A new method for the determination of clomazone, fipronil, tebuconazole, propiconazole, and azoxystrobin in samples of rice paddy soil is presented. The extraction of the pesticides from soil samples was performed by using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. Some extraction conditions such as salt addition, sample acidification, use of buffer, and cleanup step were evaluated. The optimized method dealt with a single extraction of the compounds under study with acidified acetonitrile, followed by the addition of MgSO(4) and NaCl prior to the final determination by liquid chromatography-atmospheric chemical pressure ionization-tandem mass spectrometry. Validation studies were carried out in soil samples. Recoveries of the spiked samples ranged between 70.3 and 120% with relative standard deviation lower than 18.2%. The limits of quantification were between 10 and 50 μg kg(-1). The method was applied to the analysis of real samples of soils where rice is cultivated.

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Os agrotóxicos são usados em muitas culturas para prevenir e preservar os grãos de possíveis ataques de pragas. O objetivo deste trabalho foi avaliar a distribuição dos agrotóxicos bispiribaque de sódio, carbofurano, clomazona e tebuconazol nas diferentes frações do arroz beneficiado (arroz branco, farelo de arroz, arroz com casca, arroz parboilizado beneficiado, farelo de arroz parboilizado e arroz parboilizado com casca), o qual foi cultivado em campos experimentais sob condições controladas de aplicação. Para tanto, o método QuEChERS foi otimizado para a extração dos agrotóxicos e validou-se um método utilizando CLAE-DAD para quantificação e CL-EM para confirmação. O método QuEChERS modificado foi adequado na extração dos agrotóxicos, bem como as condições cromatográficas para identificação e quantificação, conforme os indicativos de eficiência determinados: LOD de 0,07 mg kg -1 e LOQ de 0,2 mg kg -1 para a mistura dos agrotóxicos, e recuperação para arroz e farelo de arroz de 119 e 116%, 84 e 119%, 113 e 96%, 103 e 97% para carbofurano, bispiribaque de sódio, clomazona e tebuconazol, respectivamente. O método desenvolvido foi aplicado nas frações do beneficiamento e o farelo apresentou maior concentração de resíduo dos agrotóxicos, quando comparado ao arroz beneficiado, sendo 8,0, 2,3, 2,2 e 1,6 vezes mais contaminado, em média, para tebuconazol, clomazona, carbofurano e bispiribaque de sódio, respectivamente. Apenas o clomazona e o tebuconazol apresentaram concentrações dentro do limite aceitável estabelecidos pelo Codex Alimentarius (0,1 mg kg -1 ) para o arroz beneficiado nas safras analisadas.Pesticides are used to prevent pests from attacking grains in order to preserve the crops. This paper aims at evaluating the distribution of the pesticides bispyribac-sodium, carbofuran, clomazone and tebuconazole in different fractions of milled rice (white rice, rice bran, husked rice, parboiled rice, parboiled rice bran, and husked parboiled rice) which is planted on experimental fields under controlled conditions. The QuEChERS method was adapted to the extraction of pesticides and validated by using HPLC-DAD for quantification and LC-MS for confirmation. The analytical method of extracting pesticides, as well as the chromatographic conditions for identification and quantification, were suitable, according to certain efficiency indicators: 0.07 mg kg -1 LOD and 0.2 mg kg -1 LOQ for the mixture of pesticides and rice and rice bran recoveries of 119 and 116%, 84 and 119%, 113 and 96%, 103 and 97% for carbofuran, bispyribac-sodium, clomazone and tebuconazole, respectively. The method under development was applied to rice fractions: bran had the highest residue concentration of the studied pesticides, when compared to milled rice, showing 8.0, 2.3, 2.2 and 1.6 times more contamination, in average, with tebuconazole, clomazone, carbofuran and bispyribac-sodium, respectively. Only clomazone and tebuconazole were in the acceptable limits established by Codex Alimentarius (0.1 mg kg -1 ) for milled rice.

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This study aimed to evaluate the effect of fungicides on rice cultivation, regarding the occurrence and the distribution of mycotoxins in fractions of the processed grain, by a validated chromatographic method. A method based on extraction with acetonitrile:water, determination by HPLC-DAD, and confirmation by LC-MS was validated before the mycotoxin evaluation. Control samples and samples to which triazole fungicides had been applied were collected from experimental fields for four years. Results showed that 87% of the samples were contaminated with deoxynivalenol or zearalenone, and that all samples treated with fungicide were contaminated with some of these mycotoxins. Aflatoxin B(1) and ochratoxin A were found in 37% of the samples; half of them had been treated with fungicide. Therefore, fungicides tend to be stressors for toxigenic fungi found in the fields.

Considering the qualitative and quantitative losses