on first-order kinetics, incorporating crop rotation, planting date, and seed treatment history from the subject fields, was used to estimate dissipation rate from the seed zone. The estimated half-life (the time taken for 50% of the insecticide to have dissipated by all mechanisms) based on 8 yr of crop history was 0.64 (range, 0.25-1.59) yr and 0.57 (range, 0.24-2.12) yr for 2013 and 2014, respectively. In fields where neonicotinoid residues were measured in both years, the estimated mean half-life between 2013 and 2014 was 0.4 (range, 0.27-0.6) yr. If clothianidin and thiamethoxam were used annually as a seed treatment in a typical crop rotation of maize, soybean, and winter wheat over several years, residues would plateau rather than continue to accumulate. Residues of neonicotinoid insecticides after 3 yr to 4 yr of repeated annual use tend to plateau to a mean concentration of less than 6 ng/g in agricultural soils in southwestern Ontario.


Assuntos
Colinérgicos/análise , Inseticidas/análise , Sementes/química , Poluentes do Solo/análise , Zea mays/química , Agricultura , Ecossistema , Guanidinas/análise , Meia-Vida , Neonicotinoides , Nitrocompostos/análise , Ontário , Oxazinas/análise , Resíduos de Praguicidas/análise , Tiametoxam , Tiazóis/análise
20.
Chemosphere ; 144: 2321-8, 2016 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-26606186

RESUMO

Neonicotinoid insecticides (NIs) and their transformation products were detected in honey, pollen and honey bees, (Apis mellifera) from hives located within 30 km of the City of Saskatoon, Saskatchewan, Canada. Clothianidin and thiamethoxam were the most frequently detected NIs, found in 68 and 75% of honey samples at mean concentrations of 8.2 and 17.2 ng g(-1) wet mass, (wm), respectively. Clothianidin was also found in >50% of samples of bees and pollen. Concentrations of clothianidin in bees exceed the LD50 in 2 of 28 samples, while for other NIs concentrations were typically 10-100-fold less than the oral LD50. Imidaclorpid was detected in ∼30% of samples of honey, but only 5% of pollen and concentrations were

Assuntos
Abelhas/química , Guanidinas/análise , Mel/análise , Imidazóis/análise , Inseticidas/análise , Nitrocompostos/análise , Oxazinas/análise , Pólen/química , Tiazóis/análise , Animais , Abelhas/crescimento & desenvolvimento , Guanidinas/metabolismo , Imidazóis/metabolismo , Limite de Detecção , Neonicotinoides , Nitrocompostos/metabolismo , Oxazinas/metabolismo , Saskatchewan , Estações do Ano , Tiametoxam , Tiazóis/metabolismo
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