Helium in polygonal nanopores at zero temperature: Density functional theory calculations

We investigate adsorption of helium in nanoscopic polygonal pores at zero temperature using a finite-range density functional theory. The adsorption potential is computed by means of a technique denoted as the elementary source method. We analyze a rhombic pore with Cs walls, where we show the existence of multiple interfacial configurations at some linear densities, which correspond to metastable states. Shape transitions and hysterectic loops appear in patterns which are richer and more complex than in a cylindrical tube with the same transverse area.

Kinetics of phosphorus sorption in soils in the state of Paraíba¹

The soil P sorption capacity has been studied for many years, but little attention has been paid to the rate of this process, which is relevant in the planning of phosphate fertilization. The purpose of this experiment was to assess kinetics of P sorption in 12 representative soil profiles of the State of Paraíba (Brazil), select the best data fitting among four equations and relate these coefficients to the soil properties. Samples of 12 soils with wide diversity of physical, chemical and mineralogical properties were agitated in a horizontal shaker, with 10 mmo L-1 CaCl2 solution containing 6 and 60 mg L-1 P, for periods of 5, 15, 30, 45, 60, 90, 120, 420, 720, 1,020, and 1,440 min. After each shaking period, the P concentration in the equilibrium solution was measured and three equations were fitted based on the Freundlich equation and one based on the Elovich equation, to determine which soil had the highest sorption rate (kinetics) and which soil properties correlated to this rate. The kinetics of P sorption in soils with high maximum P adsorption capacity (MPAC) was fast for 30 min at the lower initial P concentration (6 mg L-1). No difference was observed between soils at the higher initial P concentration (60 mg L-1). The P adsorption kinetics were positively correlated with clay content, MPAC and the amount of Al extracted with dithionite-citrate-bicarbonate. The data fitted well to Freundlich-based equations equation, whose coefficients can be used to predict P adsorption rates in soils.

Probing vortices in 4He nanodroplets

We present static and dynamical properties of linear vortices in 4He droplets obtained from density functional calculations. By comparing the adsorption properties of different atomic impurities embedded in pure droplets and in droplets where a quantized vortex has been created, we suggest that Ca atoms should be the dopant of choice to detect vortices by means of spectroscopic experiments.

Induction of a geochemical barrier for As, Fe and S immobilization in a sulfide substrate

Acid mine drainage (AMD) is an environmental concern due to the risk of element mobilization, including toxic elements, and inclusion in the food chain. In this study, three cover layers were tested to minimize As, Fe and S mobilization from a substrate from former gold mining, containing pyrite and arsenopyrite. For this purpose, different layers (capillary break, sealant and cover layer) above the substrate and the induction of a geochemical barrier (GB) were used to provide suitable conditions for adsorption and co-precipitation of the mobilized As. Thirteen treatments were established to evaluate the leaching of As, Fe and S from a substrate in lysimeters. The pH, As, Fe, S, Na, and K concentrations and total volume of the leachates were determined. Mineralogical analyses were realized in the substrate at the end of the experimental period. Lowest amounts of As, Fe and S (average values of 5.47, 48.59 and 132.89 g/lysimeter) were leached in the treatments that received Na and K to induce GB formation. Mineralogical analyses indicated jarosite formation in the control treatment and in treatments that received Na and K salts. However, the jarosite amounts in these treatments were higher than in the control, suggesting that these salts accelerated the GB formation. High amounts of As, Fe and S (average values of 11.7, 103.94 and 201.13 g/lysimeter) were observed in the leachate from treatments without capillary break layer. The formation of geochemical barrier and the use of different layers over the sulfide substrate proved to be efficient techniques to decrease As, Fe and S mobilization and mitigate the impact of acid mine drainage.

