Herbicide Leaching in Soil with Different Properties: Perspectives from Commercial Formulations and Analytical Standards.

The leaching of herbicides into the soil is essential to control germinating seeds and parts of vegetative weeds. However, herbicide transportation to deeper soil layers can result in groundwater contamination and, consequently, environmental issues. In this research, our objective was to investigate differences in herbicide leaching between commercial formulations and analytical standards using three different soils. Leaching experiments were carried out for diuron, hexazinone, and sulfometuron-methyl herbicides isolated and in binary and ternary mixtures. The herbicide residue quantification was performed by ultra-high-performance liquid chromatography coupled to a mass spectrometer (LC-MS/MS). Diuron had less mobility in soils and was retained in the most superficial layers. Hexazinone and sulfometuron-methyl were more mobile and leached into deeper layers. The leaching process was more intense for hexazinone and sulfometuron-methyl. The additives present in the commercial formulation favored the leaching in soils of diuron, hexazinone, and sulfometuron-methyl herbicides isolated and mixture compared to the analytical standard. This fact highlights the importance of considering these effects for the positioning of herbicides in the field to increase the efficiency of weed control and minimize the potential for environmental contamination.

Interaction between herbicides applied in mixtures alters the conception of its environmental impact.

Herbicide mixtures have often been used to control weeds in crops worldwide, but the behavior of these mixtures in the environment is still poorly understood. Laboratory and greenhouse tests have been conducted to study the interaction of the herbicides diuron, hexazinone, and sulfometuron-methyl which have been applied alone and in binary and ternary mixtures in the processes of sorption, desorption, half-life, and leaching in the soil. A new index of the risk of leaching of these herbicides has also been proposed. The sorption and desorption study has been carried out by the batch equilibrium method. The dissipation of the herbicides has been evaluated for 180 days to determine the half-life (t1/2). The leaching tests have been carried out on soil columns. The herbicides isolated and in mixtures have been quantified using ultra-high performance liquid chromatography coupled to the mass spectrometer. Diuron, hexazinone, and sulfometuron-methyl in binary and ternary mixtures have less sorption capacity and greater desorption when compared to these isolated herbicides. Dissipation of diuron alone is slower, with a half-life (t1/2) = 101 days compared to mixtures (t1/2 between 44 and 66 days). For hexazinone and sulfometuron-methyl, the dissipation rate is lower in mixtures (t1/2 over 26 and 16 days), with a more pronounced effect in mixtures with the presence of diuron (t1/2 = 47 and 56 and 17 and 22 days). The binary and ternary mixtures of diuron, hexazinone, and sulfometuron-methyl promoted more significant transport in depth (with the three herbicides quantified to depth P4, P7, and P7, respectively) compared to the application of these isolated herbicides (quantified to depth P2, P4, and P5). Considering the herbicides' desorption and solubility, the new index proposed to estimate the leaching potential allowed a more rigorous assessment concerning the risk of leaching these pesticides, with hexazinone and sulfometuron-methyl presenting a higher risk of contamination of groundwater.

Detection of Mycobacterium leprae DNA in clinical and environmental samples using serological analysis and PCR.

BACKGROUND: Leprosy is a chronic infectious disease caused by Mycobacterium leprae and persists as a serious public health problem in Brazil. This microorganism is inculturable, making it difficult to diagnose and elucidate details of its transmission chain. Thus, this study aimed to analyze the dynamics of environmental transmission of M. leprae in a case-control study in the city of Mossoró, Brazil. METHODS AND RESULTS: Data of clinical, epidemiological, bacilloscopic, and serological evaluation of 22 newly diagnosed patients were compared, with molecular results of detection of specific genome regions RLEP and 16S rRNA of M. leprae in samples of the nasal swab, saliva, and house dust of these individuals and their controls (44 household contacts and 44 peridomiciliar contacts). The rapid serological tests evaluated, ML flow (IgM ND-O-BSA) and OrangeLife® (IgM and IgG anti NDO-LID 1) showed similar results, with greater positivity among paucibacillaries by OrangeLife® (54.5%). Positivity for nasal swab and saliva in multibacillary patients with RLEP primer was 16.7% and 33.3%, respectively. There was no detection of bacterial DNA in house dust or among paucibacillaries. The OrangeLife® test indicated that the lower the amount of windows, the more transmission in the house (3.79 more chances). Having a history of leprosy cases in the family increased the risk by 2.89 times, and being over 60 years of age gave 3.6 times more chances of acquiring the disease. PCR positivity was higher among all clinical samples using the M. leprae RLEP region than 16S rRNA. CONCLUSIONS: In this study, the serological and PCR analysis were capable of detecting M. leprae DNA in clinical samples but not in the environmental samples. Close monitoring of patients and household contacts appears an effective measure to reduce the transmission of leprosy in endemic areas.

