Mercury in multimedia system of Itacaiúnas Basin, Brazilian Amazon: An integrated approach to understand its distribution, origin, and ecological risk.

This study presents the first integrated study on total Hg (THg) level in surface soil (SS), bottom soil (BS), stream sediments (SD), lake sediments (LS), stream water (SW), and lake water (LW) of Itacaiúnas River Watershed (IRW), Brazil to investigate the source and distribution of Hg in different environmental media considering contrasts of geological domains and sub-basins and its potential ecological and human risk. Hg content in most of the soils and sediments were above the upper crustal average values (56 µg/kg), however, when compared to the legal limits set by the Resolution CONAMA (Conselho Nacional de Meio Ambiente: soil 500 µg/kg; sediment 486 µg/kg), only 1 soil sample from Parauapebas sub-basin and 4 sediment samples from Violão Lake exceeded the limit. None of the SW and LW samples (<0.2 µg/L; CONAMA limit for Class II freshwater) are markedly contaminated by Hg. The SS and BS show similar contents and spatial distribution of Hg with higher contents being registered mostly in the Itacaiúnas and Parauapebas sub-basins, which are closely correlated with SD. This suggests that Hg levels are largely of geogenic origin and anthropogenic effect is highly limited. Principal Component Analysis (PCA) results show that Hg is strongly associated with total organic carbon (TOC), loss on ignition (LOI), and SO3, indicating organic matter as the main factor controlling the distribution of Hg and this is the major cause of accentuated Hg enrichment in lake sediments. The ecological risk index revealed a low pollution risk for most of the solid samples, except 11% LS and <1.5% SS and SD samples, which registered moderate risk. Health risk assessment indicated no adverse non-carcinogenic health effect on either adults and children in terms of Hg contamination. This information will be useful for Hg risk assessment in the Carajás region and future environmental research in this direction in the Amazonia.

Sleep responses of young swimmers to training load and recovery during tapering / Respuestas del sueño a las cargas de entrenamiento y recuperación en jóvenes nadadores durante el tapering / Respostas do sono às cargas de treinamento e recuperação em jovens nadadores durante o polimento

ABSTRACT Introduction: Tapering is a decisive phase in planning a young swimmer's preparation for competition. During this period, not only training loads, but also recovery, which includes sleep quality, must be constantly monitored. Objective: This study aims to investigate sleep behavior as a variable directly influenced by training load during the tapering phase of training for young swimmers. Methods: A polysomnography test was performed at the beginning of the tapering phase, as a baseline for sleep variables. In each daily training session, the overload and recovery variables were measured. The internal training load was evaluated in the PSE session and the external load by quantifying the training. The recovery variables were divided into the recovery variable, assessed using the TQR questionnaire, and sleep variables, which included sleepiness, scored using the Karolinska scale, and sleep behavior, using an actigraph and a sleep diary. Conclusion: It is concluded that there is no significant influence between training loads and sleep variables. However, a strong association was observed between TST and EL (External load), in the irregular sleep group. Level of evidence III, Study of behavior.

RESUMEN Introducción: El tapering es una fase decisiva en la planificación de la preparación de un joven nadador para la competición. Durante este período, deben monitorearse constantemente no sólo las cargas de entrenamiento, sino también la recuperación, que incluye la calidad del sueño. Objetivo: Este estudio tiene como objetivo investigar el comportamiento del sueño como variable directamente influenciada por la carga de entrenamiento durante la fase de tapering del entrenamiento de jóvenes nadadores. Métodos: Se realizó una polisomnografía al inicio de la fase de tapering como base de las variables del sueño. En cada sesión diaria de entrenamiento se midieron las variables de sobrecarga y recuperación. La carga interna de entrenamiento fue evaluada por la sesión de PSE y la carga externa mediante cuantificación del entrenamiento. Las variables de recuperación se dividieron variables de recuperación, con el cuestionario QTR y variables de sueño, que incluían somnolencia mediante la escala de Karolinska y comportamiento del sueño con un actígrafo y diario de sueño. Conclusiones: Se concluyó que no existe una influencia significativa entre las cargas de entrenamiento y las variables del sueño. Sin embargo, se observó una fuerte asociación entre TTS y el CE, en el grupo de sueño irregular. Nivel de evidencia III, Estudio de comportamiento.