Phosphorus accumulation and pollution potential in a hapludult fertilized with pig manure

Successive applications of pig litter to the soil surface can increase the phosphorus (P) content and alter its adsorption, promoting P transfer to surface or subsurface waters. The purpose of this study was to evaluate P accumulation and the pollution potential of a soil after application of pig litter. In March 2010, eight years after the installation of an experiment in Braço do Norte, Santa Catarina, SC, Brazil, on a Typic Hapludult, soil was sampled (layers 0-2.5, 2.5-5, 5-10, 10-15, 15-20 and 20-30 cm) after the following fertilization treatments: no pig litter fertilization, pig slurry application and pig manure application. In this period, 694 and 1,890 kg P2O5 ha-1 were applied in the treatments with pig slurry and pig manure, respectively. The P content was determined, based on Mehlich-1, anion exchange resin (AER), 0.01 mol L-1 CaCl2 and total P in the samples. The adsorption isotherm parameters were also determined by the Langmuir and Koski-Vähälä & Hartikainem models in the layers 0-2.5 and 20-30 cm. The application of 1,890 kg P2O5 ha-1 in the form of pig manure led to P accumulation, as evidenced by Mehlich-1, down to a depth of 15 cm, by AER and 0.01 mol L-1 CaCl2 down to 20 cm and by total P to 30 cm. After application of 1,890 kg P2O5 ha-1 in the form of pig manure, the values of maximum P adsorption capacity were lowest in the deepest layer (20-30 cm), indicating the occupation of part of the adsorption sites of the particles. The application of swine manure to the soil over eight years increased the P quantity in the soil solution of the surface layer, indicating environmental contamination risk for surface and subsurface waters.

Estimating subsoil resistance to nitrate leaching from easily measurable pedological properties

Leaching of nitrate (NO3-) can increase the groundwater concentration of this anion and reduce the agronomical effectiveness of nitrogen fertilizers. The main soil property inversely related to NO3- leaching is the anion exchange capacity (AEC), whose determination is however too time-consuming for being carried out in soil testing laboratories. For this reason, this study evaluated if more easily measurable soil properties could be used to estimate the resistance of subsoils to NO3- leaching. Samples from the subsurface layer (20-40 cm) of 24 representative soils of São Paulo State were characterized for particle-size distribution and for chemical and electrochemical properties. The subsoil content of adsorbed NO3- was calculated from the difference between the NO3- contents extracted with 1 mol L-1 KCl and with water; furthermore, NO3- leaching was studied in miscible displacement experiments. The results of both adsorption and leaching experiments were consistent with the well-known role exerted by AEC on the nitrate behavior in weathered soils. Multiple regression analysis indicated that in subsoils with (i) low values of remaining phosphorus (Prem), (ii) low soil pH values measured in water (pH H2O), and (iii) high pH values measured in 1 moL L-1 KCl (pH KCl), the amounts of surface positive charges tend to be greater. For this reason, NO3- leaching tends to be slower in these subsoils, even under saturated flow condition.

Accumulation of phosphorus fractions and contamination potential in vineyard soils in the southern region of the state of Santa Catarina, Brazil

In vineyards, if phosphate is applied both before planting and at intervals during growth without consideration of technical criteria, the soil P fractions may be increased and their proportions altered. This study was carried out to evaluate the accumulation of P fractions and the parameters of the adsorption isotherm in a sandy Typic Hapludalf soil in vineyards with a history of successive and excessive phosphate fertilization. In December 2010, two vineyards were selected, one 4 and the other 15 years old, in Urussanga, State of Santa Catarina (Brazil). Three trenches were dug in each area and soil was collected from the 0-5, 5-10 and 10-20 cm depth ranges. The soil samples were dried in a forced-air oven, sieved and subjected to chemical analyses, P chemical fractionation and P adsorption isotherms. Excessive phosphate fertilization, before and during cultivation, particularly in the older vineyard and, consequently, with a longer history of phosphate fertilization, increased the inorganic P concentrations to the depth of 20 cm, especially in labile fractions extracted by anion exchange resin and NaHCO3 in the non-labile fraction, as well as in the non-labile fraction extracted by 1.0 mol L-1 HCl. The application of phosphate fertilizers and the long cultivation period increased the P levels in the organic labile fraction extracted by 0.5 mol L-1 NaHCO3, and especially in the moderately labile fraction extracted by 0.1 and 0.5 mol L-1 NaOH. Phosphate fertilization of older vineyards, i.e., cultivated for 15 years, increased the amounts of P desorbed in water, indicating a risk of contamination of surface waters and groundwater. The phosphate fertilization before planting, without considering the results of soil analysis, and during cultivation, disregarding the results of soil analysis, leaf analysis and expected yield, led to a reduction in the maximum P adsorption capacity in the 0-5 cm layer of vineyard 2, indicating saturation of part of the reactive particle adsorption sites.

