Valdemar Luiz Tornisielo

Sorption of fluoroquinolones and sulfonamides in 13 Brazilian soils

Animal production is a leading economic activity in Brazil and antibiotics are widely used. However, the occurrence, behavior, and impacts of antibiotics in Brazilian soils are still poorly known. We evaluated the sorption behavior of four fluoroquinolones (norfloxacin, ciprofloxacin, danofloxacin, and enrofloxacin) and five sulfonamides (sulfadiazine, sulfachloropyridazine, sulfamethoxazole, sulfadimidine, and sulfathiazole) in 13 Brazilian soils with contrasting physical, chemical, and mineralogical properties. Fluoroquinolone sorption was very high (Kd≥544 L kg(-1)) whereas sulfonamide sorption ranged from low to high (Kd=0.7-70.1 L kg(-1)), consistent with previous reports in the literature. Soil texture and cation exchange capacity were the soil attributes that most affected sorption. Cation exchange was the most important sorption mechanism for the fluoroquinolones in highly weathered tropical soils, although cation bridging and ion pairing could not be ruled out. Hydrophobic partition played an important role in the sorption of the sulfonamides, but sorption was also affected by non-hydrophobic interactions with organic and/or mineral surfaces. Sorption for both compound classes tended to be higher in soils with high Al and Fe oxihydroxide contents, but they were not correlated with Kd values. No direct effect of soil pH was seen. The fluoroquinolones are not expected to leach even in worst-case scenarios (soils rich in sand and poor in organic carbon), whereas soil attributes dictate leaching potential for the sulfonamides.

Critérios para avaliação do potencial de lixiviação dos herbicidas comercializados no Estado do Paraná

A survey was carried out on the commercialization of herbicides in Parana, to verify their total input in the environment. Based on the chemical properties of these herbicides, theoretical criteria ranking them according to their leaching potential were evaluated. The highest volume of commercialization was found to occur from October to November, probably related to the increased demand caused by the summer crop cycle. The mechanisms of action whose consumption is most expressive are the aminoacid synthesis inhibitors (36.9% of the total volume), followed by the photosynthesis inhibitors (31.3%), synthetic auxins (11%) and mitosis inhibitors (8.8%). The herbicides glyphosate (4526.28 t), atrazine (3075.91), 2,4-D (1659.33) and sulfosate (631.60 t) account together for around 65% of the total volume commercialized in the state. Ranking herbicides according to their leaching potential showed that acifluorfen-sodium, alachlor, atrazine, chlorimuron-ethyl, fomesafen, hexazinone, imazamox, imazapyr, imazaquin, imazethapyr, metolachlor, metribuzin, metsulfuron-methyl, nicosulfuron, picloram, sulfentrazone and tebuthiuron are potential leachers according to the three theoretical criteria adopted (GUS, CDFA and Cohen).

Sorption-Desorption of Atrazine and Diuron in Soils from Southern Brazil

The objective of this study was to investigate the behavior of sorption and desorption of the herbicides atrazine (6-chloro-N 2-ethyl-N 4-isopropyl-1,3,5-triazine-2,4-diamine) and diuron [3-(3,4-dichlorophenyl)-1,1-dimethyleurea] in soil samples from a typical lithosequence located in the municipality of Mamborê (PR), southern Brazil. Five concentrations of 14C-atrazine and 14C-diuron were used for both herbicides (0.48, 0.96, 1.92, 3.84, and 7.69 mg L−1). Sorption of both herbicides correlated positively with the organic carbon and clay content of the soil samples. Sorption isotherms were well described by the Freundlich model. The slope values of the isotherm (N) ranged from 0.84 to 0.90 (atrazine) and from 0.75 to 0.79 (diuron) for the lithosequence samples. Sorption of diuron was high regardless of the soil texture or the concentration added. The desorption isotherms for atrazine and diuron showed good fit to the Freundlich equation (R 2 ≥ 0,87). Atrazine slope values for the desorption isotherms were similar for the different concentrations and were much lower than those observed for the sorption isotherms. Significant hysteresis was observed in the herbicide desorption. When the two herbicides were compared, it was found that diuron (N = 0.06–0.22) presented more pronounced hysteresis than atrazine. The results showed that, quantitatively, a greater atrazine fraction applied to these soils remains available to be leached in the soil profile, as compared to diuron.

