RESUMO
Biobeds are presented as an alternative for good pesticide wastewater management on farms. This work proposes a new test for in-situ biomonitoring of pesticide detoxification in biobeds. It is based on the assessment of visually appreciable injuries to Eisenia fetida. The severity of the injury to each exposed individual is assessed from the morphological changes observed in comparison with the patterns established in seven categories and, an injury index is calculated. A linear relationship between the proposed injury index and the pesticide concentration was determined for each pesticide sprayed individually in the biomixture. The five pesticides used were atrazine, prometryn, clethodim, haloxyfop-P-methyl and dicamba. In addition, a multiple linear regression model (i.e., a multivariate response surface) was fitted, which showed a good generalization capacity. The sensitivity range of the injury test was tested from 0.01 to 630 mg kg-1 as the total pesticide concentration. This index is then used to monitor the detoxification of these pesticides in a biomixture (composed of wheat stubble, river waste, and soil, 50:25:25% by volume) over 210 days. The results are compared with standardized tests (Eisenia fetida avoidance test and Lactuca sativa seed germination test) carried out on the same biomixture. The results are also compared with data on the removal of pesticides. The injury test showed a better correlation with the removal of pesticides than the avoidance test and seed germination test. This simple and inexpensive test has proved to be useful for decontamination in-situ monitoring in biobeds.
Assuntos
Monitoramento Biológico , Oligoquetos , Praguicidas , Praguicidas/análise , Praguicidas/metabolismo , Oligoquetos/metabolismo , Monitoramento Biológico/métodos , Animais , Atrazina/toxicidade , Atrazina/análise , Poluentes do Solo/análise , Poluentes do Solo/toxicidade , Monitoramento Ambiental/métodos , Águas Residuárias/química , Prometrina/toxicidade , DicambaRESUMO
This research aimed to develop natural plant systems to serve as biological sentinels for the detection of organophosphate pesticides in the environment. The working hypothesis was that the presence of the pesticide in the environment caused changes in the content of pigments and in the photosynthetic functioning of the plant, which could be evaluated non-destructively through the analysis of reflected light and emitted fluorescence. The objective of the research was to furnish in vivo indicators derived from spectroscopic parameters, serving as early alert signals for the presence of organophosphates in the environment. In this context, the effects of two pesticides, Chlorpyrifos and Dimethoate, on the spectroscopic properties of aquatic plants (Vallisneria nana and Spathyfillum wallisii) were studied. Chlorophyll-a variable fluorescence allowed monitoring both pesticides' presence before any damage was observed at the naked eye, with the analysis of the fast transient (OJIP curve) proving more responsive than Kautsky kinetics, steady-state fluorescence, or reflectance measurements. Pesticides produced a decrease in the maximum quantum yield of PSII photochemistry, in the proportion of PSII photochemical deexcitation relative to PSII non photochemical decay and in the probability that trapped excitons moved electrons into the photosynthetic transport chain beyond QA-. Additionally, an increase in the proportion of absorbed energy being dissipated as heat rather than being utilized in the photosynthetic process, was notorious. The pesticides induced a higher deactivation of chlorophyll excited states by photophysical pathways (including fluorescence) with a decrease in the quantum yields of photosystem II and heat dissipation by non-photochemical quenching. The investigated aquatic plants served as sentinels for the presence of pesticides in the environment, with the alert signal starting within the first milliseconds of electronic transport in the photosynthetic chain. Organophosphates damage animals' central nervous systems similarly to certain compounds found in chemical weapons, thus raising the possibility that sentinel plants could potentially signal the presence of such weapons.
