RESUMO
Mycotoxin production by aflatoxin B1 (AFB1) -producing Aspergillus flavus Zt41 and sterigmatocystin (ST) -hyperproducer Aspergillus creber 2663 mold strains on corn and rice starch, both of high purity and nearly identical amylose-amylopectin composition, as the only source of carbon, was studied. Scanning electron microscopy revealed average starch particle sizes of 4.54 ± 0.635 µm and 10.9 ± 2.78 µm, corresponding to surface area to volume ratios of 127 1/µm for rice starch and 0.49 1/µm for corn starch. Thus, a 2.5-fold difference in particle size correlated to a larger, 259-fold difference in surface area. To allow starch, a water-absorbing powder, to be used as a sole food source for Aspergillus strains, a special glass bead system was applied. AFB1 production of A. flavus Zt41 was determined to be 437.6 ± 128.4 ng/g and 90.0 ± 44.8 ng/g on rice and corn starch, respectively, while corresponding ST production levels by A. creber 2663 were 72.8 ± 10.0 µg/g and 26.8 ± 11.6 µg/g, indicating 3-fivefold higher mycotoxin levels on rice starch than on corn starch as sole carbon and energy sources. KEY POINTS: ⢠A glass bead system ensuring the flow of air when studying powders was developed. ⢠AFB1 and ST production of A. flavus and A. creber on rice and corn starches were studied. ⢠3-fivefold higher mycotoxin levels on rice starch than on corn starch were detected.
Assuntos
Oryza , Amido , Zea mays , Oryza/química , Zea mays/química , Amido/metabolismo , Aspergillus/metabolismo , Aspergillus flavus/metabolismo , Aflatoxina B1/biossíntese , Aflatoxina B1/metabolismo , Esterigmatocistina/biossíntese , Esterigmatocistina/metabolismo , Microscopia Eletrônica de Varredura , Tamanho da Partícula , Micotoxinas/metabolismo , Micotoxinas/biossíntese , VidroRESUMO
This study aimed to determine the environmental and health risks of the heavy metal levels in the Danube River in Hungary. The metals, including Fe, Mn, Zn, Cu, Ni, Cr, Pb, and As, were measured in the period from 2013 to 2019. The Spearman correlation and heatmap cluster analysis were utilized to determine the origin of pollution and the factors that control surface water quality. Several indices, such as the heavy metal pollution index (HPI), metal index (MI), hazard quotient oral and dermal (HQ), hazard index oral and dermal (HI), and carcinogenic risk (CR), were conducted to evaluate the potential risks for the environment and human health. The values of the HPI were between the range of 15 < HPI < 30, which indicated moderate pollution; however, the MI results showed high pollution in Dunaföldvár and Hercegszántó cities. The ecological risk (RI < 30) and HI values (< 1) showed low environmental risks and non-carcinogenic impacts of the existing metals, either on adults or children. The mean CR value of oral arsenic was 2.2E-04 and 2.5E-04 during April-September and October-March, respectively, indicating that children were the most vulnerable to arsenic-carcinogenic oral effects. While lead's CR oral values for children during April-September exceeded the threshold of 1.0E-04, chromium's oral and dermal CR values for both adults and children were 2.08E-04, 6.11E-04, 1.97E-04, and 5.82E-04 during April-September and October-March, respectively. These results demonstrate the potential carcinogenic risks related to chromium exposure within the two pathways in Hungary and highlight the need for effective measures to mitigate these risks.
