Determination of CHLORPYRIFOS by GC/ECD in water and its sorption mechanism study in a RHODIC FERRALSOL.

The validation of chromatographic methods is a costly process, however necessary, especially with regard to the validation of methods that accurately determine concentrations of pesticides in different environmental compartments. This research aimed at the development and validation of a simple and fast method for the determination of chlorpyrifos concentrations in water by means of a gas chromatograph with electron capture detection (GC/ECD), and to investigate chlorpyrifos dynamics of adsorption in a Rhodic Ferralsol in Southern Brazilian conditions. The developed chromatographic method was based in EPA 8141 method. Parameters to be checked for method validation were: Selectivity/specificity, linearity, precision, accuracy, robustness, limit of detection (LOD) and limit of quantitation (LOQ). Were employed the following methodologies for the validation process: ANVISA Resolution 899, DOQ-CGCRE-008 and FDA Bioanalytical Method Validation Guide. Also, through laboratory tests, the sorption dynamics of chlorpyrifos in Rhodic Ferralsol was evaluated. Thus, the soil was contaminated with increasing concentrations of chlorpyrifos, which were subjected to solid-liquid extraction with SPE cartridge Chromabond® C18 ec. The obtained results were submitted to the models of Langmuir, Freundlich, Dubinin-Radushkevich and Sips. By this method, chlorpyrifos peaks are obtained at 16.9 min, demonstrating practicality and low cost. This method exhibits precision and sensitivity, with satisfactory LQ and LQ values. The models of Langmuir, Freundlich, Dubinin-Radushkevich and Sips suggest the occurrence of simultaneous adsorption in mono and multilayer of chlorpyrifos in Rhodic Ferralsol colloids, as well as the predominance of a chemical, high energy binding process (irreversible). However, the chemisorption of chlorpyrifos is more related to the good fit found for Dubinin-Radushkevich sorption energy values (9.861 and 11.079 KJ mol-1) and Qm values estimated by Langmuir (485.55 and 389.61 µg g-1 for linear and nonlinear model).

Phytoremediation capacity, growth and physiological responses of Crambe abyssinica Hochst on soil contaminated with Cd and Pb.

The search for vegetal species regarding effectiveness in the phytoremediation of soils is of great importance, mainly in function of the great environmental problems, such as soil contamination with heavy metals, the necessity of producing more food, among others that mankind face today. This work aimed (i) to evaluate phytoremediation capacity of Crambe abyssinica Hochst and its growth in soil artificially contaminated with Cd and Pb, and (ii) to evaluate the possible impacts of crambe cultivation in contaminated soil conditions, in order to evaluate, to test, and to question the Brazilian CONAMA 420, providing important information that can be useful for governmental and environmental purposes. Two simultaneous experiments were developed, one for each metal. The soils were contaminated with salts of CdCl2 and PbCl2H2O in five doses based on the investigation values (IV) of CONAMA Resolution 420, resulting in 0; 1.5; 3; 9 and 30 mg kg-1 for Cd and 33; 90; 180; 540 and 1800 mg kg-1 for Pb. Gaseous exchange, development, nutritional composition and production of plant components, as well as phytoavailability of metals, were evaluated. The contamination with metals reduced photosynthesis, increased breathing as well as leading to a negative effect on the mineral nutrition and productivity in general; Plants cultivated in soil with Cd presented higher phytoavailability when compared to those cultivated in the Pb conditions, being found metals in all parts of the crambe plants from 1.5 mg kg- 1 of Cd in the soil; and Pb was retained only in roots, not being translocated in the plant. Cd showed higher phytoavailability, being found in all parts of the plant and Pb was retained only in the roots. Cd showed a higher phytoavailability when compared to Pb, also being found in all parts of crambe plants from dose 1.5 mg kg-1 of Cd in soil, which is an environmental problem, since in these concentrations the cultivation of crops is allowed by Brazilian legislation CONAMA 420.

Growth and accumulation of Pb by roots and shoots of Brassica juncea L.

In this study, different soil Pb concentrations [24 (control), 80, 136, 362, and 1150 mg kg-1] were used to analyze the tolerance threshold and accumulation potential of Brassica juncea L. in a pot experiment under greenhouse conditions. In addition to growth and Pb accumulation, the following contamination indices were calculated: transfer coefficient (TC), translocation factor (TF), and tolerance index (TI). Growth and Pb accumulation were determined at 60 days after emergence. The Pb concentrations were determined using the flame atomic absorption spectrometry (FAAS). The plant height was affected by soil Pb contamination, and it decreased from 1.37 to 0.83 m when the soil Pb concentration increased from 24 (control) to 1150 mg kg-1, respectively. The Pb concentration in the shoots and roots increased as the Pb concentration in the soil increased, reaching 94 mg kg-1 in shoots and 783 mg kg-1 in roots when was grown under 1150 mg kg-1 of Pb. TF was <1 at all levels of contamination. The TI values suggested that B. juncea presented Pb tolerance in Pb contaminated soils. Our findings indicate that B. juncea has the potential to accumulate Pb in soil under tropical conditions.