Glyphosate sorption and desorption in soils with distinct phosphorus levels

A sorcao do glifosato no solo ocorre devido a formacao de complexos de esfera interna com os metais dos oxidos, o que esta relacionado a capacidade dos solos em adsorver fosfatos. Isto sugere que haja competicao entre o herbicida e os ions fosfato pelos sitios de adsorcao especifica do solo. Com isso, o presente trabalho teve o objetivo de verificar a extensao do efeito de niveis crescentes de fosforo no solo na sorcao e dessorcao do glifosato em solos com diferentes atributos mineralogicos. Os solos foram Nitossolo Vermelho eutroferrico, Latossolo Amarelo acrico e Gleissolo. Amostras dos solos foram incubadas com KH2PO4, por 30 dias, nas doses equivalentes a 0; 1000; 5000; 20000 e 50000 kg ha-1 de P2O5, que sao muito altos do ponto de vista agronomico, mas necessario para estudos de sorcao e dessorcao. O delineamento experimental foi do tipo inteiramente casualizado, em arranjo fatorial 3 (solos) X 5 (niveis de fosforo no solo), com tres repeticoes. No estudo da sorcao foram utilizadas cinco concentracoes do herbicida: 0,42; 0,84; 1,68; 3,36 e 6,72 mg L-1, com radioatividade (14C) de 0,233 kBq mL-1. Apenas para a concentracao 0,84 mg L-1 foram feitas quatro dessorcoes com CaCl2 0,01 mol L-1 e uma extracao com extrator Mehlich 3. Posteriormente, aliquotas do solo foram oxidadas em oxidador biologico para o fechamento do balanco de radioatividade. O glifosato compete com o fosforo pelos sitios de sorcao especifica no solo, mas essa competicao somente e importante quando os niveis de P atingem valores superiores a 1000 mg dm-3. A extracao do glifosato foi muito baixa e foi acrescida com aumento dos niveis de P no solo.

Sorption Kinetics of Atrazine and Diuron in Soils from Southern Brazil

Abstract Sorption kinetics of atrazine and diuron was evaluated in soil samples from a typical landscape in Paraná. Samples were collected (0–20 cm) in a no-tillage area from Mamborê, PR, which has been cultivated under a crop rotation for the last six years. Six sampling points of the slope were selected to represent a wide range of soil chemical and physical properties found in this area. Radiolabeled tracers (14C-atrazine and 14C-diuron) were used and the radioactivity was detected by liquid scintillation counting (LSC). Sorption was accomplished for increasing equilibration periods (0.5, 1.5, 3, 6, 12, 24, and 48 h). Kinetics data fitted adequately well to Elovich equation, providing evidences that soil reaction occurs in two distinct stages: a fast, initial one followed by a slower one. During the fast phase, 34–42 and 71–79% of total atrazine and diuron applied were sorbed to soil samples. No important differences were found among combinations of soil and herbicide sorption during the slow phase. The unrealistic conditions under batch experiments should be overestimating sorption in the fast phase and underestimating diffusion in the slow phase. Sorption of both herbicides was positively correlated to organic carbon and clay contents of soils, but atrazine was much less sorbed than diuron, showing its higher potential to contaminate groundwater, specially in sandy, low organic carbon soils.

Atributos de solos tropicais e a sorção de imazaquin

Imazaquin is an acid herbicide widely used in Brazil to control weeds associated to the soybean crop. The purpose of this research was to study imazaquin sorption and its relation to CEC, pH and organic carbon (OC) and clay contents of eleven tropical soil samples. In order to establish the sorption isotherms, imazaquin solutions at concentrations of 0.53, 0.88, 1.45, 2.71, and 5.20 mg mL-1 were prepared in 0.005 mol L-1 CaCl2 solution with the addition of radiolabeled tracer (14C-imazaquin). The sorption coefficients (Kf) were calculated according to the linear shape of the Freundlich isotherm equation. Imazaquin sorption ranged from low to moderate (Kf < 3.0), except for the Aquox soil. OC content and pH were the soil attributes that best correlated to imazaquin sorption. The incorporation of clay content in the regression analysis increased the model´s precision by 20 %. Imazaquin shows higher availability and, therefore, higher leaching potential when applied to soils with pH higher than 6 and low contents of OC and clay.