Assuntos
Arsênio , Boidae , Metais Pesados , Criança , Adulto , Animais , Humanos , Arsênio/toxicidade , Arsênio/análise , Rios , Hungria , Método de Monte Carlo , Monitoramento Ambiental , Metais Pesados/toxicidade , Metais Pesados/análise , Cromo/toxicidade , Cromo/análise , Medição de Risco , ChinaRESUMO
Neonicotinoid insecticides are widely used agents in agriculture to control a broad range of insect pests. Although use of neonicotinoid pesticides has resulted in the widespread contamination of surface waters, sublethal toxicity data of these products in relation to non-target aquatic biota are still poor. Therefore, the objective of this study was to assess the effects of two neonicotinoid pesticides with widespread use on the basic physiological functions: the thoracic limb activity and heart rate of Daphnia magna, and to screen for their potential to affect the cytochrome P450 monooxygenase system (ECOD activity) of daphnids. The considered pesticides were the acetamiprid- and thiacloprid based products Mospilan 20 SG and Calypso 480 SC, respectively. The dose-dependent variation in the three biological endpoints considered were assessed following 24 h exposures. The two neonicotinoid formulations elicited significant depression on the thoracic limb activity and heart rate of daphnids at doses close to the immobility thresholds of formulations (48h-EC50: Mospilan 20 SG = 190 mg L-1; Calypso 480 SC = 120 mg L-1), an effect mainly attributable to the overall drop in the general health status of the organisms. The alterations in the physiological traits were significant at exposures to 190 mg L-1 for Mospilan 20 SG and 48 mg L-1 for Calypso 480 SC. The dose related variation in the ECOD activity of daphnids exposed to the selected neonicotinoid formulations followed a biphasic pattern, with starting effective doses for Mospilan 20 SG of 6.3 mg L-1 (=1/20 of 48h-EC50 for Daphnia neonates), and for Calypso 480 SC of 0.034 mg L-1 (=1/4000 of 48h-EC50). Maximal ECOD activity (2.2 fold increase vs. controls) was induced by Mospilan 20 SG in daphnids exposed to 114 mg L-1 product (=48 h-EC20), and by Calypso 480 SC (1.8 fold increase) at 5.2 mg L-1 dose (=1/20 of 48 h-EC50). Our results outlined significant alterations in the physiological traits and ECOD activity in exposed daphnids at concentrations below the immobility thresholds (48 h-EC50) of the products used as benchmarks to rate their toxicity risks to aquatic biota. Therefore, we think our findings might deserve consideration in the environmental risk evaluation of these products.
Assuntos
Inseticidas , Poluentes Químicos da Água , Animais , Daphnia , Inseticidas/toxicidade , Neonicotinoides/toxicidade , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/toxicidadeRESUMO
An enzyme-linked fluorescent immunoassay (ELFIA) method has been developed for the quantitative analytical determination of the herbicide active ingredient glyphosate in environmental matrices (surface water, soil, and plant tissues). Glyphosate, as a ubiquitous agricultural pollutant, is a xenobiotic substance with exposure in aquatic and terrestrial ecosystems due its extremely high worldwide application rate. The immunoassay developed in Project Aquafluosense is part of a fluorescence-based instrumentation setup for the in situ determination of several characteristic water quality parameters. The 96-well microplate-based competitive immunoassay method applies fluorescence signal detection in the concentration range of 0-100 ng/mL glyphosate. Application of the fluorescent signal provides a limit of detection of 0.09 ng/mL, which is 2.5-fold lower than that obtained with a visual absorbance signal. Beside the improved limit of detection, determination by fluorescence provided a wider and steeper dynamic range for glyphosate detection. No matrix effect appeared for the undiluted surface water samples, while plant tissues and soil samples required dilution rates of 1:10 and 1:100, respectively. No cross-reaction was determined with the main metabolite of glyphosate, N-aminomethylphosphonic acid, and related compounds.
