Fatores de bioconcentração e disponibilidade de bário, cádmio, cobre, níquel e zinco em solos e em culturas de interesse agronômico

Os elementos potencialmente tóxicos (EPTs) estão presentes nos solos em concentrações dependentes do material de origem e das ações antrópicas. A adição de EPTs ao solo pelas atividades antrópicas pode ocasionar risco à saúde humana, já que estes elementos podem ser acumulados no organismo por meio do contato dérmico com o solo, da inalação de partículas em suspensão, de ingestão de solo e de alimentos contaminados. A contaminação dos alimentos ocorre pelo cultivo em áreas com alta biodisponibilidade de EPTs, e nessa condição ocorre absorção e translocação para a parte aérea, com possível acúmulo dos metais nas porções comestíveis, como raízes, frutos e grãos. A biodisponibilidade dos EPTs é regulada pelas características químicas dos elementos e por atributos do solo, como a CTC, o pH e a matéria orgânica (MO). Sintomas de toxicidade e alterações morfológicas e fisiológicas podem aparecer dependendo da absorção e da movimentação dos EPTs nas plantas. Objetivou-se neste trabalho avaliar o efeito da adição de bário (Ba), de cádmio (Cd), de cobre (Cu), de níquel (Ni) e de zinco (Zn) em amostras de um Neossolo Quartzarênico e um Latossolo Vermelho distrófico, sob duas condições de saturação por bases (30% e 50 ou 70%, dependendo da cultura), no cultivo de arroz (Oryza sativa), alface (Lactuca sativa), girassol (Helianthus annuus) e tomate (Solanum lycopersicum). Os EPTs nos solos foram extraídos com EPA 3051a, Água Régia, DTPA, Mehlich 1, Mehlich 3, HNO3 (0,43 mol L-1) e CaCl2 (0,01 mol L-1), e seus teores correlacionados com os presentes nas raízes, na parte aérea, nos frutos e com a quantidade acumulada pelas plantas. Os fatores de bioconcentração (FBC) e de transferência (FT) foram calculados para as culturas. O índice SPAD (Soil Plant Analysis Development - Chlorophyll Meter) foi determinado na fase vegetativa da alface, do arroz e do girassol, enquanto a atividade fotossintética foi determinada pelo IRGA (Infrared gas analyzer). Os maiores teores de EPTs foram observados nas plantas cultivadas no Neossolo. As quantidades de Cu, Ni e Zn acumuladas nas plantas apresentaram correlação positiva com os teores extraídos pelo EPA 3051a e pela Água Régia. Os teores extraídos com HNO3 (0,43 mol L-1) apresentaram elevada correlação positiva com os teores reativos extraídos com DTPA e com Mehlich 3, e também com as quantidades de EPTs acumuladas pelas plantas. Os FBCs foram mais altos nos solos com baixa CTC, baixos teores de MO e baixos valores de pH. O arroz apresentou a menor translocação de Cd do sistema radicular para os grãos. O Cu, o Ni e o Zn causaram alterações no desenvolvimento da alface e do girassol, e diminuíram a transpiração e a condutância estomática da alface. O arroz apresentou a menor absorção de EPTs e a maior tolerância ao Ba, ao Cd, ao Ni e ao Zn, no entanto, as plantas apresentaram maiores condutividade estomática e transpiração.

Omics for Investigating Chitosan as an Antifungal and Gene Modulator

Chitosan is a biopolymer with a wide range of applications. The use of chitosan in clinical medicine to control infections by fungal pathogens such as Candida spp. is one of its most promising applications in view of the reduced number of antifungals available. Chitosan increases intracellular oxidative stress, then permeabilizes the plasma membrane of sensitive filamentous fungus Neurospora crassa and yeast. Transcriptomics reveals plasma membrane homeostasis and oxidative metabolism genes as key players in the response of fungi to chitosan. A lipase and a monosaccharide transporter, both inner plasma membrane proteins, and a glutathione transferase are main chitosan targets in N. crassa. Biocontrol fungi such as Pochonia chlamydosporia have a low content of polyunsaturated free fatty acids in their plasma membranes and are resistant to chitosan. Genome sequencing of P. chlamydosporia reveals a wide gene machinery to degrade and assimilate chitosan. Chitosan increases P. chlamydosporia sporulation and enhances parasitism of plant parasitic nematodes by the fungus. Omics studies allow understanding the mode of action of chitosan and help its development as an antifungal and gene modulator.

