The growing awareness of health and well-being has led to increased consumption of healthy foods, such as exotic fruits, owing to their high nutritional value and global availability. However, the production and trade of exotic fruit presents significant challenges, particularly with regard to increasing supply and ensuring food safety concerning pesticide residues. This review examines modern analytical strategies employed to determine pesticide residues in exotic fruits. It is evident from the literature that ultra-high performance liquid chromatography and gas chromatography techniques, coupled with tandem mass spectrometry, remain the methods of choice for determining pesticide residues. For sample preparation, the QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) method, renowned for its simplicity and efficiency, is extensively utilized in its original form as well as in acetate, citrate, and other modified versions to enhance its effectiveness. Developing these analytical methods is crucial for ensuring the safety of exotic fruits, protecting consumer health, and facilitating exports to global markets. Further advancements in this field are essential to overcome the challenges posed by producing and trading exotic fruits, thereby promoting food safety and public health. This review also discusses the occurrence of pesticides in exotic fruits. wellbeing being foods fruits availability However ultrahigh ultra techniques spectrometry preparation Quick, Quick (Quick Easy Cheap Effective Rugged Safe method efficiency acetate citrate effectiveness markets

Resumo A maioria dos sistemas convencionais de tratamento de esgoto não é capaz de remover totalmente os micropoluentes presentes no esgoto. Assim, a degradação simultânea de 11 fármacos, detectados no efluente de uma estação de tratamento de esgoto no Sul do Brasil, foi investigada por meio de processos oxidativos avançados baseados em ozonização, radiação ultravioleta e peróxido de hidrogênio. Para detecção, as amostras foram preparadas por extração em fase sólida e os fármacos foram identificados por cromatografia líquida de ultra eficiência acoplada à espectrometria de massa em tandem. Ingredientes ativos como ciprofloxacina, oxitetraciclina, paracetamol, sulfametoxazol e trimetoprima tiveram suas concentrações aumentadas para análise de degradação. Os ensaios foram realizados em bancada a temperatura ambiente e pH neutro, com alíquotas coletadas aos 7,5 e 15 minutos. Duas doses de ozônio (0,5 e 0,9 mg por mg de carbono orgânico dissolvido) e combinações da menor dose de ozônio com fotólise (254 nm) e com 25 mg.L−1 de peróxido de hidrogênio foram avaliadas. A eficiência da mineralização dos fármacos foi verificada em um analisador de carbono orgânico total. O processo combinando de ozônio, peróxido de hidrogênio e radiação ultravioleta foi o mais eficiente na degradação de todos os fármacos detectados neste estudo, pois permitiu reduzir a oxitetraciclina em 89,32%, a cafeína em 96,79%, o trimetoprim em 97,40%, a ciprofloxacina em 97,75%, o sulfametoxazol em 99,79%, o paracetamol em 99,96% e a clindamicina, a ofloxacina, a sulfadiazina, o sulfatiazol e a tilosina em 100%. Esse processo também registrou a maior taxa de mineralização (60,52%), confirmando o potencial de redução de fármacos persistentes encontrados em sistemas convencionais de tratamento de esgoto. Assim 1 Brasil ozonização detecção tandem neutro 75 7 5 7, minutos 0,5 05 0 (0, 09 9 0, dissolvido 254 (25 nm 2 mgL1 mgL L mg.L− avaliadas total estudo 8932 89 32 89,32% 9679 96 79 96,79% 9740 97 40 97,40% 9775 97,75% 9979 99 99,79% 9996 99,96 clindamicina ofloxacina sulfadiazina 100 100% 60,52%, 6052 60,52% , 60 52 (60,52%) (0 (2 mg.L 893 8 3 89,32 967 96,79 974 4 97,40 977 97,75 997 99,79 999 99,9 10 605 60,52 6 (60,52% ( 89,3 96,7 97,4 97,7 99,7 99, 60,5 (60,52 89, 96, 97, 60, (60,5 (60, (60 (6