Assuntos
Poluentes Ambientais , Herbicidas , Ecossistema , Imunofluorescência , Glicina/análogos & derivados , Herbicidas/análise , Solo , Xenobióticos , GlifosatoRESUMO
There is a great concern about the decline of pollinators, and neonicotinoids emerging bee disorders are assumed to play a significant role. Since changes in learning ability has been observed in honey bees exposed to some acetylcholine esterase (AChE) inhibitors, we therefore, tested in vitro the effect of four neonicotinoids on purified eel AChE. AChE activity was inhibited in a concentration-dependent manner, and calculated IC50 values for thiamethoxam (IC50 = 414 µM) and clothianidin (IC50 = 160 µM) were found to be much higher compared to acetamiprid (IC50 = 75.2 µM) and thiacloprid (IC50 = 87.8 µM). The Lineweaver-Burk reciprocal plots for acetamiprid shows unchanged Vmax and increased Km values with inhibitor concentrations, while analysis of Michaelis-Menten plots shows predominantly competitive mechanism. The inhibition constant value (Ki = 24.3 µM) indicates strong binding of the acetamiprid complex to AChE. Finally, the four tested neonicotinoids are not a uniform group regarding their blocking ability. Our results suggest a previously not established, direct AChE blocking mechanism of neonicotinoids tested, thus the neuronal AChE enzyme is likely among the direct targets of the neonicotinoid insecticides. We conclude, that these AChE inhibitory effects may also contribute to toxic effects on the whole exposed animal.
Assuntos
Acetilcolinesterase/química , Inibidores da Colinesterase/química , Electrophorus , Proteínas de Peixes , Guanidinas/química , Neonicotinoides/química , Nitrocompostos/química , Oxazinas/química , Tiazóis/química , Animais , Proteínas de Peixes/antagonistas & inibidores , Proteínas de Peixes/química , TiametoxamRESUMO
Evaluation of water quality is crucial for managing surface water effectively, ensuring its suitability for human use, and sustaining the environment. In the lower Danube River basin, various methods were employed to assess surface water quality for irrigation, drinking, human health risk purposes and the main mechanism control the surface water chemistry. These methods included water quality indicators (WQIs), complex statistical analyses, geographic information systems (GIS), Monte Carlo simulation, and geochemical modeling. Physicochemical analyses of surface water samples revealed primarily Ca-Mg-HCO3- is the dominant water types. Principal component analysis (PCA), ionic ratios and piper, chloro alkaline index, Chadha, and Gibbs diagrams identified three distinct water characteristics influenced by water-rocks interaction, evaporation, ions exchange, and human activities. The geochemical modeling showed Danube River water's strong ability to dissolve gypsum, halite, and anhydrite (SI < 0) and precipitate aragonite, dolomite, and calcite with saturation index (SI) value greater than 0 along its flow path. The irrigation water quality index (IWQI = 99.6-107.6), sodium adsorption ratio (SAR = 0.37-0.68), sodium percentage (Na% = 13.7-18.7), soluble sodium percentage (SSP = 12.5-17.5), Potential Salinity (PS = 0.73-1.6), and Residual Sodium Carbonate (RSC = - 1.27-0.58) values were used, mainly indicating acceptable quality with some limitations. Danube River water was unsuitable for drinking based on WQI value (WQI = 81-104). Oral exposure of children to specific components showed a higher hazard index (HI > 1) compared to adults, indicating a 2.1 times higher overall non-carcinogenic risk hazard index. However, Monte Carlo simulation demonstrated negligible iron, manganese, and nitrate health hazards for both age groups. These findings are valuable for water quality management decisions, contributing to long-term resource sustainability.
RESUMO
The environmental load by isoxaflutole and its formulated herbicide products has increasingly become apparent because, after the ban of atrazine, isoxaflutole has become its replacement active ingredient (a.i.). Obtaining information regarding the fate of this a.i. in environmental matrices and its ecotoxicological effects on aquatic organisms is essential for the risk assessment of the herbicide. In this study, the effects of Merlin Flexx- and Merlin WG75 formulated isoxaflutole-based herbicide products and two selected additives (cyprosulfamide safener and 1,2-benzisothiazol-3(2H)-one antimicrobial agent) were investigated on Raphidocelis subcapitata in growth inhibition assays. In ecotoxicological tests, two conventional (optical density and chlorophyll-a content) and two induced fluorescence-based (Fv*/Fp: efficiency of the photosystem PSII and Rfd* changes in the observed ratio of fluorescence decrease) endpoints were determined by UV-spectrophotometer and by our FluoroMeter Module, respectively. Furthermore, dissipation of isoxaflutole alone and in its formulated products was examined by an HPLC-UV method. In ecotoxicological assays, the fluorescence-based Rfd* was observed as the most sensitive endpoint. In this study, the effects of the safener cyprosulfamide and the antimicrobial agent 1,2-benzisothiazol-3(2H)-one on R. subcapitata is firstly reported. The results indicated that the isoxaflutole-equivalent toxicity of the mixture of the isoxaflutole-safener-antimicrobial agent triggered lower toxicity (EC50 = 2.81 ± 0.22 mg/L) compared to the individual effect of the a.i. (EC50 = 0.02 ± 0.00 mg/L). The Merlin Flexx formulation (EC50 = 27.04 ± 1.41 mg/L) was found to be approximately 50-fold less toxic than Merlin WG75, which can be explained by the different chemical characteristics and quantity of additives in them. The additives influenced the dissipation of the a.i. in Z8 medium, as the DT50 value decreased by approximately 1.2- and 3.5-fold under light and dark conditions, respectively.