Caracterização in vitro de um dosímetro de fibra ótica para braquiterapia de HDR

Recentemente foi desenvolvido um dosímetro baseado em fibras cintilantes (BCF-12 da companhia Saint Gobain Crystals com 1 e 0,5 mm de diâmetro e 5 mm de comprimento) para braquiterapia de baixa taxa de dose, em particular a braquiterapia direcionada para o tratamento do cancro da próstata. Este utiliza um novo fotomultiplicador de estado sólido dado pelo nome de MPPC - MultiPixel Photon Counter da companhia Hamamatsu Photonics (Japão). Nesta dissertação é estudado o mesmo dosímetro para a modalidade de braquiterapia de elevada taxa de dose (HDR). A informação sobre a dose neste tipo de dosímetros é obtida a partir de sinais óticos (em vez de sinais elétricos), que são imunes a interferências elétricas e eletromagnéticas. Adicionalmente as pequenas dimensões das fibras oferecem uma excelente resolução espacial e uma invasão mínima para uso em dosimetria in vivo, permitindo medir a dose diretamente ou próximo ao tumor e em tempo real. A sua utilização em braquiterapia para o cancro da próstata constitui-se assim como uma vantagem, uma vez que as fibras podem ser inseridas diretamente nos aplicadores utilizados neste tipo de tratamentos. Apesar de tudo, este tipo de dosímetros possui algumas desvantagens, como por exemplo a luz de Cherenkov e a fluorescência (forma de ruído dada pelo nome de stem effect) que, e a contrário da luz produzida pela fibra cintilante, não são diretamente proporcionais à energia depositada. Contudo, e para energias praticadas em braquiterapia de HDR, nesta dissertação, mostrou-se que este problema é pouco significativo dado que a percentagem de contribuição destes efeitos para o sinal medido é menor que 1% (ou 5% para distâncias menores que 25 mm). Ao longo desta dissertação é feita a caraterização do dosímetro (em modo corrente e impulso) e das suas várias partes em ambiente de laboratório e clínico. Nestes estudos o dosímetro, além de exibir uma boa reprodutibilidade (variação máxima de 3% entre medidas), mostrou uma alta linearidade para uma ampla gama de doses, assim como uma sensibilidade (µGy) semelhante à de uma câmara de ionização, tornando-o adequado para braquiterapia de HDR (tratamento que envolve altos gradientes de dose). Complementarmente, a sua grande versatilidade e simples utilização possibilita a sua aplicação prática em outras modalidades radioterapêuticas.

The possible identification and introduction of metallothionein in Persian Sturgeon (Acipenser persicus)

Due to anthropogenic activities, toxic metals still represent a threat for various marine organisms. Metallothionein (MT) and cadmium concentration in gills, liver, and kidney tissues and cadmium partitioning in soluble (cytosol) and insoluble fractions of mentioned tissues of Persian sturgeon (Acipenser persicus) were determined following exposure to sub-lethal levels of waterborne cadmium (Cd) (50, 400 and 1000 μg L-1) after 1, 2, 4 and 14 days. The increases of MT from background levels in comparison to controls were 4.6-, 3-, and 2.8-fold for kidney, liver, and gills, respectively after 14 days. The matallothionein concentration in liver was in the range of 56.89-168.44 μgL-1 and for kidney and gills, 39.78-189.30 and 28.15-91.20 μgL-1, respectively. The results showed that MT level change in the kidney is time and concentration dependent. Also, cortisol measurement revealed elevation at the day 1 of exposure and that followed by MT increase in the liver. Cd concentrations in the cytosol of experimental tissues were measured and the results indicated that Cd levels in the cytosol of liver, kidney, and gills increased 240.71-, 32.05-, and 40.16-fold, respectively 14 days after exposure to 1000 μgL-1 Cd. The accumulation of Cd in cytosol of tissues is in the order of liver > gills > kidney. Spearman correlation coefficients showed the MT content in kidney is correlated with Cd concentration, the value of which is more than in liver and gills. Thus, kidney can be considered as a tissue indicator in Acipenser persicus for waterborne Cd contamination. Also, tissue metal accumulations (gills, liver, kidney and muscle) in Persian sturgeon (Acipenser persicus) were compared following exposure to sublethal levels of waterborne Cd (50, 400 and 1000 μg L-1) after periods of 1, 2, 4 and 14 days. Meanwhile, the trends of Cd concentration increase in different tissues during the exposure periods and concentrations were modelled as equations. The obtained results indicate that at the end of 4 and 14 days of exposure, total tissue cadmium concentration followed the pattern: liver> gill> kidney> muscle. Calculation of bioconcentration factor (BCF) after 14 days exposure showed that at low and high concentrations, highest BCFs were found in kidney and liver, respectively. According to the results, the accumulation capacity of muscle was the lowest at all exposure concentrations. The hematological parameters including osmolarity, total protein, cortisol and glucose of plasma were measured, too. Total protein of plasma was in the range of 416.90-1068.10 mg dl-1 plasma.Total protein decreased not significantly (P≥0.05) after exposure to Cd. Cortisol increased after 1 day exposure that followed by significant (P≤0.05) elevation of glucose. The range of cortisol was very vast and it was determined between 0.03 to 16.21 ng mL-1. The content of plasma osmolarity was in the range of 282.33-294.20 mOsmol L-1.Osmolarity of treated fish plasma showed no significant decrease (P≥0.05). Total protein in gills, liver, and kidney showed that at high concentrations of metal, protein content decreased significantly (P≤0.05) in the liver after 4 and 14 days exposure. Thus, total protein of liver and glucose of plasma can be used as general biomarkers of exposure to Cd. Also, the metallothionein and cadmium were measured in gills, kidney and liver of 8 wild Persian sturgeon caught in coast of Guilan Province. According to the results, the concentration of metallothionein was in the range of 45.87-154.66 microgram per liter with the maximum and minimum concentrations in liver and gills, respectively. The trend of cadmium concentration in cytosol of tissues was: liver> kidney> gills. The results of Spearman correlation test showed that there was a significant positive correlation between metallothionein and cadmium in cytosol of liver (r2= 0.850, p≤ 0.01). In the kidney, the correlation between cadmium and metallothionein was significantly positive (r2= 0.731, p≥ 0.05). But there was not such significant correlation in the gills (p≥ 0.05).

