Pyrethroid pesticide metabolite, 3-PBA, in soils: method development and application to real agricultural soils

3-Phenoxybenzoic acid (3-PBA) is a shared metabolite of several synthetic pyrethroid pesticides (SPs) resulting from environmental degradation of parent compounds and thus occurs frequently as a residue in samples. Hence, the importance of 3-PBA evaluation after pyrethroid application. There is a gap of analytical methods to determine 3-PBA in soil samples. Therefore, an analytical method that combines the solid-phase extraction (SPE) and gas chromatography-mass spectrometry (GC/MS) detection has been developed for the determination of 3-PBA in soil samples. The analytical method was validated in terms of linearity, sensitivity, intra- and inter-day batch precisions, recoveries, and quantification limits. An SPE method using a Strata X cartridge allows obtaining limits of detection and quantification equal to 4.0 and 13.3 ng g-1, respectively. Under optimized conditions, the method average recovery levels ranged from 70.3 to 93.5% with a relative standard deviation below 3.4%. Method intra- and inter-day precision was under 5.0 and 4.8%, respectively. The developed method was applied to 11 agricultural soil samples in the north of Portugal. The developed methodology allowed for the determination of the pyrethroid metabolite, 3-PBA, in agricultural soil samples at levels of few ng g-1. Graphical abstract ᅟ.I. Bragança is financially supported by FCT through the doctoral research grant financed by fellowship (SFRH/BD/52504/2014). This work was supported by the Associate Laboratory for Green Chemistry-LAQV which is financed by national funds from FCT/MCTES (UID/QUI/50006/2013) and co-financed by the ERDF under the PT2020 Partnership Agreement (POCI-01-0145-FEDER-007265).info:eu-repo/semantics/publishedVersio

Assessment of Pyrethroid Pesticides in Topsoils in Northern Portugal

Pyrethroid insecticides are emerging contam-inants broadly used for insect pest control in agriculture,veterinary, and domestic applications. Limited informa-tion can be found in literature regarding pyrethroidpesticide soil contamination in playgrounds and agricul-tural areas. The focus of this study was on new findingsrelated to the spatial and seasonal occurrence of pyre-throid pesticide contamination in soils of northern Por-tugal. The soils were tested during summer and winterseasons. Pyrethroid pesticides were not found in the tenplaygrounds sampled during both seasons. For the 18agricultural soil samples tested, deltamethrin was theonly pyrethroid detected, just during the summer sea-son. For those, three of the samples taken were found tobe positive with concentrations between 15.7 and101.7 ng g−1. The results denote the need for monitoringand assessment of pyrethroid pesticide contamination inPortuguese soil. Further research is needed to access the ecological potential impact of pyrethroid pesticides onsoil.This work was supported by the Associ-ate Laboratory for Green Chemistry - LAQV which is financed bythe national funds from FCT/MCTES (UID/QUI/50006/2013) andco-financed by the ERDF under the PT2020 Partnership Agree-ment (POCI-01-0145-FEDER - 007265).info:eu-repo/semantics/publishedVersio

Produção de óleos e fillers proteicos a partir da raspa tripa da indústria de curtumes