RESUMO
Neonicotinoids are widely used insecticides around the world and are preserved permanently in soils and appear in surface waters posing an increased threat to ecosystems. In the present study, we exposed adult specimens of amphipod Dikerogammarus villosus to environmentally relevant and higher concentrations of two widely used agricultural neonicotinoids, clothianidin (CLO) and imidacloprid (IMI), for 2â¯days. The acute effects were investigated at the behavioral (immobility time and swimming activity) and biochemical (glutathione S-transferase [GST] and acetylcholine esterase [AchE] activity) levels. All CLO concentrations used (64â¯nM, 128â¯nM, 192â¯nM) significantly decreased the immobility time and swimming activity. In the case of IMI, the immobility time decreased significantly only at the highest concentration applied (977â¯nM), but the distance travelled by the animals significantly decreased even at lower concentrations (78â¯nM and 313â¯nM). The GST enzyme activity did not change in the CLO-treated groups, however, the 626â¯nM and 977â¯nM IMI concentrations significantly increased the GST activity. Similarly, to the behavioral level, all CLO concentrations significantly decreased the AchE activity. In contrast, IMI has a significant stimulating effect on the AchE activity at the 313â¯nM, 626â¯nM, and 977â¯nM concentrations. Based on the authors' best knowledge, this is the first study to investigate the effects of CLO and IMI at environmentally-relevant concentrations on D. villosus. Our findings contribute to the understanding of the physiological effects of neonicotinoids.
Assuntos
Anfípodes , Inseticidas , Animais , Ecossistema , Guanidinas , Inseticidas/toxicidade , Neonicotinoides/toxicidade , Nitrocompostos/toxicidade , TiazóisRESUMO
Project Aquafluosense is designed to develop prototypes for a fluorescence-based instrumentation setup for in situ measurements of several characteristic parameters of water quality. In the scope of the project an enzyme-linked fluorescent immunoassay (ELFIA) method has been developed for the detection of several environmental xenobiotics, including mycotoxin zearalenone (ZON). ZON, produced by several plant pathogenic Fusarium species, has recently been identified as an emerging pollutant in surface water, presenting a hazard to aquatic ecosystems. Due to its physico-chemical properties, detection of ZON at low concentrations in surface water is a challenging task. The 96-well microplate-based fluorescence instrument is capable of detecting ZON in the concentration range of 0.09-400 ng/mL. The sensitivity and accuracy of the analytical method has been demonstrated by a comparative assessment with detection by high-performance liquid chromatography and by total internal reflection ellipsometry. The limit of detection of the method, 0.09 ng/mL, falls in the low range compared to the other reported immunoassays, but the main advantage of this ELFIA method is its efficacy in combined in situ applications for determination of various important water quality parameters detectable by induced fluorimerty-e.g., total organic carbon content, algal density or the level of other organic micropollutants detectable by immunofluorimetry. In addition, the immunofluorescence module can readily be expanded to other target analytes if proper antibodies are available for detection.