Determination of thresholds in marine molluscs as an alternative to the Environmental Quality Standards in marine water defined in the Water Framework Directive

The Water Framework Directive (WFD) establishes Environmental Quality Standards (EQS) in marine water for 34 priority substances. Among these substances, 25 are hydrophobic and bioaccumulable (2 metals and 23 organic compounds). For these 25 substances, monitoring in water matrix is not appropriate and an alternative matrix should be developed. Bivalve mollusks, particularly mussels (Mytilus edulis, Mytilus galloprovincialis), are used by Ifremer as a quantitative biological indicator since 1979 in France, to assess the marine water quality. This study has been carried out in order to determine thresholds in mussels at least as protective as EQS in marine water laid down by the WFD. Three steps are defined: - Provide an overview of knowledges about the relations between the concentrations of contaminants in the marine water and mussels through bioaccumulation factor (BAF) and bioconcentration factor (BCF). This allows to examine how a BCF or a BAF can be determined: BCF can be determined experimentally (according to US EPA or ASTM standards), or by Quantitative Activity-Structure Relationship models (QSAR): four equations can be used for mussels. BAF can be determined by field experiment; but none standards exists. It could be determined by using QSAR but this method is considered as invalid for mussels, or by using existing model: Dynamic Budget Model, but this is complex to use. - Collect concentrations data in marine water (Cwater) in bibliography for those 25 substances; and compare them with concentration in mussels (Cmussels) obtained through French monitoring network of chemicals contaminants (ROCCH) and biological integrator network RINBIO. According to available data, this leads to determine the BAF or the BCF (Cmussels /Cwater) with field data. - Compare BAF and BCF values (when available) obtained with various methods for these substances: BCF (stemming from the bibliography, using experimental process), BCF calculated by QSAR and BAF determined using field data. This study points out that experimental BCF data are available for 3 substances (Chlorpyrifos, HCH, Pentachlorobenzene). BCF by QSAR can be calculated for 20 substances. The use of field data allows to evaluate 4 BAF for organic compounds and 2 BAF for metals. Using these BAF or BCF value, thresholds in shellfish can be determined as an alternative to EQS in marine water.

Pesticide bioconcentration factor estimate in apples.

