Abstract The objective of this work was to adapt and validate a multiresidue method for pesticide analysis, to determine the influence of the current postharvest handling steps on the degradation of pesticide residues in papaya. 'THB' papaya of the Solo group were sampled at each postharvest handling step in the packinghouse. For the validation of the multiresidue analysis in papaya, the technique used for extraction was the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method, with modifications. Pesticide quantification was carried out using an ultra-high performance liquid chromatograph coupled to a triple quadrupole mass spectrometer with electrospray ionization (UHPLC-MS/MS). Fruit were analyzed before and after the handling procedures and were evaluated after ripening. The used methodology was successfully validated to detect the azoxystrobin, carbendazim, carbofuran, difenoconazole, imazalil, imidacloprid, flutriafol, prochloraz, pyraclostrobin, tebuconazole, thiabendazole, and thiacloprid pesticides in papaya. Fruit washing reduces azoxystrobin and difenoconazole residue levels in 78 to 90% and in 47 to 90% on fruit surface, respectively. Although the postharvest handling steps are ineffective in reducing the levels of thiabendazole, if this fungicide is applied at the appropriate rate, the residue levels will remain below the limits permitted by law. THB 'THB packinghouse quick easy cheap effective rugged QuEChERS (QuEChERS modifications ultrahigh ultra high UHPLCMS/MS. UHPLCMSMS UHPLC MS/MS . MS (UHPLC-MS/MS) ripening carbendazim carbofuran imazalil imidacloprid flutriafol prochloraz pyraclostrobin tebuconazole thiabendazole 7 90 4 surface respectively rate law UHPLCMS UHPLCMS/MS MSMS (UHPLC-MS/MS 9

Resumo O objetivo deste trabalho foi adaptar e validar um método multirresíduo para análise de agrotóxicos, para determinar a influência das atuais etapas de manejo pós-colheita sobre a degradação de resíduos de agrotóxicos em mamão. Mamões 'THB' do grupo Solo foram amostrados em cada etapa de manejo pós-colheita, em casa de beneficiamento. Para a validação da análise multirresíduos em mamão, a técnica de extração utilizada foi o método quick, easy, cheap, effective, rugged, and safe (QuEChERS), com modificações. A quantificação foi realizada com cromatógrafo líquido de ultraeficiência, acoplado a espectrômetro de massa triplo, quadrupolo, com ionização por eletrospray (UHPLC-MS/MS). Os frutos foram analisados antes e depois dos procedimentos de manuseio e avaliados após o amadurecimento. A metodologia utilizada foi validada com sucesso para detectar os pesticidas azoxistrobina, carbendazim, carbofuran, difenoconazol, imazalil, imidacloprid, flutriafol, prochloraz, piraclostrobina, tebuconazol, tiabendazol e thiacloprid em mamão. A lavagem dos frutos reduz os níveis de resíduos de azoxistrobina e difenoconazol em 78 a 90% e em 47 a 90% na superfície dos frutos, respectivamente. Embora as etapas de manejo pós-colheita sejam ineficazes para a redução dos níveis do tiabendazol, se este fungicida for utilizado na dose adequada, os níveis de resíduos permanecerão abaixo dos limites permitidos por lei. póscolheita pós colheita mamão THB 'THB póscolheita, colheita, beneficiamento quick easy cheap effective rugged QuEChERS, QuEChERS , (QuEChERS) modificações ultraeficiência triplo quadrupolo UHPLCMS/MS. UHPLCMSMS UHPLC MS/MS . MS (UHPLC-MS/MS) amadurecimento carbendazim carbofuran imazalil imidacloprid flutriafol prochloraz piraclostrobina tebuconazol 7 90 4 respectivamente adequada lei (QuEChERS UHPLCMS UHPLCMS/MS MSMS (UHPLC-MS/MS 9