Assuntos
Clorofila , Clorpirifos , Clorofila/metabolismo , Clorofila/química , Clorpirifos/metabolismo , Clorpirifos/toxicidade , Fluorescência , Praguicidas/toxicidade , Praguicidas/metabolismo , Fotossíntese/efeitos dos fármacos , Dimetoato/toxicidade , Dimetoato/metabolismo , Espectrometria de Fluorescência , Complexo de Proteína do Fotossistema II/metabolismo , Complexo de Proteína do Fotossistema II/química , Monitoramento Ambiental/métodos , Clorofila A/metabolismo , Clorofila A/química , Cinética , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/toxicidade , Poluentes Químicos da Água/metabolismoRESUMO
Elasmobranchs are good indicators of marine pollution as they accumulate pollutants from water and food, and occupy different trophic levels. Concentrations of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and chlorpyrifos were quantified in muscle, liver, gonads, gills, and brain in both sexes and maturity stages of the Southern Eagle Ray, Myliobatis goodei, captured in Argentine coastal waters. Moreover, possible histological alterations in the liver and gonads were analyzed. Pollutant concentrations were pervasive across all tissues, with PCBs > OCPs > chlorpyrifos. Elevated pollutant levels were notably found in the liver and gills. We identified thirty-six PCB congeners in tissues, with low-chlorine congeners prevailing. Among OCPs, ∑DDT and ∑endosulfan were predominant. Females exhibited higher pollutant levels in most tissues compared to males, except in the gonads, and adults generally displayed elevated pollutant levels. Histological analysis revealed the presence of atretic follicles and melanomacrophages (MM). Continuous monitoring of pollutant levels, alongside their effects on physiological and ecological traits, is imperative for effective management and conservation efforts.
Assuntos
Clorpirifos , Monitoramento Ambiental , Gônadas , Hidrocarbonetos Clorados , Bifenilos Policlorados , Rajidae , Poluentes Químicos da Água , Animais , Clorpirifos/análise , Poluentes Químicos da Água/análise , Bifenilos Policlorados/metabolismo , Bifenilos Policlorados/análise , Feminino , Masculino , Hidrocarbonetos Clorados/metabolismo , Praguicidas/metabolismo , Fígado , Brânquias , ArgentinaRESUMO
Atrazine (ATZ) is the third most sold herbicide in Brazil, occupying the seventh position between most widely used pesticides. Due to its easy outflow, low reactivity and solubility, moderate adsorption to organic matter and clay, and long soil persistence, residual herbicide can be identified after long periods following application, and its usage has been prohibited in diverse countries. Amphibians are important bioindicators to assess impact of pesticide like atrazine, due to having a partial aquatic life cycle. This study had as objective to assess the response of bullfrog (Lithobates catesbeianus) tadpoles when exposed to this herbicide. Animals were exposed for a total of 168h to following concentrations: negative control, 40 µg/L, 200 µg/L, 2000 µg/L, 20000 µg/L of ATZ. Analysis of swimming activity was performed, and biochemical profile was assessed by analysis of blood and plasma glucose levels, urea, creatinine, cholesterol, HDL, triglycerides, glutamic pyruvic transaminase (GPT), alkaline phosphatase (AP), calcium, total proteins, phenol, peroxidase and polyphenol oxidase activity. Results exhibited malnutrition, anemia, likely muscle mass loss, and hepatic damage, indicating that ATZ can lead to an increase in energy to maintain homeostasis for animal survival.
Assuntos
Atrazina , Herbicidas , Praguicidas , Poluentes Químicos da Água , Animais , Herbicidas/metabolismo , Larva , Praguicidas/metabolismo , Rana catesbeiana/metabolismo , Poluentes Químicos da Água/metabolismoRESUMO
Reptiles are the least studied vertebrates regarding the impact of pesticides on their health, despite being good models for ecotoxicological studies given their abundance and easy handling. Salvator merianae is widely distributed in South America and often found in agricultural cultivation areas. Here, we compared the morphological, biochemical, and physiological parameters of S. merianae from an exposed area (EA) to pesticides and a reference area (RA) or control. These parameters were measured in plasma (albumin, alanine transaminase, alkaline phosphatase, gamma-glutamyl transpeptidase, glucose, total proteins, uric acid, triglycerides, VLDL, and corticosterone) and in erythrocytes (TBARS, glutathione S-transferase, superoxide dismutase, and catalase activity). Blood samples were collected from 28 lizards (EA: three juveniles, three adult females, and three adult males; RA: nine juveniles, four females, and five males) in southern Brazil during the reproductive period. We observed a decrease in body mass, the ratio between body mass and total length and snout-vent length in juvenile lizards collected at EA. The levels of TBARS, glutathione S-transferase, triglycerides, VLDL, and uric acid were altered for juveniles in EA. When comparing the two areas, females differed in superoxide dismutase activity and total proteins, while males differed in superoxide dismutase, catalase, and glutathione S-transferase activity. This set of results shows that S. merianae, especially juveniles, suffers a negative impact when inserted in an agricultural area. The analyzed biomarkers proved suitable for monitoring these lizards and the quality of this environment.