Assuntos
Monitoramento Ambiental , Ensaio de Imunoadsorção Enzimática , Imunofluorescência , Fusarium/metabolismo , Microbiologia da Água , Zearalenona/análise , Limite de Detecção , Reprodutibilidade dos Testes , Espectrometria de Fluorescência , Qualidade da ÁguaRESUMO
The analytical detection of chlorophenoxycarboxylic-acid-type herbicides (2,4-D, dichloprop, MCPA, etc.) in environmental samples is often a problem in instrumental analysis, as these compounds containing free carboxylic groups require chemical derivatisation prior to gas chromatographic (GC) methods. Nine chlorophenoxy-acid-type herbicide active ingredients have been derivatised successfully with trimethylsilyl N,N-dimethyl carbamate and t-butyldimethylsilyl N,N-dimethyl carbamate by forming their trimethylsilyl (TMS) and t-butyldimethylsilyl (TBDMS) esters, respectively. The detection and determination of the derivatives were performed by capillary gas chromatography-mass spectrometry. The study included determination of retention indices, mass spectral properties and comparison of derivatives produced. The mass spectra of TBDMS derivatives are usually dominated by very characteristic ions [M-57](+) resulting from the cleavage of t-butyl moiety during electron impact (EI) ionisation in the mass spectrometer. Limits of detection were 5 to 100 pg applying GC with EI-MS detection in full scan mode. The method, using SPE sample preparation, was applied for the analysis of 115 ground water and surface water samples collected in Békés County, Hungary in 2009.
Assuntos
Ácidos Carboxílicos/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Herbicidas/análise , Poluentes Químicos da Água/análise , Ácidos Carboxílicos/química , Limite de DetecçãoRESUMO
Thiacloprid (TCL) uptake by maize plants that emerge from coated seeds has been investigated and characterized via measurements of the compound in the guttation liquid. TCL levels were determined in the guttation liquid: (a) under field and semi-field conditions, (b) for different maize varieties, (c) applying different dosages, and (d) as affected by cross-contamination between maize seeds via soil. Cross-contamination was described by uptake interactions between seeds coated with TCL and neighboring seeds not coated or coated with other neonicotinoids, e.g., either thiamethoxam (TMX) or clothianidin (CLO). TCL levels remained under 100 µg/mL in the guttation liquid under field conditions, and were quantifiable even on the 39th day after planting of coated seeds. Higher levels up to 188.6 µg/mL were detected in plants grown under semi-field conditions in pots. Levels in the guttation liquid were also found to be influenced by the applied dosages. The uptake of TCL was found to vary for different maize varieties. Appearance of TCL as a cross-contaminant in the guttation liquid of neighboring plants emerging from non-coated maize seeds indicates translocation of the compound via soil. Peak levels of TCL cross-contamination were found to be lower (43.6 µg/mL) than the corresponding levels in the parent maize plants emerging from coated seeds (107.5 µg/mL), but values converge to each other. Similar trends were observed with neighboring seeds coated with other neonicotinoids (TMX or CLO). The translocation rate of TCL and its uptake by other plants seem to be lower than that of TMX or CLO.
Assuntos
Inseticidas , Neonicotinoides/análise , Sementes/química , Tiazinas/análise , Zea mays/química , Inseticidas/análiseRESUMO
Research on the ability of lactic acid bacteria (LAB) to bind aflatoxin B1 (AFB1) has mostly been focusing on lactobacilli and bifidobacteria. In this study, the AFB1 binding capacities of 20 Enterococcus strains belonging to E. casseliflavus, E. faecalis, E. faecium, E. hirae, E. lactis, and E. mundtii, 24 Pediococcus strains belonging to species P. acidilactici, P. lolii, P. pentosaceus, and P. stilesii, one strain of Lactococcus formosensis and L.garviae, and 3 strains of Weissella soli were investigated in MRS broth at 37 °C at 0.2 µg/mL mycotoxin concentration. According to our results, among non-lactobacilli LAB, the genera with the best AFB1 binding abilities were genus Pediococcus, with a maximum binding percentage of 7.6% by P. acidilactici OR83, followed by genus Lactococcus. For AFB1 bio-detoxification purposes, beside lactobacilli, pediococci can also be chosen, but it is important to select a strain with better binding properties than the average value of its genus. Five Pediococcus strains have been selected to compare their sterigmatocystin (ST) binding abilities to AFB1 binding, and a 2-3-fold difference was obtained similar to previous findings for lactobacilli. The best strain was P. acidilactici OR83 with 18% ST binding capacity. This is the first report on ST binding capabilities of non-Lactobacillus LAB strains.