Ecotoxicological approaches to assess the long-term effects of four anticancer drugs and metabolites on Daphnia pulex

The aquatic environment is exposed continuously and increasingly to chemical substances such as pharmaceuticals. These medical compounds are released into the environment after having being consumed and body-excreted by patients. Pharmaceutical residues are synthetic molecules that are not always removed by traditional sewage treatment processes and thus escape degradation. Among pharmaceuticals that escape sewage treatment plants (STPs), the anticancer drugs were measured in STP effluents and natural waters. In the aquatic environment, their long-term effects at low concentrations are sparsely known on non-target species. Tamoxifen is an anticancer drug that is widely prescribed worldwide for the prevention and treatment of hormone receptor-positive breast cancers. Two of its metabolites, i.e., endoxifen and 4-hydroxy- tamoxifen (4OHTam), have high pharmacological potency in vivo and such as tamoxifen, they are excreted via faeces by patients. Tamoxifen was measured in STP effluents and natural waters but, to the best of our knowledge, its metabolites concentrations in waters have never been reported. Imatinib is another and recent anticancer compound that targets specific tumour cells. This pharmaceutical is also body excreted and because of its increasing use in cancer treatment, imatinib may reach the natural water. The effects of tamoxifen and imatinib are unknown upon more than one generation of aquatic species. And the effects of 4OHTam, endoxifen have never been studied in ecotoxicology so far. The aims of this thesis were threefold. First, the sensitivity of D. pulex exposed to tamoxifen, 4OHTam, endoxifen or imatinib was assessed using ecotoxicological experiments. Ecotoxicology is the science that considers the toxic effects of natural or synthetic substances, such as pharmaceuticals, on organisms, populations, community and ecosystem. Acute and multigenerational (2-4 generations) tests were performed on daphnids considering several studied endpoints, such as immobilisation, size, reproduction, viability and intrinsic rate of natural increase. Additional prospective assays were designed to evaluate whether 1) low concentrations of tamoxifen and 4OHTam were able to induce toxic effects when used in combination, and 2) daphnids were able to recover when offspring were withdrawn from solutions carrying the pharmaceutical. Second, the stability of tamoxifen, 4OHTam and endoxifen in incubation medium was evaluated in solution exempted from daphnids. Because the nominal concentrations of tamoxifen, 4OHTam and endoxifen did not correspond to the measured, we provide a predictive method to estimate the concentrations of these chemicals during long-term ecotoxicological tests. Finally, changes in protein expressions were analysed in D. pulex exposed 2 or 7 seven days to tamoxifen using ecotoxicoproteomic experiments with a shot-gun approach inducing a peptide fractionation step. Our results show that tamoxifen, 4OHTam and endoxifen induced adverse effects in D. pulex at environmentally relevant concentrations. At very low concentrations, these molecules displayed unusual and teratogenic effects because morphological abnormalities were observed in offspring, such as thick and short antennas, curved spines, premature neonates and aborted eggs. Tamoxifen was the most toxic compound among the test chemicals, followed by 4OHTam, endoxifen and imatinib. Tamoxifen no-observed effect concentrations (NOECs) that were calculated for size, reproduction and intrinsic rate were below or in the range of the concentrations measured in natural waters, i.e., between 0.12 µg/L and 0.67 µg/L. For instance, the tamoxifen NOECs that were calculated for reproduction were between 0.67 and 0.72 µg/L, whereas the NOEC was < 0.15 µg/L when based on morphological abnormalities. The NOECs of 4OHTam were higher but still in the same order of magnitude as tamoxifen environmental concentrations, with a value of 1.48 µg/L. Endoxifen NOEC for the intrinsic rate of natural increase (r) and the reproduction were 0.4 and 4.3 µg/L, respectively. Daphnids that were withdrawn from tamoxifen and 4OHTam were not able to recover. Also, the