RESUMO Uma possível alternativa ao uso de fármacos veterinários no tratamento e prevenção de doenças na piscicultura é o uso do óleo essencial de Piper aduncum. No entanto, são necessários dados ecotoxicológicos para garantir seu uso apropriado sem causar efeitos adversos a organismos não alvo. Esta informação é relevante, pois esse óleo essencial é descrito como tendo atividades inseticidas, moluscicidas e citotóxicas, possivelmente associadas à sua composição química. Assim, o objetivo deste estudo foi avaliar a ecotoxicidade do óleo essencial de P. aduncum para cinco organismos-teste, usando o método estatístico da Distribuição da Sensibilidade das Espécies (SSD). A composição química do óleo essencial foi caracterizada por cromatografia gasosa acoplada a espectrometria de massa (GC-MS) e cromatografia gasosa com detector de ionização de chama (GC-FID), para fins de identificação e quantificação, respectivamente. O principal componente (75,5%) do óleo essencial foi o dilapiol. A concentração perigosa para 5% de espécies biológicas (HC5) foi calculada com um nível de proteção de 95%, resultando em um valor de 0,47 mg L-1 (com intervalo de confiança de 50% = 0,028 - 1,19 mg L-1). A faixa de concentração relacionada aos níveis de proteção para comunidades aquáticas (concentração sem efeito previsto - PNEC) foi calculada através da aplicação de fatores de segurança ao valor de HC5. Os parâmetros de ecotoxicidade indicaram que o óleo essencial de P. aduncum pode ser usado com segurança em corpos d’água se a concentração for igual ou inferior a 0,09 mg L-1.

ABSTRACT One possible alternative to chemotherapeutic agents in the treatment and prevention of diseases in fish farms is the use of Piper aduncum essential oil. However, ecotoxicological data are required to ensure its proper use and to prevent adverse effects on non-target organisms. These data are relevant since this essential oil is described as having insecticidal, molluscicidal and cytotoxic activitiy that may be associated with its chemical composition. Thus, the aim of this study was to evaluate the ecotoxicity of P. aduncum essential oil to five test organisms using the species sensitivity distribution (SSD) statistical approach. The chemical composition of the essential oil was characterized by means of gas chromatography coupled to mass spectrometry (GC-MS) and gas chromatography-flame ionization detection (GC-FID) for identification and quantitation purposes, respectively. The main component (75.5%) of the essential oil was dillapiole. The hazardous concentration for 5% of biological species (HC5) was calculated to determine the 95% protection level, resulting in a value of 0.47 mg L-1 (with a confidence interval of 0.028 - 1.19 mg L-1. ). A concentration range related to the level of protection for aquatic communities (the predicted no-effect concentration, PNEC) was determined through the application of safety factors to the HC5 value. The ecotoxicity parameters showed that P. aduncum essential oil can be used safely in water bodies at a concentration equal to or below 0.09 mg L-1.

The analysis of volatiles is an alternative in the routine of quality control of fruits, since the volatile metabolites can change in the presence of microorganisms. A well-established method for extracting volatiles is the solid phase microextraction (SPME). This work aims to define some parameters (fiber coating, conditioning time and fiber exposure time) for an effective extraction. Whole papaya was inserted into a hermetically closed glass bottle and the system was left in conditioning for the volatiles accumulation. Then, extraction by SPME and subsequent desorption in a gas chromatograph was performed. Two fibers were evaluated: a 100 µm polydimethylsiloxane (PDMS) and a 65 µm polydimethylsiloxane/divinylbenzene (PDMS/DVB). The PDMS/DVB fiber extracted the highest number of volatiles. Central composite design (CCD) was performed to assess the effect of papaya conditioning time and the fiber exposure time on the response: number of detectable peaks. Both variables studied and their interactions were significant for the response. ANOVA showed that the quadratic terms and the lack of fit were not significant (p <0.05). A conditioning time of 10 min and exposure time of 30 min was sufficient for the detection of more than 100 compounds.

RESUMO: O interesse pelo ácido chiquímico (SA) tem apresentado um forte incremento nos últimos anos devido à crescente demanda da indústria farmacêutica e cosmética. O SA é utilizado como um precursor para a síntese do fosfato de oseltamivir (Tamiflu®), um potente inibidor viral. Este ácido é extraído principalmente da planta Illicium verum Hook. A disponibilidade desta planta é um fator limitante para o crescimento do mercado no futuro próximo. Este artigo propõe Urochloa plantaginea (Link.) webster tratada com sub doses de glifosato, como uma fonte alternativa de SA. Plantas de U. plantaginea com 3 - 4 perfilhos e 4 a 6 folhas foram tratadas com subdoses de glifosato e coletadas aos 0, 3, 6, 9 e 12 dias após sua aplicação (DAT). As amostras foram secas, extraídas e analisadas por HPLC e confirmadas por LC-MS/MS. As concentrações máximas de SA foram observadas aos seis dias após aplicação do glifosato a 36 g.e.a.ha-1 em plantas de U. plantaginea com 4 - 6 folhas. A capacidade anual dessa gramínea para produzir níveis elevados de SA em toda a biomassa, pode ser uma fonte economicamente viável de SA.