Abstract Most conventional sewage treatment systems are not able to fully remove micropollutants found in sewage. Thus, the simultaneous degradation of 11 pharmaceuticals identified in the effluent of a sewage treatment plant in Southern Brazil was herein investigated through advanced oxidation processes based on ozonation, ultraviolet radiation and hydrogen peroxide. For detection, samples were prepared through solid-phase extraction and pharmaceuticals were identified through ultra-high performance liquid chromatography tandem mass spectrometry. Active ingredients such as ciprofloxacin, oxytetracycline, paracetamol, sulfamethoxazole and trimethoprim had their concentrations increased for degradation analysis purposes. Trials were carried out on a bench at room temperature and neutral pH, with aliquots collected at 7.5 and 15 minutes. Two ozone doses (0.5 and 0.9 mg per mg of dissolved organic carbon), and combinations of the lowest ozone dose with photolysis (254 nm) and with 25 mg.L−1 of hydrogen peroxide were evaluated. Pharmaceuticals mineralization efficiency was assessed in a total organic carbon analyzer. The process combining ozone, hydrogen peroxide and ultraviolet radiation was the most efficient in the degradation of all pharmaceuticals detected in this study, since it enabled reducing oxytetracycline by 89.32%, caffeine by 96.79%, trimethoprim by 97.40%, ciprofloxacin by 97.75%, sulfamethoxazole by 99.79%, paracetamol by 99.96%, and clindamycin, ofloxacin, sulfadiazine, sulfathiazole and tylosin by 100%. This process also recorded the highest mineralization rate (60.52%), fact that confirmed the potential to decrease persistent pharmaceuticals found in conventional sewage treatment systems. Thus 1 ozonation detection solidphase solid phase ultrahigh ultra high spectrometry purposes pH 75 7 5 7. minutes 0.5 05 0 (0. 09 9 0. carbon, , carbon) 254 (25 nm 2 mgL1 mgL L mg.L− evaluated analyzer study 8932 89 32 89.32% 9679 96 79 96.79% 9740 97 40 97.40% 9775 97.75% 9979 99 99.79% 9996 99.96% clindamycin ofloxacin sulfadiazine 100 100% 60.52%, 6052 60.52% 60 52 (60.52%) (0 (2 mg.L 893 8 3 89.32 967 96.79 974 4 97.40 977 97.75 997 99.79 999 99.96 10 605 60.52 6 (60.52% ( 89.3 96.7 97.4 97.7 99.7 99.9 60.5 (60.52 89. 96. 97. 99. 60. (60.5 (60. (60 (6

Resumo O objetivo deste trabalho foi avaliar a qualidade fisiológica e quantificar a eficácia do polímero na retenção de perdas por lixiviação do tratamento fitossanitário em sementes de soja com diferentes diâmetros e tratadas sob diferentes formas. Foram utilizados dois lotes de sementes com diferentes diâmetros e foram realizadas duas formas de aplicação do tratamento: polímero associados ao tratamento fitossanitário na mesma calda e aplicação do polímero em camada após o tratamento, sendo os tratamentos formados da seguinte maneira: Control= sem tratamento, Treat+pol= Tratamento fitossanitário + polímero aplicados na mesma calda, Treat/pol= Tratamento fitossanitário + polímero aplicados em camadas, Treat= Tratamento fitossanitário. Para avaliação da retenção do tratamento pelo polímero foi utilizado um extrator e realizada a quantificação do ingrediente ativo tiametoxam lixiviado. Para avaliação da qualidade fisiológica foram realizados os testes de germinação, primeira contagem, emergência, envelhecimento acelerado, comprimento de plântulas, massa seca de plântulas e grau de umidade. A aplicação de polímero associado ao tratamento fitossanitário de sementes foi eficiente na diminuição das perdas por lixiviação, reduzindo em 20% a perda de produtos. Não houve diferença na capacidade de retenção e na qualidade fisiológica entre as diferentes formas de aplicação do polímero. Sementes de maior tamanho apresentam maior vigor, porém a germinação não é afetada.

Abstract This study evaluated the physiological quality and quantified the efficiency of polymer in reducing the loss of phytosanitary products by leaching from soybean seeds of different diameters and in different treatments. Two lots of seed and two types of treatments were tested: polymers associated with seed treatment, and polymer application in layers after the seed treatment. For that, the following treatments were analyzed: Control= no seed treatment; Treat+pol= seed treatment + polymers in the mix; Treat/pol= seed treatment + polymers applied in layers; Treat= seed treatment. To evaluate seed treatment retention by the polymers, extraction equipment was employed and leaching of the active ingredient thiamethoxam was quantified. Evaluation of physical quality was conducted with tests of germination rate, first count, emergence rate, accelerated aging, seedling length, seedling dry mass and moisture content. Polymer application associated with seed treatment was efficient in reducing losses by leaching, reducing product loss by 20%. No significant differences in retention and physiological quality were found when different methods for polymer application were compared. Bigger seeds presented greater vigor, but the germination rate was unaffected.

RESUMO O uso do tratamento químico de sementes é uma importante ferramenta na proteção de plântulas e tem contribuído com a elevação da produtividade de arroz (Oryza sativa L.). Objetivou-se avaliar a qualidade fisiológica e quantificar a retenção de produtos químicos em sementes de arroz tratadas com inseticida e fungicida recobertas com polímeros. Foram utilizados seis tratamentos de sementes: controle, tratamento fitossanitário e tratamento fitossanitário e recobrimento com os polímeros, Florite 1127®, Resina Sólida GV5®, Polyseed CF® e o VermDynaseed®. A qualidade fisiológica foi avaliada pelo teste de germinação e vigor pelos testes de primeira contagem, índice de velocidade de germinação, comprimento de parte aérea, comprimento de radícula, massa seca de plântulas e emergência em areia. Para determinar a retenção dos ingredientes ativos metalaxil-M e thiamethoxam, utilizou-se equipamento denominado extrator. O experimento foi organizado no delineamento inteiramente casualizado (DIC) e as médias foram separadas pelo Scott Knott (p≤0,05).O tratamento de sementes com o fungicida e inseticida, recobertos com os polímeros,Florite 1127®, ResinSolid GV5®, Polyseed CF® e o VermDynaseed®, não afetaram a qualidade fisiológica de sementes de arroz. Os polímeros ResinSolid GV5®, Polyseed CF® e o VermDynaseed® foram eficientes na retenção do thiamethoxam junto às sementes de arroz, impedindo que parte do ingrediente ativo do inseticida fosse lixiviado, através das colunas de areia, logo após a precipitação pluvial simulada.