Assuntos
Lagartos , Praguicidas , Animais , Feminino , Masculino , Praguicidas/toxicidade , Praguicidas/metabolismo , Catalase/metabolismo , Lagartos/metabolismo , Substâncias Reativas com Ácido Tiobarbitúrico/metabolismo , Ácido Úrico/metabolismo , Monitoramento Ambiental , Superóxido Dismutase/metabolismo , Glutationa Transferase/metabolismo , Triglicerídeos/metabolismo , BrasilRESUMO
Imazamox (IMX), a chiral herbicide used in cereals and oilseed crops to control weeds, is commonly sold as a racemic mixture. Its enantiomers, being chiral compounds, may exhibit unique properties when exposed to chiral environments. While IMX enantiomers have been reported to degrade differently in soil and be toxic to some species, their effects on human systems remain poorly understood. This study utilized Caco-2 (human colon adenocarcinoma cell line) cells to assess the in vitro permeability of a racemic mixture of IMX and its isolated enantiomers. Additionally, the study aimed to evaluate whether the metabolite imazamox-O-desmethyl (IMX-D) forms during the permeability process. An enantioselective chromatographic method was developed, fully validated, and the apparent permeability values were obtained. The apparent permeability of rac-IMX, (+)-IMX, and (-)-IMX was determined to be 4.15 × 10-5, 5.78 × 10-5, and 7.33 × 10-5 cm s-1, respectively. These findings suggest that IMX exhibits high intestinal permeability, with an enantioselective absorption for (-)-IMX as compared to (+)-IMX. Finally, the permeability study in Caco-2 cells revealed that the metabolite IMX-D was not generated.
Assuntos
Permeabilidade , Humanos , Células CACO-2 , Estereoisomerismo , Imidazóis/química , Imidazóis/metabolismo , Reprodutibilidade dos Testes , Limite de Detecção , Modelos Lineares , Cromatografia Líquida de Alta Pressão/métodos , Praguicidas/química , Praguicidas/metabolismoRESUMO
Biosurfactants can be applied in the formulation of personal care products, as food additives, and as biocontrol agents in the agricultural sector. Glycolipids and lipopeptides represent an important group of microbial-based biosurfactants with biostimulating properties. Among them, the mannosylerythritol lipids also presented antimicrobial activity, mostly against Gram-positive bacteria and phytopathogenic fungi. In this sense, mannosylerythritol lipids are a potential safer green alternative for partially replacing synthetic pesticides. This review aimed to critically discuss the current state of the art and future trends of mannosylerythritol lipids as green pesticides and biostimulants for seed germination and plant growth. Due to their chemical structure, mannosylerythritol lipids are likely related to energy pathways such as glycolysis and Krebs cycle, i.e. a direct cellular biostimulant potential. In this case, experimental evidence from other glycolipids indicated that structural and chemical changes as a potential drug vehicle due to morphological changes caused by biosurfactant-membrane interaction. In addition, like other biosurfactants, mannosylerythritol lipids can trigger self-defense mechanisms, leading to a lower frequency of phytopathogen infections. Therefore, mannosylerythritol lipids have the potential for biostimulation and antiphytopathogenic action, despite that to date no data are available on mannosylerythritol lipids as biostimulants and green pesticides simultaneously. Based on the current state of the art, mannosylerythritol lipids have great potential for a biotechnological advance toward more sustainable agriculture. © 2022 Society of Chemical Industry.
Assuntos
Praguicidas , Praguicidas/metabolismo , Tensoativos/química , Glicolipídeos/química , Fungos/metabolismo , Bactérias Gram-Positivas/metabolismoRESUMO
Pesticides already were detected in the oceans, and their fates require evaluation in these environmental conditions. Therefore, marine-derived fungi were assessed for Esfenvalerate biodegradation, approaching the effects of seawater and use of commercial emulsifiable formulation. Residual pesticide and four metabolites were quantified. Furthermore, kinetics were determined for the three tested strains (Microsphaeropsis sp. CBMAI 1675, Acremonium sp. CBMAI 1676, and Westerdykella sp. CBMAI 1679). These facultative marine fungi biodegraded up to 87 ± 2% of 100 mg L-1 Esfenvalerate in liquid media. However, Esfenvalerate biodegradation was faster in low salinity conditions than in artificial seawater. Moreover, rates of consumption were higher for Esfenvalerate in the pure form than for the commercial emulsifiable formulation. These results suggest that half-life of Esfenvalerate formulated with inert ingredients in seawater can have a double prolongation effect that can contribute to health and environmental issues.