A indústria de curtumes é fortemente geradora de resíduos sólidos e águas residuais pelo que a necessidade de criar alternativas para a sua valorização e minimização é premente e constante. Este trabalho teve, como principal objectivo, o aproveitamento da raspa tripa, resíduo da indústria de curtumes. Para tal, a raspa tripa foi sujeita a um processo de hidrólise térmica e/ou enzimática para obtenção de gordura e hidrolisado proteico. Na hidrólise da raspa tripa foi estudada a influência de vários factores como a quantidade de enzima e de água, a temperatura e o tempo. Constatou-se que foi para a temperatura de 60ºC, um tempo de quatro horas, uma quantidade de 2% de enzima e 100% de água, relativamente à massa de raspa utilizada, que se obteve o melhor resultado com um rendimento de extracção de 93%. A partir da gordura obtida foram produzidos óleos por sulfatação e sulfitação, designados por óleos sulfatados e sulfitados, respectivamente. O hidrolisado proteico obtido foi concentrado por evaporação para aumentar o seu teor de sólidos totais. Com este foram produzidos gluproteicos e fillers, por acção de glutaraldeído e do efeito sinérgico de outros produtos. Os óleos, o hidrolisado concentrado e seus derivados foram testados no processo de engorduramento e recurtume do couro. A avaliação dos resultados foi realizada por comparação dos resultados dos testes físico-mecânicos das amostras de pele obtidas com valores de referência e por comparação com um ensaio padrão em que se utilizaram produtos de referência do mercado. Os resultados foram muitos satisfatórios visto que foram superiores aos valores de referência e também superiores aos valores obtidos para o padrão salvo raras excepções. Reconheceu-se assim a aplicabilidade destes produtos no processo de recurtume e engorduramento que também corresponderam no que respeita a características importantes do couro como a firmeza de flor e o toque. No decorrer do trabalho constatou-se que as peles tratadas com hidrolisado proteico apresentavam uma cor mais intensa, pelo que se efectuou um estudo de colorimetria através do método CIELAB. Comprovou-se que o hidrolisado proteico e os gluproteicos quando utilizados no processo de recurtume, por substituição do Fortan A40, intensificam a cor da pele. A valorização da raspa tripa resulta numa dupla vantagem para a indústria dos curtumes. Se por um lado diminui o impacto ambiental que esta origina, por outro lado possibilita a produção de produtos que podem ser substitutos de outros produtos químicos que têm que ser adquiridos por esta indústria.The tanning industry generates a huge quantity of solid wastes and wastewater. Therefore, there is a strong and constant need to create alternatives for its valorization and minimization. The present work had as main objective the recovery of the fleshings, solid waste from the leather industry. For this, the fleshings were submitted to a thermal and/or enzymatic hydrolysis to obtain fat and protein hydrolysate. Fleshings hydrolysis was studied regarding the influence of various factors like the amount of enzyme and water, temperature and time. It was found that for the temperature of 60°C, a time of four hours, 2% of enzyme and 100% water, based on the mass of fleshings, the best extraction yield, 93 %, was obtained. Fat obtained through the hydrolysis process was used to produce oils by sulphation and sulphitation, designed as sulfated and sulfited oils, respectively. The protein hydrolyzate was neutralized and concentrated by evaporation to increase its solids content. With the protein hydrolysate, gluprotein products and fillers were prepared by the use of glutaraldehyde and by the synergistic effect of other products. The oils were applied in leather fatliquoring and the different protein hydrolysates products were tested in leather retannage. The obtained leather samples were then evaluated through the realization of physical-mechanical tests, comparing it with the results obtained through a standard process. The results were very satisfactory because they were above the reference values and also in most cases higher than the standard, with a few exceptions. It was found in the application of these products that the leather samples presented a satisfactory softness and grain firmness. On the other hand it was found that the skins treated with hydrolyzed protein had a more intense color. So, a study was made by the CIELAB colorimetric method. It was proved that protein hydrolyzate and gluprotein products, when used in the retannage process replacing Fortan A40, intensify the color of the leather. The valorization of this waste results in a double advantage for the leather industry. On the one hand it reduces the environmental impact of the leather industry and on the other hand enables the production of products that can be alternatives to some chemicals used in the leather fatliquoring and retanning

Produção de óleos e fillers proteicos a partir da raspa tripa da indústria de curtumes