RESUMO Introdução: A etapa de polimento é uma fase decisiva no planejamento da preparação de um jovem nadador para a competição. Durante esse período, não somente as cargas de treinamento, mas também a recuperação, que inclui a qualidade do sono, devem ser constantemente monitoradas. Objetivos: Este estudo objetiva investigar o comportamento do sono como variável diretamente influenciada pela carga de treinamento durante a fase de polimento do treinamento de jovens nadadores. Métodos: O exame de polissonografia foi realizado no início da fase de polimento, como base para as variáveis do sono. Em cada sessão diária de treinamento foram medidas as variáveis de sobrecarga e de recuperação. A carga interna de treinamento foi avaliada pela sessão de PSE e a carga externa, pela quantificação do treinamento. As variáveis de recuperação foram divididas em variável de recuperação, com o questionário QTR e variáveis de sono, que incluíram sonolência pela escala de Karolinska e comportamento do sono com actígrafo e diário de sono. Conclusões: Conclui-se que não há influência significativa entre as cargas de treinamento e as variáveis do sono. Entretanto, foi observada forte associação entre TTS e CE no grupo sono irregular. Nível de evidência III; Estudo de comportamento.

Anti-Inflammatory Activity of Olive Oil Polyphenols-The Role of Oleacein and Its Metabolites.

The anti-inflammatory potential of oleacein, the main polyphenolic compound found in olive oil, and its main metabolites were characterized by their effects on RAW 264.7 macrophages challenged with lipopolysaccharide (LPS), and by their ability to inhibit enzymes of the arachidonic acid metabolism with a key role in the synthesis of pro-inflammatory lipid mediators. Oleacein at 12.5 µM significantly decreased the amount of L-citrulline and ●NO generated by LPS-stimulated macrophages. Hydroxytyrosol, hydroxytyrosol acetate and hydroxytyrosol acetate sulfate were also able to reduce the cellular amount of ●NO, although to a lesser extent. In contrast, hydroxytyrosol glucuronide and sulfate did not show detectable effects. Oleacein was also able to inhibit the coupled PLA2 + 5-LOX enzyme system (IC50 = 16.11 µM), as well as the 5-LOX enzyme (IC50 = 45.02 µM). Although with lower activity, both hydroxytyrosol and hydroxytyrosol acetate were also capable of inhibiting these enzymes at a concentration of 100 µM. None of the other tested metabolites showed a capacity to inhibit these enzymes. In contrast, all compounds, including glucuronides and sulfate metabolites, showed a remarkable capacity to inhibit both cyclooxygenase isoforms, COX-1 and COX-2, with IC50 values lower than 3 µM. Therefore, oleacein and its metabolites have the ability to modulate ●NO- and arachidonic acid-dependent inflammatory cascades, contributing to the anti-inflammatory activity associated with olive oil polyphenols.

A biochemical perspective on the fate of virgin olive oil phenolic compounds in vivo.

The chemistry of the phenolic compounds found in virgin olive oil (VOO) is very complex due, not only to the different classes of polyphenols that can be found in it, but, above all, due to the existence of a very specific phenol class found only in oleaceae plants: the secoiridoids. Searching in the Scopus data base the keywords flavonoid, phenolic acid, lignin and secoiridoid, we can find a number of 148174, 79435, 11326 and 1392 research articles respectively, showing how little is devote to the latter class of compounds. Moreover, in contrast with other classes, that include only phenolic compounds, secoiridoids may include phenolic and non-phenolic compounds, being the articles concerning phenolic secoiridoids much less than the half of the abovementioned articles. Therefore, it is important to clarify the structures of these compounds and their chemistry, as this knowledge will help understand their bioactivity and metabolism studies, usually performed by researchers with a more health science's related background. In this review, all the structures found in many research articles concerning VOO phenolic compounds chemistry and metabolism was gathered, with a special attention devoted to the secoiridoids, the main phenolic compound class found in olives, VOO and olive leaf.

Olive oil oleogels as strategy to confer nutritional advantages to burgers.

