Enio Marchesan

Rice herbicide monitoring in two Brazilian rivers during the rice growing season

Irrigated rice production can involve environmental contamination with pesticides due to the proximity of the fields to rivers and to management problems. During three years (2000 to 2003) the rice herbicides clomazone, propanil and quinclorac were quantified in water during the rice growing season, in the Vacacai and Vacacai-Mirim Rivers, located in Rio Grande do Sul (RS) State, Brazil. Water samples were taken at several locations in each river, selected by their importance in terms of rice drainage area. The samples were analyzed by HPLC-UV. At least one herbicide was detected in 41% of the samples from the Vacacai River and 33% from the Vacacai-Mirim River. The most frequent herbicide in both rivers and in each year was clomazone. The amount of herbicides in the river water was dependent on the rainfall regime. River water contamination by rice herbicides is probably caused by the rice water management used in the fields. The maintenance of flooded areas makes herbicides prone to contaminate the environment. To reduce the environmental contamination risk it is necessary to adopt measures to avoid overflow of flooded rice fields, keeping paddy water in the field for time enough to reduce the herbicide concentration before its release and enhancing the quality of the levees to reduce the probability of paddy rice overflow.

Phenolic compounds and antioxidant activity of rice

ABSTRACT The aim of this work was to study the phenolic compounds identified in rice, their antioxidant activity and their potential beneficial effects on health. In vitro and in vivo studies evaluating the rice grains with different pericarp colour (light brown, red and black) showed potential beneficial effects on health related to the polyphenol content of the grain, such as reduction of oxidative stress, aid in the prevention of cancer, cardiovascular diseases and complications of diabetes, among others. Key words : rice, red rice, black rice, polyphenols, antioxidant, biological effect * Author for correspondence: melmelissaw@hotmail.com INTRODUCTION Several studies have demonstrated the importance of diet in the control of chronic diseases, such as cancer and cardiovascular problems (Birt et al., 2001; Kris-Etherton et al., 2002; Stanner et al., 2003; Houston, 2005). The consumption of fruits, legumes, vegetables and whole grains results a reduced risk of developing these diseases. This could be attributed to the presence of natural antioxidants in these foods, such as ascorbic acid, tocopherols, carotenoids and phenolic compounds (polyphenols) (Melendez-Martinez et al., 2004; Choi et al., 2007), besides other bioactive compounds. Among the compounds with antioxidant activity, polyphenols are important. These are found in a great variety of foods, such as apples, mulberries, cherries, grapes, raspberries, citric fruits, onions, spinach, peppers, oat, wheat, black tea, wine and chocolate, among others (Holden et al., 2005; Dimitrios, 2006). These compounds have demonstrated higher in vitro antioxidant capacity than other antioxidants, such as ascorbic acid and α-tocopherol (Pulido et al., 2000), emphasising the importance of polyphenols as antioxidants in the diet. Although polyphenols are found in several foods, variation is observed in the concentration and type of these compounds due to genetic and environmental factors and processing conditions (Kris-Etherton et al., 2002). Hence, the concentration of phenolic compounds varies greatly among the diets, depending on the type and quantity of food consumed. Rice, being one of the most produced and consumed cereals in the world, has an important role in the relation between the diet and health. Several compounds with antioxidant activity have been identified in rice, including phenolic compounds, tocopherols, tocotrienols and γ-oryzanol (Iqbal et al., 2005). The phenolic

Toxicological responses of Cyprinus carpio after exposure to a commercial herbicide containing imazethapyr and imazapic

Cyprinus carpio was exposed to imazethapyr and imazapic at laboratory and at field conditions. The laboratory experiment was carried out for 7 days and at rice field for 7, 30 and 90 days. Oxidative stress parameters and antioxidant profile were studied as well as metabolic parameters. After 7 days, brain AChE activity increases in laboratory and field, but in muscle, reduction was observed only in laboratory. At the same period, brain and muscle TBARS and liver CAT increase in the laboratory. Metabolic parameters showed changes in both conditions and exposure periods. After 30 days in rice field, brain AChE activity decreases and in muscle it was enhanced. After 90 days in field, only muscle AChE activity was reduced. The disorders in oxidative stress parameters and metabolism remained, indicating mainly a protein catabolism. This study pointed out short- and long-term effects of rice herbicides at environmentally relevant concentrations on toxicological parameters in tissues of C. carpio.