Salvinia auriculata in post-treatment of dairy industry wastewater.

The present study aimed to evaluate the aquatic macrophyte Savinia auriculata in post-treatment of wastewater from a dairy industry. The experiment was carried out in a greenhouse between February and March 2015. A batch system was used, each reactor was composed of polyethylene and had capacity of 250 liters of post-treated effluent. Every seven days, pH, turbidity, temperature, dissolved oxygen, chemical oxygen demand and series of solids (total, fixed and volatile) were determined in the wastewater. Besides that, the concentration of macro and micronutrients (P, N, K, Ca, Mg, Cu, Zn, Mn, and Fe) were determined in the wastewater and in plant tissue before and after the experiment. The results showed efficiency in the decrease of N, P, turbidity, pH, solids (ST, SF) and inefficiency in the reduction of volatile solids in the wastewater. The concentration of COD, Ca, Mn, Mg, and Fe increased at the end of the experiment. Due to the absorption of some nutrients such as N and P it is possible to conclude that Salvinia auriculata is a good option for the post-treatment of the wastewater from dairy industry. However, plant senescence promotes the elevation of some elements in the effluent because in this process, nutrients that were previously retained in the plant tissue are inserted into the wastewater again. Because of this it is necessary to remove plants of the reactor in the beginning of the process of senescence.

Pistia stratiotes in the phytoremediation and post-treatment of domestic sewage.

This work aimed to evaluate the potential of phytoremediation using Pistia stratiotes as a plant for post-treatment of wastewater from domestic sewage. The experiment was conducted at Toledo-PR, Brazil, for 42 days, in a pilot scale model. In order to evaluate the efficiency of Pistia as a post-treatment of domestic sewage, parameters such temperature, pH, turbidity, total solids, COD, Ntotal and Ptotal contents were determined in the effluent, as well as the total contents of K, Ca, Mg, Cu, Zn, Fe, Mn, Cd, and Pb. The bioaccumulation of K, Ca, Mg, Cu, Zn, Fe, Mn, Cd, and Pb in the living tissues of P. stratiotes have also been detected. The results demonstrate efficiency removal of turbidity, Ntotal, Ptotal and COD of 98.5, 100, 100, and 79.18%, respectively. The effluent contents of nutrients and toxic metals fluctuated during the study. This can have occurred due to photosynthetic activities of microorganisms and the plant senescence. The evaluation of some parameters in the effluent, such as temperature, DO, and organic matter, influenced these facts. Low levels of DO were observed, in function to the physical barrier of macrophytes in water surface, preventing the entry of air and light. The use of P. stratiotes proved to be a good complement for post-treatment of wastewater from domestic sewage.

Removal of toxic metals using endocarp of açaí berry as biosorbent.

The effectiveness of açaí endocarp as biosorbent for removal of Cd2+, Pb2+ and Cr3+ from single solute solutions was analyzed. The biomass of açaí endocarp was characterized by scanning electron microscopy, infrared spectroscopy and determining the point of zero charge. The optimum conditions for adsorption process were obtained at solution pH 6.0 for Cd(II) removal, pH 5.0 for Pb(II) removal, and, pH 4.0 for Cr(III). Furthermore, the average optimum efficiency of biosorbent in the optimum conditions was 8, 20 and 12 g of biosorbent per litre of contaminant solution, respectively, for Cd(II), Pb(II) and Cr(III). The best dynamic equilibrium time was reached at 60 min and Langmuir's model had the best fit for Cd(II) and Cr(III) biosorption, indicating a monolayer adsorption. Freundlich's model exhibited the best fit for Pb(II) ion. Elution rates were low, indicating a strong metal interaction with the adsorbent's surface. Thermodynamic parameters showed a spontaneous and endothermal process in the case of Cd(II) and Pb(II) ions, but not for Cr(III) ion, which appears to be an exothermic process. Results show that the use of the açaí biosorbent may be a promising alternative for the remediation of polluted water, due to its low cost and highly availability.

Adsorption mechanism of chromium(III) using biosorbents of Jatropha curcas L.