The effect of bovine back fat replacement by oleogels containing pork skin and olive oil on the oxidative stability, physicochemical, technological, nutritional, and sensory parameters of burgers was evaluated. Four different hamburger (H) were manufactured: with 90 % of lean beef and 10 % of bovine back fat (control, HC), or with 10 % of pork skin/water/virgin olive oil (HVOO), stripped olive oil added of an olive leaf extract (HESOO) or stripped olive oil (HSOO) oleogels, at 20:60:20 ratio. Physical-chemical stability was assessed after storage for 7 days at 4 °C and for 90 days at -20 °C, under non-vacuum and vacuum packaging. A reduction in the fat content by 80 % and in the energy content by 35 %, an increase in the protein content by 15 % and a better fatty acid profile were achieved in the oleogel containing burgers. After processing at 180 °C (grill), hardness, chewiness, sensory parameters and overall acceptability were high and comparable to control. All burgers were oxidative stable during 7 days at 4 °C. After storage for 90 days at -20 °C, only HSOO samples stored under non-vacuum packaging were oxidized. The antioxidant content in samples HVOO and HESOO efficiently prevented the oxidation of these samples.

Soil-sediment linkage and trace element contamination in forested/deforested areas of the Itacaiúnas River Watershed, Brazil: To what extent land-use change plays a role?

Trace elements (TE) contamination in forested areas of the Itacaiúnas River Watershed (IRW), Brazilian Amazon, arouses growing interest owing to the rapid deforestation and mining activities. In this study, soils (surface, SS; bottom, BS) and stream sediments (SD) from forested/deforested areas of IRW were analyzed with the aim of (1) evaluating the major sources of TE (mainly As, Ba, Cd, Cu, Co, Cr, Hg, Mo, Mn, Ni, Pb, V, and Zn), and (2) examining the soil-sediment TE link related to land-use change and/or geologic factors. Compositional data analysis (CoDA) was used to eliminate data closure issues and the centred log-ratio (clr) transformation yielded better results in Principal Component Analysis (PCA). The TE distribution pattern was significantly different (p < 0.05) between forested and deforested areas, but in both areas the TE distribution pattern is significantly correlated between SS, BS, and SD, indicating a strong lithogenic control. PCA (clr-transformed) identified the major geochemical bedrock signature as Fe-Ti-V-Cu-Cr-Ni, which is nearly similar in soil and sediments. The more accentuated enrichment and the maximum number of anomalies of these elements were found in the Carajás Basin and are highly coincident with mineral deposits/local lithologies without clear indication of anthropogenic contamination from point sources. Besides geogenic factors, deforestation is also affecting TE distribution in the basin. In deforested areas, Mn was significantly enriched in the surface horizon. Furthermore, linear regression analysis shows stronger TE relationships between soils and sediments in deforested areas than in forested ones, reflecting higher erosion in the former. This could be the reason for the relatively higher enrichment of TE (e.g., Fe, Mn, Cu, Cr, Ni) in deforested sediments. The TE contamination using regional background values provides more accurate results than worldwide reference values. Thus, the former should be considered for a more realistic environmental risk assessment in IRW and other forest ecosystems in the Brazilian Amazon.

Unexpected Antioxidant Efficiency of Chlorogenic Acid Phenolipids in Fish Oil-in-Water Nanoemulsions: An Example of How Relatively Low Interfacial Concentrations Can Make Antioxidants to Be Inefficient.

Selecting effective antioxidants is challenging since their efficiency in inhibiting lipid oxidation depends on the rate constants of the chemical reactions involved and their concentration at the reaction site, i.e., at the interfacial region. Accumulation of antioxidants at the interface of emulsions is key to modulate their efficiency in inhibiting lipid oxidation but its control was not well understood, especially in emulsions. It can be optimized by modifying the physicochemical properties of antioxidants or the environmental conditions. In this work, we analyze the effects of surfactant concentration, droplet size, and oil to water ratio on the effective interfacial concentration of a set of chlorogenic acid (CGA) esters in fish oil-in-water (O/W) emulsions and nanoemulsions and on their antioxidant efficiency. A well-established pseudophase kinetic model is used to determine in the intact emulsified systems the effective concentrations of the antioxidants (AOs). The relative oxidative stability of the emulsions is assessed by monitoring the formation of primary oxidation products with time. Results show that the concentration of all AOs at the interfacial region is much higher (20-90 fold) than the stoichiometric one but is much lower than those of other phenolipid series such as caffeic or hydroxytyrosol derivatives. The main parameter controlling the interfacial concentration of antioxidants is the surfactant volume fraction, ΦI, followed by the O/W ratio. Changes in the droplet sizes (emulsions and nanoemulsions) have no influence on the interfacial concentrations. Despite the high radical scavenging capacity of CGA derivatives and their being concentrated at the interfacial region, the investigated AOs do not show a significant effect in inhibiting lipid oxidation in contrast with what is observed using other series of homologous antioxidants with similar reactivity. Results are tentatively interpreted in terms of the relatively low interfacial concentrations of the antioxidants, which may not be high enough to make the rate of the inhibition reaction faster than the rate of radical propagation.

