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.

Sensibility, multiple tolerance and degradation capacity of forest species to sequential contamination of herbicides in groundwaters.

Herbicides have already reported environmental contamination in several countries with intense agricultural activity. The transport of these molecules due to leaching and surface runoff has frequently caused contamination of rivers, groundwater and soil in non-agricultural areas. Thereby, we propose to investigate the sensitivity and phytoremediation capacity of 5 native Cerrado species to sequential exposure to 2,4-D, atrazine, diuron and hexazinone. We hypothesized that species have different sensitivity levels to sequential exposure to these herbicides absorbed from contaminated simulated groundwater model. The objectives of this work were: i) to determine the sensitivity of native cerrado species by sequential exposure to 2,4-D, atrazine, diuron and hexazinone via contaminated simulated groundwater model; ii) to evaluate the presence and degradation capacity of these herbicides in the soil and water leached by tolerant species. Some species showed high phytoremediation potential for groundwater already contaminated with 2,4-D, atrazine, diuron and hexazinone. S. macranthera and C. antiphilitica are tolerant and reduce the concentration of herbicides in simulated groundwater model. Among these species, C. antiphilitica reduces the concentration of all herbicides, suggesting greater adaptability to compose decontamination strategies in areas close to agricultural systems that use 2,4-D herbicides, atrazine, diuron and hexazinone. Also, our results show that herbicides can act as a selection factor for Cerrado forest species, however, two species can mitigate the effects of contamination due to their ability to degrade herbicides.

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.

Influence of Glyphosate Formulations on the Behavior of Sulfentrazone in Soil in Mixed Applications.

The selection of weed biotypes that are resistant to glyphosate has increased the demand for its use mixed with other herbicides, such as sulfentrazone. However, when chemical molecules are mixed, interactions may occur, modifying the behavior of these molecules in the environment, such as the sorption and desorption in soil. In this study, we hypothesized that the presence of glyphosate-formulated products might increase the sorption or decrease the desorption of sulfentrazone, thereby increasing the risk of the contamination of water resources. Therefore, our work aimed to evaluate the sorption, desorption, and leaching of sulfentrazone in the soil in an isolated and mixed application with different glyphosate formulations. The sorption coefficients (Kfs) for the sulfentrazone, sulfentrazone + Roundup Ready, sulfentrazone + Roundup Ultra, and sulfentrazone + Zapp Qi foram were 1.3, 2.1, 2.3, and 1.9, respectively. The desorption coefficients (Kfd) for the sulfentrazone, sulfentrazone + Roundup Ready, sulfentrazone + Roundup Ultra, and sulfentrazone + Zapp Qi foram were 65.7, 125.2, 733.3 and 239.8, respectively. The experiments demonstrated that the sorption and desorption of sulfentrazone in combination with the other formulated glyphosate products are altered, supporting the hypothesis suggested by this work, i.e., that the presence of other molecules is a factor that affects the behavior of herbicides in the soil. This phenomenon altered the vertical mobility of sulfentrazone. Situations involving mixtures of pesticides should be evaluated in order to improve our understanding of the dynamics of these molecules and thus avoid environmental contamination.

Metagenomic analysis reveals mechanisms of atrazine biodegradation promoted by tree species.

Metagenomics has provided the discovery of genes and metabolic pathways involved in the degradation of xenobiotics. Some microorganisms can metabolize these compounds, potentiating phytoremediation in association with plant. This study aimed to study the metagenome and the occurrence of atrazine degradation genes in rhizospheric soils of the phytoremediation species Inga striata and Caesalphinea ferrea. The genera of microorganisms predominant in the rhizospheric soils of I. striata and C. ferrea were Mycobacterium, Conexibacter, Bradyrhizobium, Solirubrobacter, Rhodoplanes, Streptomyces, Geothrix, Gaiella, Nitrospira, and Haliangium. The atzD, atzE, and atzF genes were detected in the rhizospheric soils of I. striata and atzE and atzF in the rhizospheric soils of C. ferrea. The rhizodegradation by both tree species accelerates the degradation of atrazine residues, eliminating toxic effects on plants highly sensitive to this herbicide. This is the first report for the species Agrobacterium rhizogenes and Candidatus Muproteobacteria bacterium and Micromonospora genera as atrazine degraders.