A indústria de curtumes é fortemente geradora de resíduos sólidos e águas residuais pelo que a necessidade de criar alternativas para a sua valorização e minimização é premente e constante. Este trabalho teve, como principal objectivo, o aproveitamento da raspa tripa, resíduo da indústria de curtumes. Para tal, a raspa tripa foi sujeita a um processo de hidrólise térmica e/ou enzimática para obtenção de gordura e hidrolisado proteico. Na hidrólise da raspa tripa foi estudada a influência de vários factores como a quantidade de enzima e de água, a temperatura e o tempo. Constatou-se que foi para a temperatura de 60ºC, um tempo de quatro horas, uma quantidade de 2% de enzima e 100% de água, relativamente à massa de raspa utilizada, que se obteve o melhor resultado com um rendimento de extracção de 93%. A partir da gordura obtida foram produzidos óleos por sulfatação e sulfitação, designados por óleos sulfatados e sulfitados, respectivamente. O hidrolisado proteico obtido foi concentrado por evaporação para aumentar o seu teor de sólidos totais. Com este foram produzidos gluproteicos e fillers, por acção de glutaraldeído e do efeito sinérgico de outros produtos. Os óleos, o hidrolisado concentrado e seus derivados foram testados no processo de engorduramento e recurtume do couro. A avaliação dos resultados foi realizada por comparação dos resultados dos testes físico-mecânicos das amostras de pele obtidas com valores de referência e por comparação com um ensaio padrão em que se utilizaram produtos de referência do mercado. Os resultados foram muitos satisfatórios visto que foram superiores aos valores de referência e também superiores aos valores obtidos para o padrão salvo raras excepções. Reconheceu-se assim a aplicabilidade destes produtos no processo de recurtume e engorduramento que também corresponderam no que respeita a características importantes do couro como a firmeza de flor e o toque. No decorrer do trabalho constatou-se que as peles tratadas com hidrolisado proteico apresentavam uma cor mais intensa, pelo que se efectuou um estudo de colorimetria através do método CIELAB. Comprovou-se que o hidrolisado proteico e os gluproteicos quando utilizados no processo de recurtume, por substituição do Fortan A40, intensificam a cor da pele. A valorização da raspa tripa resulta numa dupla vantagem para a indústria dos curtumes. Se por um lado diminui o impacto ambiental que esta origina, por outro lado possibilita a produção de produtos que podem ser substitutos de outros produtos químicos que têm que ser adquiridos por esta indústria.The tanning industry generates a huge quantity of solid wastes and wastewater. Therefore, there is a strong and constant need to create alternatives for its valorization and minimization. The present work had as main objective the recovery of the fleshings, solid waste from the leather industry. For this, the fleshings were submitted to a thermal and/or enzymatic hydrolysis to obtain fat and protein hydrolysate. Fleshings hydrolysis was studied regarding the influence of various factors like the amount of enzyme and water, temperature and time. It was found that for the temperature of 60°C, a time of four hours, 2% of enzyme and 100% water, based on the mass of fleshings, the best extraction yield, 93 %, was obtained. Fat obtained through the hydrolysis process was used to produce oils by sulphation and sulphitation, designed as sulfated and sulfited oils, respectively. The protein hydrolyzate was neutralized and concentrated by evaporation to increase its solids content. With the protein hydrolysate, gluprotein products and fillers were prepared by the use of glutaraldehyde and by the synergistic effect of other products. The oils were applied in leather fatliquoring and the different protein hydrolysates products were tested in leather retannage. The obtained leather samples were then evaluated through the realization of physical-mechanical tests, comparing it with the results obtained through a standard process. The results were very satisfactory because they were above the reference values and also in most cases higher than the standard, with a few exceptions. It was found in the application of these products that the leather samples presented a satisfactory softness and grain firmness. On the other hand it was found that the skins treated with hydrolyzed protein had a more intense color. So, a study was made by the CIELAB colorimetric method. It was proved that protein hydrolyzate and gluprotein products, when used in the retannage process replacing Fortan A40, intensify the color of the leather. The valorization of this waste results in a double advantage for the leather industry. On the one hand it reduces the environmental impact of the leather industry and on the other hand enables the production of products that can be alternatives to some chemicals used in the leather fatliquoring and retanning

Adding value [valorization] to tannery fleshings: part II – effect of protein hydrolysates on leather dyeing