The removal of Cr3+ from water solutions by biosorbents from the rind, endosperm, and endosperm + episperm of the Jatropha curcas was evaluated. Adsorption tests were performed in batch systems for evaluating the influence of the solution's pH, adsorbent mass, contact time, initial Cr3+ concentrations, and solution temperature during the adsorption process. Kinetic, adsorption isotherm, and thermodynamic studies were performed to investigate the mechanisms that control adsorption. Ideal conditions for the adsorption process included pH of the solution of 5.5 and 8 g L-1 adsorbent mass, within 60 min time contact between adsorbent and adsorbate. Maximum adsorption capacities by Langmuir model for rind, endosperm, and endosperm + episperm of the J. curcas were, respectively, 22.11, 18.20, and 22.88 mg g-1, with the occurrence of chemosorption in mono and multilayers. Results show that the biosorbents obtained from J. curcas have a high potential to recuperate Cr3+ from contaminated water sources.

Produção da amoreira-preta 'Tupy' sob diferentes épocas de poda / Productive of 'Tupy' blackberry under different pruning time

A amora-preta é uma opção importante para fruticultura paranaense, porém não há informações a respeito do cultivo dessa frutífera nas condições subtropicais do Estado. O objetivo deste trabalho foi avaliar a influência da época de poda na produção da amoreira-preta 'Tupy'. O trabalho foi realizado em um pomar comercial, conduzido em sistema agroecológico. O delineamento experimental foi em blocos ao acaso, com quatro blocos e seis tratamentos (podas quinzenais realizadas durante o inverno). Em cada parcela, constituída de três plantas úteis, foram coletados dados fenológicos, produtivos e físico-químicos no ciclo de produção 2008/09 e 2009/10. Podas efetuadas no início de julho são as mais indicadas e podas tardias podem prejudicar o desempenho produtivo das amoreiras-pretas 'Tupy' no oeste do Paraná.

The blackberry is an important option to fruit growers in Paraná State. However, there aren't trials performed in subtropical area in that State. The objective of this research was to evaluate the pruning time effects at season production of 'Tupy' blackberry. The research was conducted in a commercial orchard, in an agroecological system. The experimental design was randomized blocks with four blocks and six treatments (pruning time by fifteen days during the winter pruning). In each plot, which was consisted of three plants, it was collected phenological, productive and physical-chemical production cycle in 2008/09 and 2009/10. Pruning made in early July are the most suitable and late pruning can harm the productive performance of blackberry 'Tupy' in western Paraná.

Enraizamento de estacas caulinares e radiculares de cultivares de amoreira-preta coletadas em diferentes épocas, armazenadas a frio e tratadas com AIB / Rooting of stems and root cutting of blackberry cultivars collected in different times, cold storage and treatment with IBA

O objetivo do presente trabalho foi avaliar o enraizamento de estacas caulinares e radiculares de cultivares de amoreira-preta, coletadas em diferentes épocas, armazenadas a frio e tratadas com AIB. No primeiro experimento, estacas radiculares e caulinares da amoreira-preta 'Tupy' foram coletadas no momento da poda hibernal, realizada nas seguintes épocas: 07/06, 22/06, 08/07, 22/07, 06/08 e 20/08 de 2009. Já no segundo experimento, metade das estacas caulinares e radiculares da mesma cultivar foi armazenada a frio por 30 dias e a outra metade das estacas foi colocada diretamente para enraizar. Todas as estacas foram tratadas com diferentes concentrações de ácido indolbutírico (AIB): 1000, 2000, 3000 e 4000mg L-1 por 10s., além do controle composto somente por água. No terceiro experimento, foram coletadas estacas radiculares das cultivares 'Choctaw', 'Ébano', 'Guarani', 'Arapaho', 'Brazos', 'Cherokee', 'Comanche', 'Caingangue', 'Tupy' e 'Xavante' na poda realizada no dia 22 de junho do ano seguinte. As estacas foram armazenadas a frio por 30 dias e não foi realizado tratamento com AIB. Em ambos os experimentos, as estacas caulinares foram enterradas 2/3 de seu comprimento na posição vertical e as estacas radiculares foram totalmente imersas na posição horizontal, utilizando a vermiculita de grânulos finos como substrato, em telado com sombreamento de 50 por cento. Após 90 dias, pode-se concluir que as estacas radiculares apresentam melhores resultados, devendo ser armazenadas a frio e não tratadas com AIB, mas há diferença do potencial propagativo entre os cultivares de amoreira-preta.