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.

Seed germination of Bidens subalternans DC. exposed to different environmental factors.

Bidens subalternans DC. is a weed found in several tropical countries such as Brazil. Large number of produced seeds and easy dispersion favor the colonization of agricultural fields by this species. To know the factors that affect the germination of B. subalternans can help to understand its ecology, permitting to develop control strategies. Laboratory experiments were carried out to evaluate how the temperature, photoperiod, burial depth, water deficit, and salt stress affect the seed germination of B. subalternans. The means of the treatments of each experiment were shown in scatter plots with the bars indicating the least significant difference (LSD, p≤0.05). The results showed a germination percentage above 77% for a wide alternating temperature (15/20 C to 30/35 C night/day). The highest germination and uniformity occurred at 25/30°C night/day. Only 11% of the seeds germinated at a temperature of 35/40°C night/day. The deeper burial of seeds reduced their germination. Only 17% of the seeds germinated in darkness conditions. However, in constant light and 12 hours of light/dark conditions the germination percentage was over 96%, confirming the light dependence of the B. subalternans during germination. In constant light and 12 hours of light/dark, the germination was over 96%. B. subalternans seeds showed sensitivity to water and salt stress, and their germination was inhibited under a water potential of -0.4 MPa and 100.09 mM, respectively. The sensitivity of B. subalternans seeds to high temperatures, water stress, and salt stress explains the high frequency of this weed in south-central Brazil. The light and sowing depth showed that burial of seeds by mechanical control is a strategy to reduce the high infestation of B. subalternans.

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.

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.

Sensitivity of the macrophytes Pistia stratiotes and Eichhornia crassipes to hexazinone and dissipation of this pesticide in aquatic ecosystems.

Herbicide wastes from agriculture areas can contaminate water resources and affect non-target organisms. Since herbicides reach groundwater and rivers, these residues can damage the aquatic ecosystem. Hexazinone is an herbicide widely used in sugarcane cultivation and has a potential to contaminate water resources. Therefore, studies are necessary to know the possible damages of this herbicide on aquatic organisms, as well as the behavior of this pesticide in those systems. In this study, our objective was to evaluate the sensitivity of the macrophytes Pistia stratiotes and Eichhornia crassipes to hexazinone, as well as the dissipation of these pesticides. The variables intoxication, fresh matter accumulation, and leaf anatomy were used to evaluate the sensitivity of the macrophytes to hexazinone. The hexazinone concentration in water was performed by HPLC-MS. Hexazinone concentrations equivalent to 111 and 333 µg L-1 were toxic to the macrophytes. Pistia stratiotes produced less fresh matter production than Eichhornia crassipes when exposed to the hexazinone. The hexazinone application did not change the adaxial epidermic (EAD), abaxial epidermic (EAB), palisade parenchyma (PP), aerenchyma (AER) and leaf blade (LAF) of Pistia stratiotes at any concentration tested. Concentrations equivalent to 333 µg L-1 changed the PP and LAF of Eichhornia crassipes. The presence of this herbicide in water negatively affects the fresh matter accumulation and leaf structure of the Pistia stratiotes and Eichhornia crassipes, respectively. The presence of these macrophytes delayed the dissipation of hexazinone due to them impair other pathways of degradation of this herbicide in aquatic environments. The presence of this herbicide in water negatively affects the growth and development of the Pistia stratiotes and Eichhornia crassipes.