Assuntos
Praguicidas , Piretrinas , Piretrinas/metabolismo , Fungos/metabolismo , Praguicidas/metabolismo , Água do Mar/microbiologia , Biodegradação AmbientalRESUMO
The organophosphorus pesticide chlorpyrifos, detected in water and food worldwide, has also been found in the Río Negro and Neuquén Valley, North Patagonia, Argentina, where the rainbow trout, Oncorhynchus mykiss, is one of the most abundant fish species. We analyzed whether chlorpyrifos affects the transport activity of the ATP-binding cassette protein transporters from the subfamily C (ABCC), which are critical components of multixenobiotic resistance. We exposed ex vivo O. mykiss middle intestine strips (non-polarized) and segments (polarized) for one hour to 0 (solvent control), 3, 10, and 20 µg L-1 and to 0, 10, and 20 µg L-1 chlorpyrifos, respectively. We estimated the Abcc-mediated transport rate by measuring the transport rate of the specific Abcc substrate 2,4-dinitrophenyl-S-glutathione (DNP-SG). In addition, we measured the enzymatic activity of cholinesterase, carboxylesterase, glutathione-S-transferase, and 7-ethoxyresorufin-O-deethylase (EROD, indicative of the activity of cytochrome P450 monooxygenase 1A, CYP1A). We also measured lipid peroxidation using the thiobarbituric acid reactive substances method and the gene expression of Abcc2 and genes of the AhR pathway, AhR, ARNT, and cyp1a, by qRT-PCR. Chlorpyrifos induced the DNP-SG transport rate in middle intestine strips in a concentration-dependent manner (49-71%). In polarized preparations, the induction of the DNP-SG transport rate was observed only in everted segments exposed to 20 µg L-1 chlorpyrifos (40%), indicating that CPF only stimulated the apical (luminal) transport flux. Exposure to chlorpyrifos increased GST activity by 42% in intestine strips and inhibited EROD activity (47.5%). In addition, chlorpyrifos exposure inhibited cholinesterase (34-55%) and carboxylesterase (33-42.5%) activities at all the concentrations assayed and increased TBARS levels in a concentration-dependent manner (71-123%). Exposure to 20 µgL-1 chlorpyrifos did not affect the mRNA expression of the studied genes. The lack of inhibition of DNP-SG transport suggests that chlorpyrifos is not an Abcc substrate. Instead, CPF induces the activity of Abcc proteins in the apical membrane of enterocytes, likely through a post-translational pathway.
Assuntos
Clorpirifos , Oncorhynchus mykiss , Praguicidas , Poluentes Químicos da Água , Transportadores de Cassetes de Ligação de ATP , Trifosfato de Adenosina/metabolismo , Animais , Hidrolases de Éster Carboxílico/metabolismo , Clorpirifos/farmacologia , Colinesterases , Citocromo P-450 CYP1A1/genética , Citocromo P-450 CYP1A1/metabolismo , Sistema Enzimático do Citocromo P-450/metabolismo , Glutationa/metabolismo , Glutationa Transferase/genética , Glutationa Transferase/metabolismo , Intestinos , Oncorhynchus mykiss/genética , Oncorhynchus mykiss/metabolismo , Compostos Organofosforados/metabolismo , Praguicidas/metabolismo , RNA Mensageiro/metabolismo , Solventes , Substâncias Reativas com Ácido Tiobarbitúrico/metabolismo , Água/metabolismo , Poluentes Químicos da Água/toxicidadeRESUMO
This work attempts to evaluate dermal exposure (DE) of farm workers to dimethoate after 4 h of routine application to a lemon plantation. Dimethoate was measured on the workers' clothes as well as in stratum corneum (SC) and in saliva. In vitro permeation tests (IVPT) were performed through rat, pig and human skin and pig buccal, esophageal and sublingual mucosas. The mean of dimethoate DE was 342.19 ± 487.14 mg/d, the percentage of toxic dose per hour was higher than the other pesticides, and the SC penetration factors ranged between 0.5 and 14.81 and 0.05-53.96 % for back of neck and arms respectively. In the supporting IVPT study, dimethoate absorption through human skin was 14.75 % and the default value in the absence of experimental data for this product is 70%. These results show that in family farming the deficiency of correct clothing during the application of pesticides leaves workers more vulnerable.