Polyphenols as Antioxidants for Extending Food Shelf-Life and in the Prevention of Health Diseases: Encapsulation and Interfacial Phenomena.

Toxicity caused by the exposure to human-made chemicals and environmental conditions has become a major health concern because they may significantly increase the formation of reactive oxygen species (ROS), negatively affecting the endogenous antioxidant defense. Living systems have evolved complex antioxidant mechanisms to protect cells from oxidative conditions. Although oxidative stress contributes to various pathologies, the intake of molecules such as polyphenols, obtained from natural sources, may limit their effects because of their antioxidant and antimicrobial properties against lipid peroxidation and against a broad range of foodborne pathogens. Ingestion of polyphenol-rich foods, such as fruits and vegetables, help to reduce the harmful effects of ROS, but the use of supramolecular and nanomaterials as delivery systems has emerged as an efficient method to improve their pharmacological and therapeutic effects. Suitable exogenous polyphenolic antioxidants should be readily absorbed and delivered to sites where pathological oxidative damage may take place, for instance, intracellular locations. Many potential antioxidants have a poor bioavailability, but they can be encapsulated to improve their ideal solubility and permeability profile. Development of effective antioxidant strategies requires the creation of new nanoscale drug delivery systems to significantly reduce oxidative stress. In this review we provide an overview of the oxidative stress process, highlight some properties of ROS, and discuss the role of natural polyphenols as bioactives in controlling the overproduction of ROS and bacterial and fungal growth, paying special attention to their encapsulation in suitable delivery systems and to their location in colloidal systems where interfaces play a crucial role.

Effects of Surfactant Volume Fraction on the Antioxidant Efficiency and on The Interfacial Concentrations of Octyl and Tetradecyl p-Coumarates in Corn Oil-in-Water Emulsions.

Surfactants have been used for decades in the food industry for the preparation of lipid-based emulsified food stuffs. They play two main roles in the emulsification processes: first they decrease the interfacial tension between the oil and water, facilitating droplet deformation and rupture; second, they reduce droplet coalescence by forming steric barriers. However, addition of surfactants to binary oil-water mixtures also brings up the formation of three-dimensional interfacial layers, surrounding each emulsion droplet, that significantly alter chemical reactivity. This is the case, for instance, in the inhibition reaction between antioxidants and the lipid radicals formed in the course of the spontaneous oxidation reaction of unsaturated lipids, which are commonly employed in the preparation of food-grade emulsions. The rate of the inhibition reaction depends on the effective concentrations of antioxidants, which are mostly controlled by the amount of surfactant employed in the preparation of the emulsion. In this work, we analyze the effects of the surfactant Tween 20 on the oxidative stability and on the effective concentrations of two model antioxidants derived from cinnamic acid, determining their interfacial concentrations in the intact emulsions to avoid disrupting the existing equilibria and biasing results. For this purpose, a recently developed methodology was employed, and experimental results were interpreted on the grounds of a pseudophase kinetic model.

Caffeic acid phenolipids in the protection of cell membranes from oxidative injuries. Interaction with the membrane phospholipid bilayer.

Caffeic acid (CA) has demonstrated a strong intracellular antioxidant ability by scavenging ROS, contributing to the maintenance of cell membrane structural integrity and to reduce oxidative injuries in other cell components. Nevertheless, caffeic acid has limited usage, due to its hydrophilic character. In this work, the introduction of alkyl chains in the caffeic acid molecule by esterification (methyl - C1, ethyl - C2, butyl - C4, hexyl - C6, octyl - C8 and hexadecyl - C16), significantly increased its lipophilicity. All caffeates tested showed a much higher protective activity than caffeic acid against red blood cells (RBCs) AAPH-induced oxidative stress; this protection was heavily dependent on the length of the alkyl chain of the esters, and on their concentration. At 2.5 and 5 µM, the more lipophilic compounds (C8 and C16) showed a remarkable antioxidant activity, inhibiting hemolysis; probably, their better location within the membrane leads to a better antioxidative protection; however, at 50 µM, the more hydrophilic compounds (C1-C4) showed a better activity against hemolysis than the more lipophilic ones (C8-C16). At this higher concentration, the better interaction of the more lipophilic compounds with the membrane seems to cause changes in RBC membrane fluidity, disturbing membrane integrity. Our data show that the antioxidant activity of these compounds could play an important role for the protection of different tissues and organs, by protecting cell membranes from oxidative injuries.