Machine learning models as an alternative to determine productivity losses caused by weeds.

BACKGROUND: Weed control can be economically viable if implemented at the necessary time to minimize interference. Empirical mathematical models have been used to determine when to start the weed control in many crops. Furthermore, empirical models have a low generalization capacity to understand different scenarios. However, computational development facilitated the implementation of supervised machine learning models, as artificial neural networks (ANNs), capable of understanding complex relationships. The objectives of our work were to evaluate the ability of ANNs to estimate yield losses in onion (model crop) due to weed interference and compare with multiple linear regression (MLR) and empirical models. RESULTS: MLR constructed from non-destructive and destructive methods show R2 and root mean square error (RMSE) values varying between 0.75% and 0.82%, 13.0% and 19.0%, respectively, during testing step. The ANNs has higher R2 (higher than 0.95) and lower RMSE (less than 6.95%) compared to MLR and empirical models for training and testing steps. ANNs considering only the coexistence period and system have similar performance to MLR models. However, the insertion of variables related to weed density (non-destructive ANN) or fresh matter (destructive ANN) increases the predictive capacity of the networks to values close to 99% correct. CONCLUSION: The best performing ANNs can indicate the beginning of weed control since they can accurately estimate losses due to competition. These results encourage future studies implementing ANNs based on computer vision to extract information about the weed community.

Sorption kinetics of sulfometuron-methyl in different Brazilian soils.

The speed of the sorption reaction alters the bioavailability of herbicides in the soil and, consequently, the transport and transformation processes of the molecule in the environment. In this research, the sorption kinetics of sulfometuron-methyl was evaluated in different Brazilian soils in which sugarcane is grown. The sorption speed was carried out by the batch equilibrium method. The amount of sulfometuron-methyl adsorbed and remaining in the soil solution was used to build kinetic models in fifteen soils. Pearson's correlation coefficients were determined between maximum sorption capacity and soil properties. The pseudo-second-order model presented the best fit to report the sorption kinetics of sulfometuron-methyl in soils. The sorption equilibrium time varied between 69.1 and 524.7 min. The properties of cation exchange capacity (CEC), soil hydrogenionic potential (pH), and total organic carbon (TOC) affected the sorption kinetics of sulfometuron-methyl. The pH showed a negative correlation with the maximum adsorption capacity at equilibrium, while TOC and CEC positively correlated with the maximum adsorption. The results demonstrate that the sorption speed of sulfometuron-methyl varies between soils; this must be considered when defining the rate of use of the herbicide for weed control, minimizing the risk of environmental contamination.

Glyphosate effects on tree species natives from Cerrado and Caatinga Brazilian biome: Assessing sensitivity to two ways of contamination.

Glyphosate is applied for dissection in no-till and post-emergence management in transgenic crops in agricultural fields near the Cerrado and Caatinga biomes. These biomes together represent 33.8% of the Brazilian territory, contributing to the maintenance of great world diversity in flora and fauna. Despite actions to protect them, the proximity with agricultural areas and intense use of glyphosate puts at risk the preservation of native vegetation due to the contamination via herbicide transport processes. Our objectives were: i) to determine the sensitivity of native species from the Cerrado and Caatinga to glyphosate contamination via drift and groundwater; ii) evaluate the level of sensitivity to glyphosate among the different organs of plants. The highest intoxications (upper 80%) were observed for Bauhinia cheilantha, Mimosa caesalpiniaefolia, Mimosa tenuiflora and Amburana cearensis due to drift simullation. The species with 90% of total dry matter reduction were Bauhinia cheilantha, Enterolobium contortisiliquum, Mimosa caesalpiniaefolia, Mimosa tenuiflora, Tabebuia aurea. B. cheilantha and M. tenuiflora are most affected by exposure to glyphosate drift, with 50% of total dry matter reduction when exposed to doses below 444,0 g ha-1. Leaf growth is more sensitive to glyphosate for drift exposure for most species. Hymenaea courbaril is an exception, with greater sensitivity to root growth (50% dry matter reduction at doses below 666,0 g ha-1). B. cheilantha is the species most sensitive to drift exposure; however, it showed complete tolerance to contamination in subsurface waters. Other species such as Anadenanthera macrocarpa and M. caesalpiniifolia are also sensitive to drift, but without reach 90% of total dry matter reduction. A. macrocarpa, M. caesalpiniifolia and T. aurea were tolerant to contamination by subsurface water. The differential tolerance of trees confirms glyphosate's potential as a species selection agent in the Cerrado and Caatinga biomes.