Assuntos
Aflatoxina B1/metabolismo , Animais de Zoológico/metabolismo , Animais de Zoológico/microbiologia , Lactobacillales/metabolismo , Lactobacillus , Esterigmatocistina/metabolismo , Aflatoxina B1/genética , Aflatoxina B1/isolamento & purificação , Animais , Cromatografia Líquida de Alta Pressão/métodos , Lactobacillales/genética , Lactobacillales/isolamento & purificação , Micotoxinas/genética , Micotoxinas/isolamento & purificação , Micotoxinas/metabolismo , Ligação Proteica/fisiologia , Esterigmatocistina/isolamento & purificaçãoRESUMO
Due to global climate change, mould strains causing problems with their mycotoxin production in the tropical-subtropical climate zone have also appeared in countries belonging to the temperate zone. Biodetoxification of crops and raw materials for food and feed industries including the aflatoxin B1 (AFB1) binding abilities of lactobacilli is of growing interest. Despite the massive quantities of papers dealing with AFB1-binding of lactobacilli, there are no data for microbial binding of the structurally similar mycotoxin sterigmatocystin (ST). In addition, previous works focused on the detection of AFB1 in extracts, while in this case, analytical determination was necessary for the microbial biomass as well. To test binding capacities, a rapid instrumental analytical method using high-performance liquid chromatography was developed and applied for measurement of AFB1 and ST in the biomass of the cultured bacteria and its supernatant, containing the mycotoxin fraction bound by the bacteria and the fraction that remained unbound, respectively. For our AFB1 and ST adsorption studies, 80 strains of the genus Lactobacillus were selected. Broths containing 0.2 µg/mL AFB1and ST were inoculated with the Lactobacillus test strains. Before screening the strains for binding capacities, optimisation of the experiment parameters was carried out. Mycotoxin binding was detectable from a germ count of 107 cells/mL. By studying the incubation time of the cells with the mycotoxins needed for mycotoxin-binding, co-incubation for 10 min was found sufficient. The presence of mycotoxins did not affect the growth of bacterial strains. Three strains of L. plantarum had the best AFB1 adsorption capacities, binding nearly 10% of the mycotoxin present, and in the case of ST, the degree of binding was over 20%.
Assuntos
Aflatoxina B1/química , Lactobacillales/química , Esterigmatocistina/químicaRESUMO
Various environmental and ecotoxicological aspects related to applications of neonicotinoid insecticides are assessed. Dosages of neonicotinoids applied in seed coating materials were determined and are compared to other applications (spray and granule). Environmental levels in soils and affecting factors in translocation are discussed. Excretion of neonicotinoids via guttation from coated maize seeds up to two months upon emergence, as well as cross-contamination of plants emerged from non-coated seeds or weeds nearby have been demonstrated. Contamination of surface waters is discussed in scope of a worldwide review and the environmental fate of the neonicotinoid active ingredients and the formulating surfactant appeared to be mutually affected by each other. Toxicity of neonicotinoid active ingredients and formulations on Daphnia magna completed with some investigations of activity of the detoxifying glutathione S-transferase enzyme demonstrated the modified toxicity due to the formulating agents. Electrophysiological results on identified central neurons of the terrestrial snail Helixpomatia showed acetylcholine antagonist (inhibitory) effects of neonicotinoid insecticide products, but no agonist (ACh-like) effects were recorded. These data also suggested different molecular targets (nicotinergic acetylcholine receptors and acetylcholine esterase enzyme) of neonicotinoids in the snail central nervous system.