Modeling Chemical Reactivity at the Interfaces of Emulsions: Effects of Partitioning and Temperature.

Bulk phase chemistry is hardly ever a reasonable approximation to interpret chemical reactivity in compartmentalized systems, because multiphasic systems may alter the course of chemical reactions by modifying the local concentrations and orientations of reactants and by modifying their physical properties (acid-base equilibria, redox potentials, etc.), making them-or inducing them-to react in a selective manner. Exploiting multiphasic systems as beneficial reaction media requires an understanding of their effects on chemical reactivity. Chemical reactions in multiphasic systems follow the same laws as in bulk solution, and the measured or observed rate constant of bimolecular reactions can be expressed, under dynamic equilibrium conditions, in terms of the product of the rate constant and of the concentrations of reactants. In emulsions, reactants distribute between the oil, water, and interfacial regions according to their polarity. However, determining the distributions of reactive components in intact emulsions is arduous because it is physically impossible to separate the interfacial region from the oil and aqueous ones without disrupting the existing equilibria and, therefore, need to be determined in the intact emulsions. The challenge is, thus, to develop models to correctly interpret chemical reactivity. Here, we will review the application of the pseudophase kinetic model to emulsions, which allows us to model chemical reactivity under a variety of experimental conditions and, by carrying out an appropriate kinetic analysis, will provide important kineticparameters.

Interfacial kinetics in olive oil-in-water nanoemulsions: Relationships between rates of initiation of lipid peroxidation, induction times and effective interfacial antioxidant concentrations.

HYPOTHESIS: A detailed quantitative description of the effects of antioxidants in inhibiting lipid peroxidation in oil-in-water emulsions can be achieved by determining the relationships between the rates of initiation of the lipid peroxidation reaction, the length of the induction period preceding the propagation step of the radical oxidation process and the effective antioxidant interfacial concentrations. EXPERIMENTS: We successfully prepared and characterized a series of olive oil-in-water nanoemulsions and allowed them to spontaneously oxidize. Their oxidative stability was evaluated by carrying out in the presence, and absence, of antioxidants derived from gallic acid, by monitoring the formation of primary oxidation products with time, by determining the corresponding induction periods, and by determining the effective interfacial concentrations of the antioxidants in the intact emulsions. FINDINGS: Results show that both, the length of the induction periods and the antioxidant interfacial concentrations change concomitantly, increasing with the hydrophobicity of the antioxidant up to a maximum at the octyl derivative; longer aliphatic chains decrease their efficiency. The ratio between the interfacial antioxidant concentration and the induction period remains constant independently of the antioxidant, demonstrating that the effective concentrations of antioxidant at the interface control their efficiencies in emulsions.

Effects of the Reactive Moiety of Phenolipids on Their Antioxidant Efficiency in Model Emulsified Systems.

Our previous research was focused on the effects of hydrophobicity on the antioxidant (AO) efficiency of series of homologous antioxidants with the same reactive moieties. In this work we evaluate the antioxidant efficiency of hydrophobic phenolipids in 4:6 olive oil-in-water emulsions, with different phenolic moieties (derived from caffeic, 4-hydroxycinnamic, dihydrocaffeic acids, tyrosol and hydroxytyrosol), with alkyl chains of 8 and 16 carbons, and compare the antioxidant efficiency with that of the parent compounds. All catecholic phenolipids, in particular the C8 derivatives, have proven to be better antioxidants for the oxidative protection of emulsions than their parental compounds with octyl dihydrocafffeate being the most efficient (16-fold increase in relation to the control). To understand the importance of some factors on the antioxidant efficiency of compounds in emulsions, Pearson's correlation analysis was carried out between antioxidant activity and the first anodic potential (Epa), reducing capacity (FRAP value), DPPH radical scavenging activity (EC50) and the concentration of antioxidants in each region of the emulsified system. Results confirm the importance of the effective concentration of AOs in the interfacial region (AOI) (ρ = 0.820) and of the Epa (ρ = -0.677) in predicting their antioxidant efficiency in olive oil-in-water emulsions.