The objective of the present research was to quantify the rizogenic potential of stems and root cuttings of blackberry cultivars, collected in different times, cold storage and treated with indolbutyric acid. In the first experiment, roots and stems cuttings of 'Tupy' blackberry were collected close to it hibernal prune and accomplished in the following times: 07/06, 22/06, 08/07, 22/07, 06/08 and 20/08 of 2009. Already in the second experiment, half of the stems and roots cuttings of 'Tupy' blackberry were submitted to cold storage for 30 days and the other amount of cuttings were placed directly for rooting. The whole cuttings were treated with different concentrations of indolbutyric acid (IBA): 1000, 2000, 3000 and 4000mg L-1 for 10 seconds, and control only for water. In the third experiment, roots cuttings of 'Choctaw', 'Ébano', 'Guarani', 'Arapaho', 'Brazos', 'Cherokee', 'Comanche', 'Caingangue', 'Tupy' and 'Xavante' blackberry cultivars were collected in the pruning accomplished in june 22 of the following year. The cuttings were cold storage for 30 days and treatment was not accomplished with IBA. In both experiments, the stems cuttings were buried 2/3 of its length in the vertical position and the roots cuttings were totally immerged in the horizontal position, using vermiculita as substrate, in greenhouse with 50 percent of light. After 90 days, it can be concluded that the roots cuttings presents better results, owing cold storage and without IBA, but there is difference of propagation potential among blackberry cultivars.

Production of quince nursery trees by different grafting methods / Produção de mudas de marmeleiro por diferentes métodos de enxertia

Cutting propagation was the system to produce quince nursery trees (Cydonia oblonga). Experiments have been carried out in order to identify news propagations methods. As a result of this research, the 'Japonês' quince (Chaenomeles sinensis) was selected with rootstock, due to its good plant vigor for grafting, rusticity, and adequate performance in the field, mainly in the first years after planting. However, the best grafting period and grafting method must be determined for this rootstock. This research evaluated three grafting methods and five quince scion cultivars on 'Japonês' rootstock. The quince cultivars 'Provence', 'Mendoza Inta-37', 'Portugal', 'Smyrna', and 'Japonês' were grafted by winter cleft grafting, winter budding, and summer budding on 90cm long plants of 'Japonês' quince rootstock seedlings, cultivated in 3-liter plastic bags. Plant growth evaluations started as early as 60 days, and were concluded 150 days after grafting. Cleft grafting resulted in the highest graft survival rate for 'Smyrna', 'Mendoza Inta-37' and 'Japonês' cultivars. Although the higher graft survival rate was recorded in the winter, the buds grafted in the summer had better development.

Propagação por estaquia foi o sistema adotado no passado para produzir mudas de marmelo (Cydonia oblonga). Atualmente, pesquisas têm sido desenvolvidas para identificar novos métodos de propagação. A partir dos resultados dessas pesquisas, neste trabalho, o marmelo Japonês (Chaenomeles sinensis) foi selecionado como porta-enxerto, pelo seu bom vigor, pela sua rusticidade e pelo seu desempenho adequado no campo, principalmente nos primeiros anos depois do plantio. Porém, devem ser determinados a melhor época para a realização da enxertia e o método mais adequado quando se utiliza esse porta-enxerto. O presente trabalho avaliou três métodos de enxerto e cinco cultivares de marmelo enxertadas no porta-enxerto 'Japonês'. As cultivares de marmelo 'Provence', 'Mendoza Inta-37', 'Portugal', 'Smyrna' e 'Japonês' foram enxertadas por meio de três métodos: por garfagem em fenda cheia (julho), borbulhia de inverno (julho) e borbulhia de verão (janeiro), em mudas do porta-enxerto 'Japonês', com 90cm de comprimento e diâmetro próximo a 8mm, 15cm acima do colo da planta, mantidas em sacos plásticos com capacidade de 3L. As avaliações de crescimento tiveram incício aos 60 dias e foram concluídas 150 dias depois da enxertia. A enxertia realizada pelo processo de garfagem favorece a maior porcentagem de enxertos brotados, chegando próximo a 100 por cento de sucesso para 'Smyrna', 'Mendoza Inta-37' e 'Japonês'. Embora a taxa de sobrevivência de enxerto mais alta tenha sido registrada na enxertia por borbulhia realizada no inverno, os enxertos realizados no verão tiveram melhor desenvolvimento.