Nematicidal potential of essential oils of Ageratum fastigiatum, Callistemon viminalis and Schinus terebinthifolius / Potencial nematicida de óleos essenciais de Ageratum fastigiatum, Callistemon viminalis e Schinus terebinthifolius

Some essential oils are rich in nematicidal compounds and can be used for the management of plant-parasitic nematodes. Laboratory and field studies aiming to evaluate the efficiency of this compounds are necessary. The objective of this research was to assess the nematicidal potential of essential oils from leaves of Ageratum fastigiatum and Callistemon viminalis, and green and mature fruits of Schinus terebinthifolius on the root-knot nematode Meloidogyne javanica. In laboratory, the essential oil of S. terebinthifolius green fruits reduced hatching by more than 80% and increased juvenile mortality by 300% when compared to Tween 20 + water. In the field, none of the essential oils controlled M. javanica in lettuce. In conclusion, the essential oil of S. terebinthifolius green fruits reduces the egg hatching and kills J2 of M. javanica in laboratory. In an infested field with an average of 555 J2/100 cm3 of soil, the application of the essential oils of S. terebinthifolius, C. viminalis and A. fastigiatum does not control M. javanica in lettuce.

Alguns óleos essenciais são ricos em compostos nematicidas e poderiam ser usados no manejo de fitonematoides. Estudos laboratoriais e de campo que visam avaliar a eficiência desses compostos são necessários. O objetivo desta pesquisa foi avaliar o potencial nematicida de óleos essenciais de folhas de Ageratum fastigiatum e Callistemon viminalis e frutos verdes e maduros de Schinus terebinthifolius sobre o nematoide de galhas Meloidogyne javanica. Em laboratório, o óleo essencial de frutos verdes de S. terebinthifolius reduziu mais de 80% a eclosão e aumentou em 300% a mortalidade de juvenis em comparação com Tween 20 + água. No campo, nenhum óleo essencial controlou M. javanica em alface. Em conclusão, o óleo de frutos verdes de S. terebinthifolius reduz a eclosão e mata J2 de M. javanica em laboratório. Em campo com infestação média de 555 J2/100 cm3 de solo, a aplicação dos óleos essenciais de S. terebinthifolius, C. viminalis e A. fastigiatum não controla M. javanica em alface.

Brachiaria physiological parameters in agroforestry systems / Parâmetros fisiológicos da braquiária em diferentes arranjos do sistema agrossilvipastoril

ABSTRACT: This study aimed to assess the effects of Eucalyptus and maize shading on characteristics related to water use by Brachiaria in agroforestry systems. Treatments were arranged in a split-split-plot design, with plots consisting of different spacing between Eucalyptus plants (12.0×2.0m and 12.0×4.0m), split-plots of different distances between Brachiaria and Eucalyptus (6.0, 4.0, and 2.0m), and split-split-plots of Brachiaria sowing sites (maize row and inter-row). One treatment with Brachiaria under full sunlight was included. Bread grass intercropping in maize inter-rows associated with the densest Eucalyptus spacing and bread grass proximity to Eucalyptus tree crowns adversely affected the stomatal conductance, internal carbon, and transpiration rate of bread grass. Water use efficiency of bread grass intercropped in maize rows decreased, regardless of the Eucalyptus plot design and distance between forages and trees.

RESUMO: O objetivo desta pesquisa foi avaliar os efeitos do sombreamento ocasionado por plantas de eucalipto e milho nas características relacionadas ao uso da água da braquiária em sistema agrossilvipastoril. O experimento foi realizado no delineamento em blocos casualizados, com quatro repetições. Os tratamentos foram arranjados em esquema de parcelas subsubdivididas, comas parcelas representadas constituídas pelos espaçamentos de plantio do eucalipto (12x2 e 12x4m), as sub-parcelas da distância da braquiaria e o eucalipto (6; 4 e 2m) e a subparcela do local de cultivo da braquiária (linha e entrelinha do milho). Além disso, foi adicionado um tratamento composto pela braquiária cultivada a pleno sol. O cultivo do capim-maradu na entrelinha do milho associado ao sombreamento intenso proporcionado pelo espaçamento mais adensado de eucalipto (12x2m) e a proximidade das plantas de capim-marandu às copas das árvores de eucalipto altera negativamente a condutância estomática, o carbo interno e a taxa transpiratória das plantas de capim-marandu. A eficiência no uso da água das plantas de capim - maradu é reduzida independente do arranjo espacial do eucalipto e da distância entre aforrageira e as árvores quando a forrageira é cultivada na linha do milho.