Polyphenolic Antioxidants in Lipid Emulsions: Partitioning Effects and Interfacial Phenomena.

The autoxidation of lipids in complex systems such as emulsions or biological membranes, although known to occur readily and to be associated with important pathological events, is lacking in quantitative data in spite of the huge efforts that have been made in attempting to unravel the complex mechanisms of lipid oxidation and its inhibition by antioxidants. Lipids are present as oil-in-water emulsions in many foods and pharmaceutical formulations, and the prevalent role of the interfacial region is critical to understand the antioxidant behavior and to correctly interpret antioxidant efficiencies. The aim of this review is to summarize the current knowledge on the chemical fate of antioxidants before they react with peroxyl radicals. Many researchers highlighted the predominant role of interfaces, and although some attempts have been made to understand their role, in most instances, they were essentially qualitative and based on putative hypotheses. It is only recently that quantitative reports have been published. Indeed, knowledge on the effects of relevant experimental variables on the effective concentrations of antioxidants is necessary for a successful design of alternate, effective antioxidative solutions.

A new family of hydroxytyrosol phenolipids for the antioxidant protection of liposomal systems.

Hydroxytyrosol (HT) is a well-known olive oil polyphenol for its high antioxidant capacity and important cardio and neuroprotective effects. However, its use in lipidic systems is limited, due to its hydrophilic character. In this study, we approach the particular structure of xanthophylls and synthetize HT esters specially designed for the protection of liposomal systems. These HT esters contain two polyphenolic moieties separated by a lipophilic alkyl spacer of different length (12, 16 or 22 carbons). To evaluate the antioxidant activity of these compounds against the 2,2'-azobis(2-amidinopropane) hydrochloride induced oxidation, soybean phospholipid liposomes were used. Fluorescence quenching studies were used to assess the insertion of the compounds in the liposomes. The synthetized HT derivatives were able to protect liposomes from induced oxidation when added to the suspensions. The rank of activity was severely influenced by the alkyl chain length of the spacer molecule, being the C12 derivative the most active antioxidant, with an increase in the oxidative stability of liposomes of 2.2 times when compared with the control. The incorporation of compounds during liposome preparation improved the antioxidant capacity of all HT derivatives by about 2.8 times, when compared to the control. This is probably due to a similar transmembrane position with both polyphenolic rings located at the phospholipid polar heads. The synthesis of bis-ester derivatives seems to be a promising strategy to fine-tune antioxidant molecules at biomembranes, thus increasing the oxidative stability of liposomal systems by improving the antioxidant activity of hydrophilic phenolic compounds with high free radical scavenging activity.

Interfacial Concentrations of Hydroxytyrosol Derivatives in Fish Oil-in-Water Emulsions and Nanoemulsions and Its Influence on Their Lipid Oxidation: Droplet Size Effects.

Reports on the effect of droplet size on the oxidative stability of emulsions and nanoemulsions are scarce in the literature and frequently contradictory. Here, we have employed a set of hydroxytyrosol (HT) esters of different hydrophobicity and fish oil-in-water emulsified systems containing droplets of different sizes to evaluate the effect of the droplet size, surfactant, (ΦI) and oil (ΦO) volume fractions on their oxidative stability. To quantitatively unravel the observed findings, we employed a well-established pseudophase kinetic model to determine the distribution and interfacial concentrations of the antioxidants (AOs) in the intact emulsions and nanoemulsions. Results show that there is a direct correlation between antioxidant efficiency and the concentration of the AOs in the interfacial region, which is much higher (20-200 fold) than the stoichiometric one. In both emulsified systems, the highest interfacial concentration and the highest antioxidant efficiency was found for hydroxytyrosol octanoate. Results clearly show that the principal parameter controlling the partitioning of antioxidants is the surfactant volume fraction, ΦI, followed by the O/W ratio; meanwhile, the droplet size has no influence on their interfacial concentrations and, therefore, on their antioxidant efficiency. Moreover, no correlation was seen between droplet size and oxidative stability of both emulsions and nanoemulsions.