Adsorption mechanisms of atrazine isolated and mixed with glyphosate formulations in soil.

In Brazil, the atrazine has been applied frequently to join with glyphosate to control resistant biotypes and weed tolerant species to glyphosate. However, there are no studies about atrazine's behavior in soil when applied in admixture with glyphosate. Knowledge of atrazine's sorption and desorption mixed with glyphosate is necessary because the lower sorption and higher desorption may increase the leaching and runoff of pesticides, reaching groundwaters and rivers. Thereby, the objective of this study was to evaluate the adsorption mechanisms of atrazine when isolated and mixed with glyphosate formulations in a Red-Yellow Latosol. The maximum adsorbed amount of atrazine in equilibrium (qe) was not altered due to glyphosate formulations. The time to reach equilibrium was shortest when atrazine was mixed with the Roundup Ready® (te = 4.3 hours) due to the higher adsorption velocity (k2 = 2.3 mg min-1) in the soil. The highest sorption of atrazine occurred when mixed with the Roundup WG®, with the Freundlich sorption coefficient (Kf) equal to 2.51 and 2.43 for both formulation concentrations. However, other glyphosate formulations did not affect the sorption of atrazine. The desorption of atrazine was high for all treatments, with values close to 80% of the initial adsorbed amount, without differences among isolated and mixed treatments. The change in the velocity and capacity of sorption for the atrazine mixed with some glyphosate formulations indicates that further studies should be conducted to identify the mechanisms involved in this process.

Phytoextraction of diuron, hexazinone, and sulfometuron-methyl from the soil by green manure species.

The herbicides diuron, hexazinone, and sulfometuron-methyl present a potential risk of environmental contamination and are widely used for weed control in sugarcane cultivation. Our objectives were to measure the tolerance of Canavalia ensiformes (L.) DC., Stilizobium aterrimum L., Raphanus sativus L., Crotalaria spectabilis Röth, Lupinus albus L., and Pennisetum glaucum (L.) R. Br. To the herbicides diuron, hexazinone, and sulfometuron-methyl to assess the capacity of these species to extract and accumulate the herbicides in their tissues. Before sowing the green manure species, the soils were individually contaminated with the three 14C-radiolabeled herbicides. 14C-diuron and 14C-sulfometuron-methyl showed higher values remaining in the soil (>90%) for all species of green manure compared to hexazinone (<80%). The green manure species analyzed showed greater potential to remedy soils contaminated with hexazinone than the other herbicides. C. ensiformes showed high phytoextraction of hexazinone when compared to the other species, removing 11.2% of the pollutant from the soil, followed by L. albus (8.6%), S. aterrimum (7.3%), R. sativus (4.8%), C. spectabilis (2.5%), and P. glaucum (1.1%). The results indicate that the phytoextraction of diuron, hexazinone and sulfometuron-methyl is dependent on the species of green manure and can be an important tool for the decontamination of areas polluted by these herbicides.

Sorption and desorption of ametryn in different types of soils / Sorção e dessorção do ametryn em diferentes tipos de solos

Knowledge of factors related to the dynamics of herbicides in the environment is of fundamental importance to predicting the behavior of herbicides in soils with different attributes, to select appropriate dosages, as well as to avoid harmful effects on the environment and subsequent crops. The objective of this work was to evaluate the sorption and desorption of ametryn in seven soils with different attributes. Initially, the equilibrium time was determined by the "Batch Equilibrium". Then, it was performed the sorption test with different concentrations (0.5; 1; 2; 4; 8; 16; 24 and 32 mg L-1) of ametryn in 0.01 mol L-1CaCl2. 10 mL of these solutions were added to samples of 2.00 g of each soil, remaining under rotary shaking for 4 hours. After centrifugation and filtration, the ametryn concentration in the supernatant was determined by high-performance liquid chromatography. Desorption was evaluated using the tubes containing 16 mg L-1 prior to sorption testing. The results indicated that the sorption and desorption of ametryn depend on the physicochemical attributes of the soil. Sorption was higher in soils with high organic matter content and high ion exchange capacity, while desorption was inversely proportional to sorption.