Armazenamento a frio de ramos porta-borbulhas e métodos de enxertia de cultivares de marmeleiro / Cold storage of budsticks and grafting methods of quince cultivars

Visando a aumentar o aproveitamento do material propagativo, ampliar o período de oferta das mudas de marmeleiro e dinamizar o uso da mão-de-obra no viveiro, faz-se necessário o armazenamento dos ramos porta-borbulhas. Sendo assim, o presente trabalho teve por objetivos estudar a viabilidade da manutenção dos ramos porta-borbulhas de diferentes cultivares de marmeleiro, por meio do armazenamento a frio, e diagnosticar o método de enxertia para promover melhor desenvolvimento do enxerto. Ramos dos marmeleiros 'Japonês' (Chaenomeles sinensis), 'Smyrna', 'Portugal', 'Mendoza Inta-37' e 'Provence' (Cydonia oblonga) foram coletados em julho de 2008. Uma parte dos ramos foi utilizada para a realização da enxertia (métodos de borbulhia e garfagem) em mudas de seis meses de idade do porta-enxerto 'Japonês', e a outra parte foi armazenada sob baixa temperatura (estacas envoltas em papel umedecido, embrulhadas em sacos de polietileno colocadas em câmara fria a 4°C), por 30 e 60 dias. Passados 60 dias, foi mensurada a porcentagem de brotação dos enxertos e, ao final de 120 dias da realização das enxertias, foram mensurados o comprimento, o diâmetro e a massa seca média dos enxertos. Concluiu-se que, apesar de as cultivares apresentarem diferença, recomenda-se que os ramos sejam armazenados por até 30 dias, sendo utilizada a enxertia pelo método de garfagem.

In order to increase the use of propagation material, enlarge the offer period of the quince seedlings production and dynamic use of the labor in the nursery, it becomes necessary to store the of budsticks. Thus, the present research aimed to study the feasibility of the maintaining budstick of different quince cultivars, through cold storage and to verify the grafting method to promote better development of the graft. Branches of the 'Japonês' (Chaenomeles sinensis), 'Smyrna', 'Portugal', 'Mendoza Inta-37' and 'Provence' (Cydonia oblonga) quince cultivars were collected in July, 2008. One of the branches was used for grafting (methods budding and cleft grafting methods) in 'Japonês' rootstock seedlings of six months of age and other part was stored at e low temperature (wrapped up cutting in humidified paper and wrapped up in polyethylene sacks, placed in cold chamber for 4°C) for 30 and 60 days. After 60 days, the percentage of sprouting was measured and 120 days after grafting, the length, diameter and mass dries average of the grafts were measured. It was concluded that, despite the cultivars presented anydifference, it is recommended that the branches need to be stored for up to 30 days, if the cleft grafting is used.

Sistema desponte na produção de figos verdes 'Roxo de Valinhos' / Lopping system in the production of 'Roxo de Valinhos' green fig

O objetivo deste trabalho foi estudar o efeito do sistema desponte sobre o desenvolvimento e a produção de figos verdes 'Roxo de Valinhos'. O experimento utilizando plantas de quatro anos de idade, com espaçamento 3 x 2m, foi conduzido de julho de 2007 a março de 2008, em Quatro Pontes, Paraná (PR). O delineamento utilizado foi em blocos ao acaso, com quatro blocos, e os tratamentos foram arranjados em fatorial 2 x 5, tomando por fatores o número de ramos produtivos (plantas conduzidas com seis ou 12 ramos) e o número de despontes (um, dois, três ou quatro, além do controle sem desponte). No sistema desponte, após a emissão da 16a folha, o ramo foi despontado (gema apical removida), selecionando-se duas brotações por ramo produtivo. Novos despontes foram realizados posteriormente, sempre após a emissão da sexta folha. Em cada parcela, constituída de três plantas úteis, foram coletados dados no ciclo de produção 2007/08. A maior produção (2.208,87g planta-1) e produtividade estimada (3.681,19kg ha-1) observada de figos verdes foram obtidas quando as plantas foram conduzidas com 12 ramos produtivos, efetuando-se três despontes.

The objective of this research was to study the effect of the lopping system on the development and production of green figs 'Roxo de Valinhos'. The experiment using plants of four years of age, with spaced 3 x 2m, was conducted from July/2007 to March/2008 in Quatro Pontes, PR. The design was randomized blocks with four blocks, and the treatments arranged in a 2 x 5, taking as factors the number of productive branches (plants conducted with six or twelve branches) and the number of loppings (one, two, three or four, besides the control without lopping). In the lopping system, after the emission of the 16th leaf, the branch was blunted (apical bud removed), selecting two sprouting per productive branches. New lopping was accomplished later, always after the emission of sixth leaf. In each plot, consisting of the three plants, data were collected in the production cycles 2007/2008. The highest yield (2,208.87g planta-1) and estimated yield (3,681.19kg ha-1) observed of green figs were obtained when plants were conducted with twelve branches of production, effecting three loopings.