ABSTRACT The use of chemical seed treatment is an important tool in the protection of seedlings and has contributed to the increase of rice yield (Oryza sativa L.). The objective of this study was to evaluate the physiological quality and quantify the retention of chemical products in rice seeds treated with insecticide and fungicide coated with polymers. Six seed treatments were used: control, phytosanitary treatment and phytosanitary treatment and coating with the polymers, Florite 1127®, GV5® Solid Resin, Polyseed CF® and VermDynaseed®. The physiological quality was evaluated by the test of germination and vigor by first count tests, germination speed index, shoot length, radicle length, seedling dry mass and sand emergence. To determine the retention of the active ingredients metalaxyl-M and thiamethoxam, an equipment called extractor was used. The experiment was organized in a completely randomized design (DIC) and the averages were separated by the Scott Knott test (p≤0.05). Seed treatment with the fungicide and insecticide, coated with the polymers, Florite 1127®, Solid Resin GV5®, Polyseed CF® and VermDynaseed®, did not affect the physiological quality of rice seeds. Solid Resin GV5®, Polyseed CF® and VermDynaseed® polymers were efficient at retaining thiamethoxam in the rice seeds, preventing some of the active ingredients of the insecticide from being leached through the sand columns immediately after the simulated pluvial precipitation.

RESUMO. O estudo objetivou analisar resíduos de fungicidas e inseticidas nos grãos de arroz submetidos a diferentes formas de processamento. O trabalho foi realizado no campo durante três safras agrícolas com a aplicação de fungicidas e inseticidas sobre a parte aérea das plantas de arroz. Foi realizado um tratamento com a aplicação dos fungicidas azoxystrobin, difenoconazole, propiconazole, tebuconazole, trifloxystrobin no estádio de desenvolvimento R2, e outro tratamento com os mesmos fungicidas com duas aplicações nos estádios R2 e R4 em parcelas individuais. Um tratamento com inseticida consistiu na aplicação de cypermethrin, lambda-cyhalothrin, permethrin, thiamethoxam no estádio R2, e outro tratamento na aplicação de permethrin com intervalo de cinco dias entre as aplicações a partir do estádio de desenvolvimento R4 até um dia antes da colheita. Foram analisados resíduos de fungicida e inseticida nos grãos polidos e integral, cru, cozido e parboilizado, e na casca de arroz, totalizando 1.458 amostras. As amostras foram analisadas por cromatografia em fase gasosa com detecção por captura de elétrons (GC-ECD) usando QuEChERS modificados como método de extração. Resíduos de fungicidas e inseticidas não foram detectados nos grãos de arroz. No entanto, resíduos de azoxystrobin e cypermethrin foram detectados na casca de arroz.

ABSTRACT. The objective of this study was to analyse residues of fungicides and insecticides in rice grains that were subjected to different forms of processing. Field work was conducted during three crop seasons, and fungicides and insecticides were applied at different crop growth stages on the aerial portion of the rice plants. Azoxystrobin, difenoconazole, propiconazole, tebuconazole, and trifloxystrobin fungicides were sprayed only once at the R2 growth stage or twice at the R2 and R4 growth stages; cypermethrin, lambda-cyhalothrin, permethrin, and thiamethoxam insecticides were sprayed at the R2 growth stage; and permethrin was sprayed at 5-day intervals from the R4 growth stage up to one day prior to harvest. Pesticide residues were analysed in uncooked, cooked, parboiled, polished and brown rice grains as well as rice hulls during the three crop seasons, for a total of 1,458 samples. The samples were analysed by gas chromatography with electron capture detection (GC-ECD) using modified QuEChERS as the extraction method. No fungicide or insecticide residues were detected in rice grain samples; however, azoxystrobin and cypermethrin residues were detected in rice hull samples.

The determination of pesticide residues in water samples by Liquid Chromatography require sample preparation for extraction and enrichment of the analytes with the minimization of interferences to achieve adequate detection limits. The Solid Phase Extraction (SPE), Solid Phase Microextraction (SPME), Stir Bar Sorptive Extraction (SBSE) and Dispersive Liquid-Liquid Microextraction (DLLME) techniques have been widely used for extraction of pesticides in water. In this review, the principles of these sample preparation techniques associated with the analysis by Liquid Chromatography with Diode Array Detection (LC-DAD) or Mass Spectrometry (LC-MS) are described and an overview of several applications were presented and discussed.

This paper reports the development of an easy, fast and effective procedure for the verification of the ideal gas law in splitless injection systems in order to improve the response. Results of a group of pesticides were used to demonstrate the suitability of the approach. The procedure helps establish experimental parameters through theoretical aspects. The improved instrumental response allowed extraction with lower sample volumes, the minimization of time and costs and the simplification of sample preparation.