Source and background threshold values of potentially toxic elements in soils by multivariate statistics and GIS-based mapping: a high density sampling survey in the Parauapebas basin, Brazilian Amazon.

A high-density regional-scale soil geochemical survey comprising 727 samples (one sample per each 5 × 5 km grid) was carried out in the Parauapebas sub-basin of the Brazilian Amazonia, under the Itacaiúnas Basin Geochemical Mapping and Background Project. Samples were taken from two depths at each site: surface soil, 0-20 cm and deep soil, 30-50 cm. The ground and sieved (< 75 µm) fraction was digested using aqua regia and analyzed for 51 elements by inductively coupled plasma mass spectrometry (ICPMS). All data were used here, but the principal focus was on the potential toxic elements (PTEs) and Fe and Mn to evaluate the spatial distribution patterns and to establish their geochemical background concentrations in soils. Geochemical maps as well as principal component analysis (PCA) show that the distribution patterns of the elements are very similar between surface and deep soils. The PCA, applied on clr-transformed data, identified four major associations: Fe-Ti-V-Sc-Cu-Cr-Ni (Gp-1); Zr-Hf-U-Nb-Th-Al-P-Mo-Ga (Gp-2); K-Na-Ca-Mg-Ba-Rb-Sr (Gp-3); and La-Ce-Co-Mn-Y-Zn-Cd (Gp-4). Moreover, the distribution patterns of elements varied significantly among the three major geological domains. The whole data indicate a strong imprint of local geological setting in the geochemical associations and point to a dominant geogenic origin for the analyzed elements. Copper and Fe in Gp-1 were enriched in the Carajás basin and are associated with metavolcanic rocks and banded-iron formations, respectively. However, the spatial distribution of Cu is also highly influenced by two hydrothermal mineralized copper belts. Ni-Cr in Gp-1 are highly correlated and spatially associated with mafic and ultramafic units. The Gp-2 is partially composed of high field strength elements (Zr, Hf, Nb, U, Th) that could be linked to occurrences of A-type Neoarchean granites. The Gp-3 elements are mobile elements which are commonly found in feldspars and other rock-forming minerals being liberated by chemical weathering. The background threshold values (BTV) were estimated separately for surface and deep soils using different methods. The '75th percentile', which commonly used for the estimation of the quality reference values (QRVs) following the Brazilian regulation, gave more restrictive or conservative (low) BTVs, while the 'MMAD' was more realistic to define high BTVs that can better represent the so-called mineralized/normal background. Compared with CONAMA Resolution (No. 420/2009), the conservative BTVs of most of the toxic elements were below the prevention limits (PV), except Cu, but when the high BTVs are considered, Cu, Co, Cr and Ni exceeded the PV limits. The degree of contamination (Cdeg), based on the conservative BTVs, indicates low contamination, except in the Carajás basin, which shows many anomalies and had high contamination mainly from Cu, Cr and Ni, but this is similar between surface and deep soils indicating that the observed high anomalies are strictly related to geogenic control. This is supported when the Cdeg is calculated using the high BTVs, which indicates low contamination. This suggests that the use of only conservative BTVs for the entire region might overestimate the significance of anthropogenic contamination; thus, we suggest the use of high BTVs for effective assessment of soil contamination in this region. The methodology and results of this study may help developing strategies for geochemical mapping in other Carajás soils or in other Amazonian soils with similar characteristics.

Effects of droplet size on the interfacial concentrations of antioxidants in fish and olive oil-in-water emulsions and nanoemulsions and on their oxidative stability.

HYPOTHESIS: One fundamental and unsolved question in colloid chemistry, and also in the food industry, is whether molecular distributions, specifically the interfacial concentrations of antioxidants (AOI), are independent of the droplet sizes. Pseudophase kinetic models, widely employed to interpret chemical reactivity in colloidal systems and to determine antioxidant distributions, assume that they are independent. EXPERIMENTS: To prove, or discard, the above hypothesis, we prepared and characterized a series of olive and fish oil-in-water nanoemulsions with different droplet sizes, carried out a kinetic study to evaluate their oxidative stability, both in the presence and absence of gallic acid (GA), and determined its interfacial concentrations. FINDINGS: Results indicate that a change in the droplet size (80-1300 nm) does not alter the oxidative stability of the nanoemulsions in the absence of GA. Addition of GA increases their oxidative shelf-life and, at constant surfactant volume fraction, ΦI, the oxidative stability and the antioxidant distribution do not depend on the droplet size. Overall, results suggest that the droplet size does not affect the ratio between the rates of radical production and of inhibition by antioxidants, ratio that defines an "efficient" (or inefficient) antioxidant, providing experimental evidence supporting the operative assumption of pseudophase kinetic models.