Assuntos
Inseticidas , Neonicotinoides , Nitrocompostos , Poluentes da Água , Animais , Daphnia , Neonicotinoides/toxicidade , Sementes , Poluentes da Água/toxicidadeRESUMO
Glyphosate-based herbicides (GBH) are currently the most widely used agrochemicals for weed control. Environmental risk assessments (ERA) on nontarget organisms mostly consider the active ingredients (AIs) of these herbicides, while much less is known on effects of commercial GBH formulations that are actually applied in the field. Moreover, it is largely unknown to what extent different soil characteristics alter potential side effects of herbicides. We conducted a greenhouse experiment growing a model weed population of Amaranthus retroflexus in arable field soil with either 3.0 or 4.1% soil organic matter (SOM) content and treated these weeds either with GBHs (Roundup LB Plus, Touchdown Quattro, Roundup PowerFlex) or their respective AIs (isopropylammonium, diammonium or potassium salts of glyphosate) at recommended dosages. Control pots were mechanically weeded. Nontarget effects were assessed on the surface activity of the springtail species Sminthurinus niger (pitfall trapping) and litter decomposition in the soil (teabag approach). Both GBHs and AIs increased the surface activity of springtails compared to control pots; springtail activity was higher under GBHs than under corresponding AIs. Stimulation of springtail activity was much higher in soil with higher SOM content than with low SOM content (significant treatment x SOM interaction). Litter decomposition was unaffected by GBHs, AIs or SOM levels. We suggest that ERAs for pesticides should be performed with actually applied herbicides rather than only on AIs and should also consider influences of different soil properties.
Assuntos
Artrópodes , Herbicidas , Animais , Glicina/análogos & derivados , Solo , GlifosatoRESUMO
Neonicotinoid uptake by maize plants emerged from coated seeds and by two common weeds grown in close proximity to coated seeds has been studied. Uptake of thiamethoxam (TMX) and clothianidin (CLO) have been characterized via guttation liquid measurements. The creeping thistle (Cirsium arvense), a well-known maize weed, as well as red poppy or Flanders poppy (Papaver rhoeas) were chosen as model species. The results confirmed that cross-contamination may occur by uptake of the neonicotinoid AIs through soil from neighbouring plants that emerged from coated seeds. Although the levels of these neonicotinoids were substantially lower in the guttation liquid of the weeds than in that of maize plants emerged from coated seeds, the compounds were detected up to 36th day after planting of the maize seeds. The highest peak concentrations of TMX were around 150 and 21â¯mgâ¯L-1, while similar data for CLO were around 70 and 21â¯mgâ¯L-1 for maize and creeping thistle, respectively. Mostly due to its higher guttation intensity significantly lower values were determined for red poppy (0.740â¯mgâ¯L-1).
Assuntos
Guanidinas/metabolismo , Inseticidas/metabolismo , Neonicotinoides/metabolismo , Nitrocompostos/metabolismo , Oxazinas/metabolismo , Plantas Daninhas/metabolismo , Tiazóis/metabolismo , Controle de Plantas Daninhas , Zea mays/metabolismo , Cirsium/metabolismo , Papaver/metabolismo , Sementes/química , TiametoxamRESUMO
Substance losses of linear alkylbenzene sulfonates (LASs) in a neat surfactant mixture, in an insecticide formulation Mospilan 20 SG, and in solutions with different neonicotinoid active ingredients (AIs) was studied in distilled water and in surface water samples originated from River Danube. Analytical measurements were performed both by HPLC-UV and commercial ELISA methods. Loss rates of LASs were found different in these aqueous matrices, with decomposition rates higher for the neat surfactant mixture than for Mospilan 20 SG (nearly 2- and 9-fold in distilled water and in surface water from River Danube, respectively). Half-lives determined in surface water from River Danube were shown to be affected by the presence of neonicotinoid AIs thiaclopridâ¯>â¯imidaclopridâ¯>â¯acetamiprid (ACE), while clothianidin and thiamethoxam did not affect LAS decomposition. Aquatic toxicity of Mospilan 20 SG, along with that of its AI ACE and co-formulant LAS, as well as the mixture of ACE and LAS was also investigated in the 48-h acute immobilisation assay on the water flea (Daphnia magna) aquatic indicator organism. LAS appeared to be significantly (8-fold) more toxic in the D. magna test than ACE, and the toxicity of the formulated insecticide was found to be 1.3 and 19.6 times higher than explained by its AI and LAS content, respectively, indicating synergistic toxicity. The strongest synergy between ACE and LASs was observed, when the neat forms of the two substances were applied in combination at concentrations equivalent to those in Mospilan 20 SG.
