CONTATO Tempo (dias)

0 15 30 45 60 75 90 Sa fr ol (µ g kg -1 ) 0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 B. FUMIGAÇÃO Tempo (dias) 0 15 30 45 60 75 90 Sa fr ol (µg kg -1 ) 0,0 0,5 1,0 1,5 2,0 2,5

Figura 5. Persistência do resíduo de safrol em feijão-caupi tratado com óleo essencial de Piper hispidinervum por contato (a) e por fumigação (b) durante o armazenamento.

O efeito residual do OEPH em grãos de feijão-caupi e milho armazenados por até 120 dias, para C. maculatus e Sitophilus zeamais Mots. (Coleoptera: Curculionidae) foi avaliado por Pereira et al. (2009) e Coitinho et al. (2010). A toxicidade do OEPH foi maior logo após a contaminação dos grãos, com valores de 100 a 93,8% de mortalidade. Após 30 dias de armazenamento, observou-se baixo efeito residual, com mortalidade inferior a 17,5%. Neste estudo a degradação de 99% do OEPH ocorreu após 5 dias de armazenamento, o que pode explicar a baixa toxicidade encontrada por Pereira et al. (2009) e Coitinho et al. (2010), após 30 dias de armazenamento.

Estudos demostram que inseticidas botânicos apresentam baixa persistência em produtos armazenados (Pereira et al., 2009; Coitinho et al., 2010; Lu et al., 2013). A alicina, composto majoritário do OE de Allium sativum L (Amaryllidaceae), foi monitorada durante e após a fumigação do trigo; sendo que após a fumigação os grãos foram aerados (Lu et al., 2013). Esses autores constataram que a concentração de alicina reduziu à medida que o tempo de fumigação e aeração aumentou. O decaimento da concentração apresentou comportamento exponencial. A concentração de alicina utilizada para a fumigação dos grãos de trigo foi de 615 μL L-1 _{de ar. Após um dia da fumigação, a concentração reduziu em 98,99% e com 16}

dias de aeração, a redução da concentração de alicina atingiu 99,99%. A degradação dos óleos essenciais é explicada pela instabilidade química dos seus constituintes. É comum ocorrer reações de oxidação, isomerização, ciclização ou desidrogenação as quais são desencadeadas por enzimas ou por outras moléculas, como o oxigênio. A temperatura, a luz e a

disponibilidade de oxigênio atmosférico também influenciam a estabilidade dos óleos essenciais (Turek e Stintzing, 2013).

Conclusão

O método de microextração fase sólida em headspace acoplado com o cromatógrafo a gás com detector por ionização em chama para extrair o safrol do feijão-caupi tratado com OEPH foi otimizado. A condição ótima para extração do safrol foi a temperatura de 60 ºC e tempo de 10 min utilizando a fibra DVB/CAR/PDMS stableflex de 50/30 μm. O método otimizado apresentou uma boa linearidade nas faixas testadas, com repetibilidade, bons limites de detecção e quantificação. As concentrações de safrol avaliadas durante o armazenamento do feijão-caupi tratado com o OEPH por contato variaram de 1,0945 a 0,0513 µg kg-1 _{e por fumigação de 2,1606 a 0,1239 µg kg}-1_{. As concentrações detectadas a partir do}

quinto dia representam menos de 1% da concentração inicial, o que mostra que o safrol apresenta baixa persistência nos grãos de feijão-caupi.

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