Influence of AO chain length, droplet size and oil to water ratio on the distribution and on the activity of gallates in fish oil-in-water emulsified systems: Emulsion and nanoemulsion comparison.

The distribution of a homologous series of polyphenol derivatives of increasing lipophilicity has been determined in fish oil-in-water emulsions and nanoemulsions by the pseudophase model. One of the hypotheses on which the pseudophase model is based, is that its application is independent of the size of emulsion droplets. In agreement with our hypothesis, results showed that the smaller droplet size found in nanoemulsions does not affect partition constants of gallic acid (GA) and its esters. The antioxidant efficiency of GA and gallates in the emulsified systems used, correlated positively with the concentration of antioxidant at the interfacial region. The increase in the oil/water ratio increased the overall oxidative stability of emulsions but decreased the antioxidant efficiency of the more lipophilic derivatives. This can be assigned to the fact that, increasing the oil phase volume, the interfacial concentration decreased for the more lipophilic antioxidants.

Body segments and biological maturation to estimate the propulsive force of the arm in young swimmers / Segmentos corporais e maturação biológica para estimar a força propulsiva da braçada em jovens nadadores

Abstract This study aimed to estimate the propulsive force of the arm (PFA) in young freestyle swimmers and propose an equation to estimate propulsive force, considering anthropometric variables and maturity offset. Seventy-six competitive swimmers [boys: n= 53; age= 13.58 ± 1.79; girls: n= 23; age= 12.98 ± 1.79] participated in this study. Height, lean mass, sitting height, leg length, arm span, triceps skinfold, arm muscle area (AMA), and maturity offset were assessed. The propulsive force of the arm was measured by the tethered swim test. A multiple linear regression (concurrent model) was used to develop the equation using the variables AMA, arm span, and maturity offset. The Bland-Altman method was used to compare the values found between PFA and propulsive force-estimated (PFE). There was a significant correlation between the variables PFA and AMA (R²=0.12; p<0.01), arm span (R²=0.21; p<0.01), and maturity offset (R²=0.20; p<0.01) for boys, whilst in girls theses values were: AMA (R²=0.07;p=0.20), arm span (R²=0.50;p<0.01), and maturity offset (R²=0.44;p<0.01). Two linear equations were established to predict the PFA in boys and girls Bland-Altman analysis showed an agreement between PFA and PFE. In conclusion, the equation is a valuable tool to monitor training and help improve swimmer performance.

Resumo Este estudo teve como objetivo estimar a força propulsora da braçada(FPB) em jovens nadadores do estilo livre e propor uma equação para estimar a força propulsora, considerando variáveis antropométricas e a maturação. Setenta e seis nadadores competitivos [meninos: n = 53; idade = 13,58 ± 1,79; meninas: n = 23; idade = 12,98 ± 1,79] participaram deste estudo. Foram avaliados: altura, massa magra, estatura sentada, comprimento da perna, envergadura, dobra cutânea do tríceps, área muscular do braço (AMB) e maturação. A força propulsiva da braçada foi medida pelo teste de nado atado. Uma regressão linear múltipla (modelo concorrente) foi usada para desenvolver a equação usando as variáveis AMB, envergadura e maturação. O método de Bland - Altman foi utilizado para comparar os valores encontrados entre FPB e força propulsiva estimada (FPE). Houve correlação significativa entre as variáveis FPB e AMB (R² = 0,12; p <0,01), envergadura (R² = 0,21; p <0,01) e maturação (R² = 0,20; p <0,01) para meninos, enquanto os valores das meninas foram: AMB (R² = 0,07; p = 0,20), envergadura (R² = 0,50; p <0,01) e maturação (R² = 0,44; p <0,01). Duas equações lineares foram estabelecidas para predizer a FPB em meninos e meninas. A análise de Bland-Altman mostrou concordância entre FPB e FPE. Em conclusão, a equação é uma ferramenta valiosa para monitorar o treinamento e ajudar a melhorar o desempenho do nadador.