Assuntos
Ácidos Alcanossulfônicos/toxicidade , Inseticidas/toxicidade , Neonicotinoides/toxicidade , Poluentes Químicos da Água/toxicidade , Animais , Organismos Aquáticos , Chironomidae , Cladocera , Daphnia , Tensoativos , Testes de ToxicidadeRESUMO
A rapid and simple method is described for the simultaneous determination of 6 phenols (phenol, o-, m-, p-cresol, catechol and resorcinol) and 19 chlorophenols (all mono-, di-, tri-, and tetrachlorophenol isomers and pentachlorophenol) present in aqueous samples. The method is based on derivatization with trimethylsilyl-N,N-dimethylcarbamate (TMSDMC). In contrast to other derivatization agents, TMSDMC instantaneously reacts with the phenolic compounds at room temperature and no further sample processing is necessary prior to instrumental analysis. The determination of the derivatives was performed by capillary gas chromatography-mass spectrometry (GC-MS). The stability of the most instable trimethylsilyl derivative (pentachlorophenol) was studied using different excess levels of the derivatization reagent. The derivatization method was tested on spiked water samples preconcentrated by solid phase extraction on Isolute ENV+ cartridge. The overall method gave detection limits of 0.01-0.25 microg/L for all compounds and < 0.05 microg/L for 17 of them.
Assuntos
Clorofenóis/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Fenóis/análise , Compostos de Trimetilsilil/química , Calibragem , Reprodutibilidade dos Testes , Sensibilidade e EspecificidadeRESUMO
Mussels are among the most frequently used invertebrate animals in aquatic toxicology to detect toxic exposure in the environment. The presence and activity of a cellular defence system, the multixenobiotic resistance (MXR) mechanism, was also established in these organisms. In isolated gill tissues of dreissenid mussels (D. bugensis) the MXR activity was assayed after treatment by commercially available insecticides (formulated products) which contain neonicotinoids as their active ingredients: Actara (thiamethoxam), Apacs (clothianidin), Calypso (thiacloprid) and Kohinor (imidacloprid), respectively. While applying the accumulation assay method, 0.5 µM rhodamine B was used as model substrate and 20 µM verapamil as model inhibitor of the MXR mechanism. In acute (in vitro) experiments when isolated gills were co-incubated in graded concentrations of insecticides and rhodamine B simultaneously, Calypso and Kohinor treatment resulted increasing rhodamine accumulation. Chemical analysis of gills in vitro incubated in insecticides demonstrated higher tissue concentrations of thiamethoxam, clothianidin and thiacloprid in the presence of verapamil suggesting that the active ingredients of Actara, Apacs and Calypso are potential substrates of the MXR mediated cellular efflux. In contrast, verapamil did significantly alter the accumulated imidacloprid concentrations in gills, suggesting that the active component of Kohinor is not transported by the MXR mechanism. Chronic (in vivo) exposures of the intact animals in lower, 1, 10 mg/L concentration of neonicotinoid products, resulted in a decreased level of both rhodamine accumulation and verapamil inhibition by the 12th-14th days of treatment. These results suggest an enhancement of MXR activity (chemostimulation), building up gradually in the animals exposed to Actara, Apacs and Kohinor, respectively. Neonicotinoid-type insecticides are generally considered as selective neurotoxins for insects, targeting the nicotinic type acetylcholine receptors (nAChRs) in their central nervous system. Our present results provide the first evidences that neonicotinoid insecticides are also able to alter the transmembrane transport mechanisms related to the MXR system.