Banana Peel as an Adsorbent for Removing Atrazine and Ametryne from Waters

The feasibility of using banana peel for removal of the pesticides atrazine and ametryne from river and treated waters has been demonstrated, allowing the design of an efficient, fast, and low-cost strategy for remediation of polluted waters. The conditions for removal of these pesticides in a laboratory scale were optimized as sample volume = 50 mL, banana mass = 3.0 g, stirring time = 40 min, and no pH adjustment necessary. KF(sor) values for atrazine and ametryne were evaluated as 35.8 and 54.1 μg g(-1) (μL mL(-1)) by using liquid scintillation spectrometry. Adsorption was also evaluated by LC-ESI-MS/MS. As quantification limits were 0.10 and 0.14 μg L(-1) for both pesticides, sample preconcentration was not needed. Linear analytical curves (up to 10 μg L(-1)), precise results (RSD < 4.5%), good recoveries (82.9-106.6%), and a > 90% removal efficiency were attained for both pesticides. Water samples collected near an intensively cultivated area were adequately remedied.

Absorção e translocação do herbicida diuron por espécies suscetível e tolerante de capim-colchão (Digitaria spp.)

The objective of this research was to compare the tolerance of two crabgrass species (Digitaria nuda and D. ciliaris) to diuron and to evaluate whether absorption and/or translocation are involved in the mechanism of tolerance to the herbicide. In order to determine the tolerance of the crabgrass species, plants at the vegetative growth stage of three true leaves were sprayed with different rates of diuron. Dose-response curves were adjusted to plant dry biomatter at 21 days after application. The absorption and translocation studies were conducted using 14C-diuron, measuring radioactivity in different plant parts at 0, 3, 6, 12, 24 and 48 hours after application. The results were expressed as percentage related to the total radioactivity recovered. The relation (T/S) between the rate required to reduce plant dry matter (GR50) at 21 DAA of the species D. nuda and the GR50 of D. ciliaris was 2.7, showing differential susceptibility of the species. There was no difference in the absorption by the species. Translocation was minimum in both species. It was concluded that differential absorption and/or translocation were not involved in the mechanism of tolerance to diuron present in Digitaria nuda crabgrass species.

INFLUÊNCIA DA MATÉRIA ORGÂNICA NA SORÇÃO E DESSORÇÃO DO GLIFOSATO EM SOLOS COM DIFERENTES ATRIBUTOS MINERALÓGICOS

The aim of this study was to evaluate the effects of soil organic matter on the sorption and desorption of glyphosate in three soils with different mineralogical attributes. The experiments were carried out at the Laboratorio de Ecotoxicologia of the Centro de Energia Nuclear na Agricultura (CENA/USP), Piracicaba, SP (Brazil). The soils were classified as: Rhodic Kandiudalf (NVef), Anionic Acrudox (LAw) and Typic Humaquept (G). In order to evaluate the influence of organic matter on the ghyphosate sorption, the soils were oxidized with H2O2 (30%). The design was completely randomized with a 2 x 3 factorial experiment. For the sorption experiment, five gliphosate solutions were employed with concentrations of 0.42, 0.84, 1.68, 3.36 and 6.72 mg L-1 and radioactivity of 0.233 kBq mL-1. The desorption experiments were performed at concentration of 0.84 mg L-1. The results showed that glyphosate was extremely sorbed to all soils, regardless of the presence of organic matter. The glyphosate sorption was related mainly to the mineral fraction of the soils, i.e., to the Fe and Al oxides. However, the organic fraction only played a secondary role. It was not observed glyphosate desorption, mostly forming soil bound residues.

Genotoxic responses of juvenile tilapia (Oreochromis niloticus) exposed to florfenicol and oxytetracycline

Florfenicol (FLC) and oxytetracycline (OTC) are the two most commonly used antibiotics for bacterial treatment in fish farming in Brazil, and because of their intensive use, the potential harmful effects on aquatic organisms are of great concern. This study evaluated the effects of environmental concentrations of FLC and OTC on the genetic material of juvenile tilapia (Oreochromis niloticus) erythrocytes by using the comet assay and the occurrence of micronuclei (MN) and other erythrocytic nuclear abnormalities (ENAs) after exposure to 96hour. The comet assay showed that fish erythrocytes exhibited significantly higher DNA damage after exposure to environmental concentrations of FLC and OTC. Although MN was not observed, ENAs were significantly higher after exposure to FLC, indicating that ENAs are a better biomarker for FLC than MN. The results showed that environmental concentrations of FLC and OTC were genotoxic to erythrocytes of O. niloticus; however, future studies on DNA damage recovery are needed.