This work objective was to estimate the bioconcentration factor (BCF) of thirty six pesticides used in the Brazilian integrated apple production systems (IAP), in order to select priority pesticides to be monitored in apples. A hypothetical apple orchard was assumed and the model applied was according to Paraíba (2007) [Pesticide bioconcentration modeling for fruit trees. Chemosphere (66:1468-1475)]. The model relates BCF with plant and pesticide characteristics. The octanol-water partition coefficients of pesticides and their degradation rates in the soil were used. The following plant variables were considered: growth rate, total dry biomass, daily water transpiration rate, and total volume of water necessary to produce one kg of fresh fruit per plant. The pesticide stem-water partition coefficient and the transpiration stream concentration factor were calculated using equations that relate each coefficient with the octanol-water partition coefficient. The pesticide BCF in fruits is an important indicator of the pesticide affinity to fruits, and helps to improve the integrated production systems.

Pesticide bioconcentration modelling for fruit trees.

The model presented allows simulating the pesticide concentration in fruit trees and estimating the pesticide bioconcentration factor in fruits of woody species. The model allows estimating the pesticide uptake by plants through the water transpiration stream and also the time in which maximum pesticide concentration occur in the fruits. The equation proposed presents the relationships between bioconcentration factor (BCF) and the following variables: plant water transpiration volume (Q), pesticide transpiration stream concentration factor (TSCF), pesticide stem-water partition coefficient (KWood,w), stem dry biomass (M) and pesticide dissipation rate in the soil-plant system (kEGS). The modeling started and was developed from a previous model ?Fruit Tree Model? (FTM), reported by Trapp and collaborators in 2003, to which was added the hypothesis that the pesticide degradation in the soil follows a first order kinetic equation. The model fitness was evaluated through the sensitivity analysis of the pesticide BCF values in fruits with respect to the model entry data variability.

The bioconcentration factor of pesticides in potatoes.

We presented a model that estimates the bioconcentration factor (BCF) of pesticides in potatoes supposing that the pesticide in the soil solution is absorbed by the potato by passive diffusion, following Fick?s second law. The pesticides in the model are nonionic organic substances, traditionally used in potato crops that degrade in the soil according to a first order kinetic equation. This presents an expression that relates BCF with the pesticide elimination rate by the potato, with the pesticide accumulation rate within the potato, with the rate of growth of the potato and with the pesticide degradation rate in the soil. BCF was estimated supposing steady state equilibrium of the quotient between the pesticide concentration in the potato and the pesticide concentration in the soil solution. It is suggested that a negative correlation exists between the pesticide BCF and the soil sorption partition coefficient. The model was built based on the work of Trapp et al. (2007), [Diffusion of PAH in Potato and Carrot Slices and Applications for a Potato Model] in which an expression to calculate the diffusivity of persistent organic substances in potatoes is presented. The model consists in adding to the expression of Trapp et al. (2007) the hypothesis that the pesticide degrades in the soil. The value of BCF suggests which pesticides should be monitored in potatoes.

Multiscale Modeling and Simulation of Stepped Crystal Surfaces

A primary goal of this dissertation is to understand the links between mathematical models that describe crystal surfaces at three fundamental length scales: The scale of individual atoms, the scale of collections of atoms forming crystal defects, and macroscopic scale. Characterizing connections between different classes of models is a critical task for gaining insight into the physics they describe, a long-standing objective in applied analysis, and also highly relevant in engineering applications. The key concept I use in each problem addressed in this thesis is coarse graining, which is a strategy for connecting fine representations or models with coarser representations. Often this idea is invoked to reduce a large discrete system to an appropriate continuum description, e.g. individual particles are represented by a continuous density. While there is no general theory of coarse graining, one closely related mathematical approach is asymptotic analysis, i.e. the description of limiting behavior as some parameter becomes very large or very small. In the case of crystalline solids, it is natural to consider cases where the number of particles is large or where the lattice spacing is small. Limits such as these often make explicit the nature of links between models capturing different scales, and, once established, provide a means of improving our understanding, or the models themselves. Finding appropriate variables whose limits illustrate the important connections between models is no easy task, however. This is one area where computer simulation is extremely helpful, as it allows us to see the results of complex dynamics and gather clues regarding the roles of different physical quantities. On the other hand, connections between models enable the development of novel multiscale computational schemes, so understanding can assist computation and vice versa. Some of these ideas are demonstrated in this thesis. The important outcomes of this thesis include: (1) a systematic derivation of the step-flow model of Burton, Cabrera, and Frank, with corrections, from an atomistic solid-on-solid-type models in 1+1 dimensions; (2) the inclusion of an atomistically motivated transport mechanism in an island dynamics model allowing for a more detailed account of mound evolution; and (3) the development of a hybrid discrete-continuum scheme for simulating the relaxation of a faceted crystal mound. Central to all of these modeling and simulation efforts is the presence of steps composed of individual layers of atoms on vicinal crystal surfaces. Consequently, a recurring theme in this research is the observation that mesoscale defects play a crucial role in crystal morphological evolution.