O conhecimento dos fatores relacionados à dinâmica de herbicidas no ambiente é de fundamental importância para prever o comportamento de herbicidas em solos com diferentes atributos e para seleção de dosagens adequadas, bem como para evitar efeitos prejudiciais ao ambiente e às culturas subsequentes. O objetivo do trabalho foi avaliar a sorção e dessorção do ametryn em sete solos com diferentes atributos. Inicialmente, foi determinado o tempo de equilíbrio pelo método "Batch Equilibrium". Em seguida foi realizado o ensaio de sorção com diferentes concentrações (0,5; 1; 2; 4; 8; 16; 24 e 32 mg L-1) de ametryn em CaCl2 0,01 mol L-1. Foram adicionadas 10 mL destas soluções a amostras de 2,00 g de cada solo, permanecendo sob agitação rotatória por 4 horas. Após centrifugação e filtração, a concentração do ametryn no sobrenadante foi determinada por cromatografia líquida de alta eficiência. A dessorção foi avaliada utilizando os tubos que continham 16 mg L-1 antes do ensaio de sorção. Os resultados indicaram que a sorção e a dessorção do ametryn depende dos atributos físico-químicos do solo. A sorção foi maior em solos com alto teor matéria orgânica e alta capacidade de troca iônica, enquanto que a dessorção foi inversamente proporcional à sorção.

Use of neural networks to estimate the sorption and desorption coefficients of herbicides: A case study of diuron, hexazinone, and sulfometuron-methyl in Brazil.

The use of herbicides in Brazil has been carried out based on the manufacturer's recommendation, often disregarding the high variability of soil attributes. The use of statistical methods to predict the herbicide retention processes in the soil can contribute to the improvement of weed control efficiency associated with the lower risk of environmental contamination. This research evaluated the use of Artificial Neural Networks (ANNs) to predict soil sorption and desorption, as well as the environmental contamination potential of diuron, hexazinone and sulfometuron-methyl herbicides in Brazilian soils. The sorption and desorption coefficients of the three herbicides were determined in laboratory tests for 15 soils from different Brazilian states. To predict the sorption and desorption of diuron, hexazinone and sulfometuron-methyl were used a multilayer perceptron ANNs (MLP). The inputs were the characteristics of the herbicides and the physical and chemical attributes of the soils, and the outputs of were the sorption and desorption coefficients (Kfs and Kfd). The risk of leaching of diuron, hexazinone, and sulfometuron-methyl herbicides were evaluated considering the sorption values observed and those estimated by the models. The Artificial Neural Network (ANN) models were efficient for the prediction of sorption and desorption of diuron, hexazinone, and sulfometuron-methyl herbicides. The physicochemical properties of the herbicides were more important for the modeling of multilayer perceptron ANNs than the soil attributes. The herbicides diuron, hexazinone, and sulfometuron-methyl have a high potential risk for contamination of groundwater in different Brazilian states.

Multivariate analysis reveals significant diuron-related changes in the soil composition of different Brazilian regions.

Sorption and desorption determine the amount of an herbicide in soil solution. Therefore, knowledge of the sorption and desorption coefficients in different soils is an essential factor to estimate the potential for environmental contamination by herbicides. We evaluated the feasibility of multivariate and linear discriminant analyses to predict the sorption and desorption capacity of a soil for diuron, one of the most used herbicides on sugarcane plantations. The adsorptive capacity in twenty-seven Brazilian soil samples was estimated using the sorption constant (Kfs) and desorption constant (Kfd) obtained by the Freundlich isotherms. The regression model was created from the sorbed and nonsorbed concentrations of diuron in soils. Ultra-performance liquid chromatography was applied to quantify the diuron concentrations. The multivariate analysis separated the soils into four groups considering the similarity of the following attributes: pH, organic matter, clay, and base saturation. The groups showed a similar pattern of sorption and desorption for diuron: Lom-Lclay: low sorption (5.9 ± 1.2) and high desorption (10.9 ± 0.6); Lclay: low sorption (7.5 ± 1.1) and high desorption (11.4 ± 1.3); Hom-Hclay: high sorption (11.2 ± 1.2) and low desorption (13.8 ± 1.2); HpH-Hclay: high sorption (10.1 ± 1.1) and medium desorption (11.5 ± 1.4). Linear discriminant analysis of these soil attributes was used to classify other soils described in the literature with adsorption capacity. This analysis was able to identify soils with high and low sorption using the pH, organic matter, clay, and base saturation, demonstrating the enormous potential of the technique to group soils with different contamination risks for subterranean waters. Sugarcane crops in northeastern Brazil showed a higher pollution risk through the leaching of diuron. Multivariate analysis revealed significant diuron-related changes in the soil composition of different Brazilian regions; therefore, this statistical analysis can be used to improve understanding of herbicide behavior in soils.