Acetylcholinesterase enzyme activity in carp brain and muscle after acute exposure to diafuran

Exposicao a inseticidas em concentracoes elevadas no ambiente podem ocasionar efeitos adversos subletais em organismos aquaticos. Alevinos de carpa hungara (Cyprinus carpio, Linnaeus, 1758), carpa capim (Ctenopharyngodon idella, Valenciennes, 1844) e carpa cabeca grande (Aristichthys nobilis, Richardson, 1845) foram expostos ao diafuran, um inseticida utilizado na cultura do arroz no sul do Brasil. O objetivo deste estudo foi verificar a relacao entre concentracao letal mediana (CL50) do diafuran e a atividade da enzima acetilcolinesterase (AChE) em cerebro e musculo dessas especies, como um possivel biomarcador inicial da exposicao a este inseticida. A CL50 foi determinada com peixes expostos a concentracoes de diafuran em 96 h: carpa hungara: controle; 0,5; 1,0; 1,5; 2,0; 2,5 e 3,0 mg L-1; carpa capim: controle; 1,0; 2,0; 3,0 e 3,5 mg L-1 e carpa cabeca grande: controle; 0,5; 1,0; 1,5; 2,0; 3,0 e 4,0 mg L-1, bem como a determinacao da AChE em concentracoes proximas da CL50 para essas especies. Valores de CL50 (concentracoes nominais) foram de 1,81 mg L-1 para carpa hungara, 2,71 mg L-1 para carpa capim e 2,37 mg L-1 para carpa cabeca grande. Todas as carpas expostas ao diafuran estavam letargicas (menores concentracoes) ou imoveis. Diafuran inibiu significativamente a atividade da AChE em cerebro (~38 %) e musculo (~50 %) de todas as especies estudadas. Atividade da AChE em musculo para carpa cabeca grande foi mais alta que cerebro (14,44 contra 5,94 µmol min-1 g proteina-1, respectivamente). Este estudo demonstrou que concentracoes de diafuran utilizadas na cultura do arroz podem afetar o comportamento de Cyprinus carpio, Ctenopharyngodon idella e Aristichthys nobilis, e a atividade da acetilcolinesterase cerebral e muscular pode ser um biomarcador inicial de toxicidade deste inseticida.Exposicao a inseticidas em concentracoes elevadas no ambiente podem ocasionar efeitos adversos subletais em organismos aquaticos. Alevinos de carpa hungara (Cyprinus carpio, Linnaeus, 1758), carpa capim (Ctenopharyngodon idella, Valenciennes, 1844) e carpa cabeca grande (Aristichthys nobilis, Richardson, 1845) foram expostos ao diafuran, um inseticida utilizado na cultura do arroz no sul do Brasil. O objetivo deste estudo foi verificar a relacao entre concentracao letal mediana (CL50) do diafuran e a atividade da enzima acetilcolinesterase (AChE) em cerebro e musculo dessas especies, como um possivel biomarcador inicial da exposicao a este inseticida. A CL50 foi determinada com peixes expostos a concentracoes de diafuran em 96 h: carpa hungara: controle; 0,5; 1,0; 1,5; 2,0; 2,5 e 3,0 mg L-1; carpa capim: controle; 1,0; 2,0; 3,0 e 3,5 mg L-1 e carpa cabeca grande: controle; 0,5; 1,0; 1,5; 2,0; 3,0 e 4,0 mg L-1, bem como a determinacao da AChE em concentracoes proximas da CL50 para essas especies. Valores de CL50 (concentracoes nominais) foram de 1,81 mg L-1 para carpa hungara, 2,71 mg L-1 para carpa capim e 2,37 mg L-1 para carpa cabeca grande. Todas as carpas expostas ao diafuran estavam letargicas (menores concentracoes) ou imoveis. Diafuran inibiu significativamente a atividade da AChE em cerebro (~38 %) e musculo (~50 %) de todas as especies estudadas. Atividade da AChE em musculo para carpa cabeca grande foi mais alta que cerebro (14,44 contra 5,94 µmol min-1 g proteina-1, respectivamente). Este estudo demonstrou que concentracoes de diafuran utilizadas na cultura do arroz podem afetar o comportamento de Cyprinus carpio, Ctenopharyngodon idella e Aristichthys nobilis, e a atividade da acetilcolinesterase cerebral e muscular pode ser um biomarcador inicial de toxicidade deste inseticida.

Risk assessment of surface water contamination by herbicide residues: monitoring of propanil degradation in irrigated rice field waters using HPLC-UV and confirmation by GC-MS

This study evaluates the degradation of the herbicide propanil and of its major degradation product, 3,4-dichloroaniline (3,4-DCA) in water from irrigated rice farming in the State of Rio Grande do Sul, Brazil. It also assesses the contamination risk of surrounding surface waters. After a solid phase extraction step, the concentration of both compounds was determined by high performance liquid chromatography with ultraviolet detection. Confirmation was conducted by gas chromatography-mass spectrometry. Concentrations of propanil in water samples varied from 0.1 to 3600 µg L-1. Propanil was degraded very rapidly to 3,4-DCA and high concentrations of this product were found, varying from 1.0 to 567.5 µg L-1 in water. The obtained half-life times for propanil in water under real conditions for the 2001, 2002 and 2003 harvests were 18.2, 12.5 and 12.2 h, respectively.