ABSTRACT: Shikimic acid (SA) has witnessed a strong increase in recent years due to the increasing demand of the pharmaceutical and cosmetic industry. The SA is used as a precursor for the synthesis of oseltamivir phosphate (Tamiflu®), a potent viral inhibitor and is extracted from the plant Illicium verum Hook which has a limited availability. This article proposed the use of Urochloa plantaginea (Link.) webster and glyphosate, as an alternative source of SA. U. plantaginea plants with 3 - 4 tillers and 4 - 6 leaves were harvest at 3, 6, 9 and 12 days after application (DAT) of low rates of glyphosate. Samples were dried, extracted, analyzed by HPLC and LC-MS/MS. The maximum SA concentrations were observed at 6 days after glyphosate at 36 g.a.e.ha-1 was applied in plants of U. plantaginea with 4 to 6 leaves. The capability of this annual gramineae to produce elevated SA levels throughout the entire biomass affords its potential for a greater yield on a per hectare basis.

Resumo Há preocupação em relação a problemas causados por pesticidas no ser humano, o que levou uma parcela de viticultores a adotar procedimentos de agricultura orgânica em seus vinhedos. Assim, devido a essa preocupação, eles estão produzindo uva pelo sistema orgânico, sendo que uma parte dessa produção é direcionada à elaboração de vinho. Apesar de essas uvas terem sido aprovadas por entidades certificadoras, houve demanda para a realização de um levantamento para determinar a composição dos vinhos delas derivados. Portanto, cinco garrafas de cada tipo de vinho foram coletadas em vinícolas e supermercados da Serra Gaúcha, Rio Grande do Sul, sendo uma parte de vinhos varietais e outra, de cortes de diferentes variedades. As análises foram feitas por métodos físico-químicos: compostos voláteis, por cromatografia gasosa; minerais e elementos-traço, por espectrometria de emissão ótica com plasma acoplado indutivamente, e resíduos de pesticidas, por cromatografia líquida-espectrometria de massa. Os resultados mostram que a composição físico-química desses vinhos e dos minerais situou-se, em geral, dentro dos limites da legislação brasileira. As concentrações de minerais e de elementos-traço foram muito baixas, e não foram detectados resíduos de pesticidas (LMR = 10 μg.kg–1) em nenhum vinho.

Summary There is concern about the health problems caused by pesticides in humans, which has led some grape producers to adopt organic procedures in their vineyards, and a certain amount of these grapes are directed to winemaking. Despite the approval awarded to this organic grape production by the certified organizations, there has been a demand to carry out a survey to determine the physicochemical composition of the wine derived from these products. Some of these wines were made from a single grape variety and others from more than one. For this survey, the samples consisted of five bottles of each type of wine, acquired from wineries and supermarkets in the Serra Gaúcha region, RS, Brazil. The analyses were carried out by physicochemical methods: volatile compounds by gas chromatography; minerals and trace elements by inductively coupled plasma optical emission spectrometry; and pesticide residues by liquid chromatography-mass spectrometry. The results showed that in general the physicochemical composition of these wines was within the limits established by Brazilian legislation. The mineral and trace element concentrations were very low and pesticide residues were not detected (MRL = 10 μg.kg–1) in any of the wines.

Demand for organic products is intensified in many countries each year. Following this trend, Brazil produces increasing volumes of organic grape juice. In this way, a survey of organic grape juices made from grapes produced according to this system was carried out where physicochemical composition, minerals, trace elements, and pesticide residues were determined. Variables related to grape juice composition were performed by physicochemical procedures; minerals and trace elements, by inductively plasma optical emission spectrometry; pesticide residues, by liquid chromatography-mass spectrometry. Main results show that the physicochemical composition of organic grape juices was in general in accordance to the Brazilian legislation. The mean concentrations of trace elements were very low, varying from 0.002 (Cd) to 0.970 (Ba) mg L–1. Pesticide residues were not detected in any sample analyzed (MRL= 10 µg L–1). These results show that the Serra Gaúcha viticultural region present conditions to produce organic grape juices, despite the adverse climate factors that occurs in some years. Nevertheless, these products should be made with grape varieties, such as the labrusca ones, less susceptibles to the main grapevine pathogens.

This paper describes the use of pesticides in agriculture. Research has shown that significant quantities of pesticide residues have been found in many types of foods. Thus, an overview is given of pesticide residue determinations in fruits and vegetables, with special attention to apples. The toxicity and the adverse effects possibly caused by the exposure of these compounds are alerting the scientific community to develop studies about the validation of analytical methods for multiresidue pesticide determination in these samples. This review shows that pesticide-residue determination in apples is becoming a very important and challenging issue.