Modelagem da bioconcetração de pesticidas em batatas.

Apresentamos um modelo que estima o fator de bioconcentracão (BCF) de pesticidas em batatas supondo que o pesticida na solução do solo é absorvido pela batata por difusão passiva,seguindo a segunda lei de Fick.Os pesticidas do modelo são compostos orgânicos não-iônicos, tradicionalmente utilizados no cultivo de batatas que degradam no solo de acordo com uma equação cinética de primeira ordem. Este trabalho apresenta uma expressão que relaciona o BCF com a taxa de eliminação do pesticida pela batata, com a taxa de acumulação do pesticida na batata, com a taxa de crescimento da batata, e com a taxa de degradação do pesticida no solo. O BCF foi estimado supondo-se estado de equilíbrio estacionário do quociente entre a concentração do pesticida na batata e a concentração do pesticida na solução do solo. O modelo foi construído baseado no trabalho de Trapp et al. (2007), [Diffusion of PAH in Potato and Carrrot Slices and Applications for a Potato Model] no qual é apresentada uma expressão para calcular a difusividade de substâncias orgânicas persistentes em batatas. A modelagem consistiu em adicionar ao modelo de Trapp et al. (2007) a hipótese de que o pesticida degrada no solo. O valor do BCF sugere um conjunto de pesticidas que devem ser prioritariamente monitorados em cultivos de batatas. Foi estimado o BCF dos pesticidas methamidophos, cymoxanil, carbofuran, aldicarb, metalaxyl, fenamiphos, carbaryl, triazophos, tebuconazole, propiconazole, chlorothalonil e cypermethrin.

Estimativa do fator de bioconcentração de pesticidas em maçãs.

O objetivo desse trabalho foi estimar o fator de bioconcentração (BCF) de trinta e seis pesticidas do sistema brasileiro de produção integrada de maçãs (PIM) e indicar quais deles devem ser monitorados em maçãs. Foi assumido um cultivo hipotético de macieiras e usado o modelo de Paraíba (2007) [Pesticide bioconcentration modelling for fruit trees Chemosphere, v.66, p.1468-1475, 2007].O modelo relaciona o BCF com características da planta e do pesticida.

Bioaccumulation and elimination of Endosulfan in zebra fish (Brachydanio rerio).

The bioaccumulation and elimination of endosulfan in zebra fish (Brachydanio rerio) were investigated in a semi-static bioassay. The pesticide mean concentration in water was 03ug litre(-1) and the level of endosulfan residues (x(alfa)+B(beta)-isomers+endosulfan sulfate) in the exposed fish at day 21 was 0.81 (+-0.12)ug g(-1) body weight. The estimated value of the bioconcentration factor (BCF) was 2650 (+-441), the total endosulfan residues being eliminated with a biological half-life of four days. Histopathological studies showed predominantly lipid accumulation in the liver and necrotic focus in the gills of exposed fish.

Bioconcentration of selected personal care products in Ruditapes philippinarum (Manila clam)

The Bioconcentration Factor (BCF) is the principal source of information used to assess and regulate the potential hazard and risk for a chemical that has the potential to bioaccumulate in the marine environment, according to the Marine Strategy Framework Directive (MSFD). The main objective of this thesis was to estimate the BCFs of two different emerging contaminants in Ruditapes philippinarum (Manila clam) under controlled laboratory conditions: the UV filter 4-methylbenzylidene camphor (4-MBC) commonly used in skincare products, and the artificial sweetener Acesulfame potassium (ACE-K) used as a food additive. Ruditapes philippinarum organisms were exposed directly to 4-MBC and ACE-K nominal concentration of 1, 10 and 100 μg L-1 during 10 days. Bioconcentration factors (BCFs) were estimated according to 3 different models for both compounds. The 4-MBC estimated BCFs fall in range of 61553 - 539143 L Kg-1, showing that this compound is very bioaccumulative and could also undergo biomagnification in the marine food chain. On the contrary, estimated ACE-K BCF is consistently lower, in order of 7 L Kg-1 for the nominal exposure concentration of 100 μg L-1. The low ACE-K BCF could be explained by its high solubility in water and thus a rapid metabolization by clams during the experiments. In summary, future research focusing on the marine environment is needed on these two emerging compounds.