Resíduos de agrotóxicos na água de rios da Depressão Central do Estado do Rio Grande do Sul, Brasil

The rice-growing activity is conducted out with intensive use of agrochemicals, which, depending on the management and rainfall can reach rivers. The study aimed to determine the residues of herbicides clomazone, quinclorac, propanil, bentazone, 2,4-D and imazethapyr and insecticides carbofuran and fipronil in the Vacacai and Vacacai-Mirim rivers, located in the Central Depression of Rio Grande do Sul, in the crop of 2003/04 untill 2007/08. Samples were collected from November to February (rice growing season). Analysis of herbicides and carbofuran were performed by HPLC-DAD and fipronil by GC-ECD. During 2003/04, in both rivers, the herbicide clomazone, 2,4-D and propanil were the most frequent in water samples. In 2004/05, the quinclorac was detected in many samples and in 2005/06 and 2006/07 seasons fipronil was the most common pesticide in the samples in Vacacai and Vacacai-Mirim rivers. In the 2007/08 crop, there were less residues of pesticides in Vacacai and Vacacai-Mirim rivers. There is presence of pesticides used in rice farming in the Vacacai and Vacacai-Mirim rivers during the rice crop, especially among those analyzed, the herbicides clomazone and quinclorac and the insecticide fipronil.

Destino ambiental dos herbicidas do grupo das imidazolinonas: revisão

The herbicides of the imidazolinone group control a wide range of weed species. They are absorbed by weed roots and leaves and transported through the phloem and xylem, accumulating in the plant growing points. They inhibit the enzyme acetolactate synthase (ALS), which synthesizes the branched chain amino acids. When used in the field, a large portion of these herbicides reach the soil, where they can be absorbed by the roots of plants, sorbed into the soil colloids, or dissolved in soil solution, going through photolysis, hydrolysis, microbial degradation or leaching. The sorption of imidazolinone is faster and affects other processes. High contents of clay, organic matter and pH lower than 6.0 contribute to enhance the sorption and persistence of imidazolinones in soil. The most important way of dissipation is by microbial degradation, thus conditions favoring microbial development will also enhance imidazolinone degradation.

Study of the Degradation of the Herbicide Clomazone in Distilled and in Irrigated Rice Field Waters using HPLC-DAD and GC-MS

This study evaluated the degradation of the herbicide clomazone in distilled water and from irrigated rice fields, through UV irradiation and under natural conditions. After a solid phase extraction (SPE) as preconcentration step, the remained concentration of clomazone was determined by high performance liquid chromatography with diode array detection (HPLC-DAD) and the identification of the degradation products was achieved by gas chromatography-mass spectrometry (GC-MS). Under UV irradiation, the clomazone was degraded faster in distilled water than in surface water. In irrigated rice water, under sunlight irradiation, clomazone presented a half-life time average of 3.2 days in three consecutive harvests, and after application the concentration in water remained higher than 0.1 μg L-1 for 20 days. Several by-products, like 2-chlorobenzaldehyde and 2-chlorobenzene methanol, were identified by GC-MS, which evidenced that the concentration of intermediates at the begining increase and then they also undergo degradation.

Persistence of the herbicides imazethapyr and imazapic in irrigated rice soil

The mixture of herbicides imazethapyr and imazapic is used to control red rice in irrigated rice crops. However, such herbicides might persist on the soil for a long period causing phytotoxicity on susceptible rice grown in succession. The objective of this work was to determine the effect of different soil tillage systems during the off-season on the residual phytotoxicity of imazethapyr and imazapic on non tolerant rice. Herbicide residues caused phytotoxicity on susceptible rice with the highest values being registered 25 days after emergence and decreasing after this period until almost disappearing 60 days after emergence. Herbicide residues affected plant stand, number of stems per m2, number of panicles per m2 and plant height, but did not affect grain yield. Soil movement decreased herbicide activity on the superficial soil layer (0-3 cm).

Controle químico de arroz-vermelho na cultura do arroz irrigado

Red rice (Oryza spp.) reduces rice (Oryza sativa L.) grain yield and quality. A field study was conducted to compare two red rice control tools, the first using the Clearfield™ system and the second using high rates of clomazone and rice seeds treated with safener to suppress red rice emergence. The treatments included: check control without herbicide application, three treatments for the formulated herbicide mixture (imazethapyr 75 g i.a. L-1 + imazapic 25 g i.a. L-1) under the Clearfield system, and three clomazone treatments (clomazone 500 g i.a. L-1). The most efficient treatment for red rice control was the formulated mixture of imazethapyr + imazapic (0.7 L ha-1 PRE followed by 0.7 L ha-1 POST). This treatment promoted 100% red rice control, without affecting plant stand and promoting high grain yield.