The tanning industry generates a high quantity of solid wastes. Therefore, there is a need to create valorization [added value] options for these wastes. The main objective of the present work was to study the effect of protein hydrolysates (HP) prepared from fleshings on leather dyeing. During previous studies it was found that the application of HP products, obtained from fleshings, in leather retannage intensified the colour of crust leather. In this work the CIELAB colour system was used to evaluate the effect of HP on retannage processes. The main conclusions of this study were: (i) HP can be used instead of a dicyanodiamide resin (Fortan DC) if the colour parameters of the standard procedure are to be maintained, and (ii) the replacement of an acrylic resin (Fortan A40) by glutaraldehyde-modified HP (GHP) results in a darker skin, and can therefore be interesting for the reduction of the quantity of dye used

QuEChERS: a new sample preparation approach for the determination of ibuprofen and its metabolites in soils

Ibuprofen is one of the most used active pharmaceutical ingredients worldwide. A new method for the analysis of ibuprofen and its metabolites, hydroxyibuprofen and carboxyibuprofen, in soils is presented. The extraction of these compounds from the soil matrices was performed by using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. The method involves a single extraction of the investigated compounds with purified water (acidified at pH 2.5 with hydrochloric acid), and a slow and continuous addition of the QuEChERS content, followed by the addition of acidified acetonitrile (1% acetic acid), prior to the determination by liquid chromatography coupled with fluorescence detection (LC–FLD). Validation studies were carried out using soil samples with a range of organic carbon contents. Recoveries of the fortified samples ranged from 79.5% to 101%. Relative standard deviations for all matrix–compound combinations did not exceed 3%. The method quantification limits were ≤22.4 μg kg−1 in all cases. The developed method was applied to the analysis of sixteen real samples

Use of cashew gum for development of LBL films with antibacterial actibity for applicantion against foodborne pathogens

Escherichia coli are one ofthe most common etiological agents of diarrhea in developing countries. The appearance of resistant E. coliprevents these infections treatment, thus antimicrobial peptides and their biotechnological applications can make good alternatives to treat and prevent intestinal infections by these bacteria. The aim of this study was to evaluate the antibacterial activity of PcL342-354C peptide, derived from Cry1Ab16 Toxinfrom Bacillus thuringiensis, againsts trains of E. coli, as well as the synthesis, characterization and evaluation of the antibacterial activity of layer-by-layer(LbL) films containing PcL342-354C. The results showed that the PcL342-354Cpeptide inhibited the growth of E. coliATCC 25922 (Minimal Inhibitory Concentration -MIC-: 31.25 μg/mL), E. coliML1 (MIC: 31.25 μg/mL) and E. coli ATCC 35218 (MIC: 15.62 μg/mL). The Minimal Bactericidal Concentration was250 μg/mL for all strains used,proving a potential antibacterial activity against these Gram-negative bacteria. Morphological effect on E. coli,produced by Cry1Ab16 Toxin derived peptide at MIC, was significant. The morphology of the ITO/Cashew gum/PcL342-354C film was analysed using Atomic Force Microscopy (AFM) which showed an increase of roughness due to the increase in the number of layers. LbL film has antibacterial activity against E. coli NCTC 9001 in both tested conditions (10 and 20 bilayers). Our results indicate that the peptide exhibits an antibacterial potential that can be tapped to develop biomaterials with antibacterial activity for use against foodborne pathogens.Fil: Placido, Alexandra. Universidad de Porto; PortugalFil: Bragança, Idalina. Universidad de Porto; PortugalFil: Marani, Mariela Mirta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Centro Nacional Patagónico. Instituto Patagónico para el Estudio de los Ecosistemas Continentales; ArgentinaFil: Rodrigues de Araujo, Alyne. Universidade Federal do Piaui; BrasilFil: Vasconcelos, Adreanne G.. Universidade Federal do Piaui; BrasilFil: Batziou, Krystallenia. Universidad de Porto; PortugalFil: Domingues, Valentina. Universidad de Porto; PortugalFil: Eaton, Peter. Universidad de Porto; PortugalFil: de Souza de Almedia Leite, José Roberto. Universidade Federal do Piaui; BrasilFil: Delerue Matos, Cristina. Universidad de Porto; PortugalXIII Encontro de Química dos AlimentosPortoPortugalUniversidade do PortoSociedade Portuguesa de Químic