reproduction of D. pulex was reduced when the treated animals were exposed to the combination of tamoxifen and 4OHTam while no effects were observed when these chemicals were tested individually at the same concentration. Among the anticancer drugs that were tested during this thesis, imatinib was the less toxic molecule towards D. pulex. No effects on size and reproduction were observed within two generations, except for the first whose reproduction decreased at the highest test concentration, i.e., 626 µg/L. Our results also underline the need to use measured or predicted concentrations instead of the nominal during aquatic experiments, particularly when lipophilic molecules are tested. Indeed, notable differences between nominal (i.e., theoretical) and measured concentrations were found with tamoxifen, 4OHTam and endoxifen at all test concentrations. A cost and time sustainable method was proposed to predict the test exposure levels of these chemicals during long-term experiments. This predictive method was efficient particularly for low concentrations, which corresponded to the test concentrations in multigenerational tests. In the ecotoxicoproteomic experiments a total of 3940 proteins were identified and quantified in D. pulex exposed to tamoxifen. These results are currently the largest dataset from D. pulex that is published and the results of proteomic analyses are available for the scientific community. Among these 3940 proteins, 189 were significantly different from controls. After protein annotation, we assumed that treated daphnids with tamoxifen had shifted cost-energy functions, such as reproduction, to maintain their basic metabolism necessary to survive. This metabolic cost hypothesis was supported by the presence of proteins involved in oxidative stress. Biomarkers for early detection of tamoxifen harmful effects on D. pulex were not discovered but the proteins of the vitellogenin-2 family (E9H8K5) and the ryanodine receptor (E9FTU9) are promising potential biomarkers because their expression was already modified after 2 days of treatment. In this thesis, the effects of tamoxifen, 4OHTam and endoxifen on daphnids raise questions about the potential impact of tamoxifen and 4OHTam in other aquatic ecosystems, and therefore, about metabolites in ecotoxicology. Because the NOECs were environmentally relevant, these results suggest that tamoxifen and 4OHTam may be interesting pharmaceuticals to consider in risk assessment. Our findings also emphasize the importance of performing long-term experiments and of considering multi-endpoints instead of the standard reproductive endpoint. Finally, we open the discussion about the importance to measure test exposures or not, during ecotoxicological studies. -- Les milieux aquatiques sont exposés continuellement à un nombre croissant de substances chimiques, notamment les médicaments issus de la médecine vétérinaire et humaine. Chez les patients, les substances administrées sont utilisées par le corps avant d'être éliminées par l'intermédiaire des excrétas dans le système d'eaux usées de la ville. Ces eaux rejoignent ensuite une station de traitement afin d'y éliminer les déchets. Dans le cas des molécules chimiques, il arrive que les processus de traitement d'eaux usées ne soient pas suffisamment efficaces et que ces molécules ne soient pas dégradées. Elles sont alors libérées dans le milieu aquatique avec les effluents de la station d'épuration. Une fois dans l'environnement, ces résidus de médicaments sont susceptibles d'induire des effets sur la faune et la flore aquatique, dont les conséquences à long terme et à faibles concentrations sont peu connues. Les anticancéreux sont une famille de médicaments qui peuvent échapper aux traitements des stations d'épuration et qui sont retrouvées dans le milieu aquatique naturel. Parmi ces substances, le tamoxifen est une molécule utilisée dans le monde entier pour prévenir et traiter les cancers hormonaux dépendant du sein, notamment. Une fois ingéré, le tamoxifen est transformé par le foie en métabolites dont deux d'entre eux, le 4-hydroxy-tamoxifen (4OHTam) et l'endoxifen, possèdent un affinité pour les récepteurs aux estrogènes et une efficacité sur les cellules tumorales supérieure au tamoxifen lui- même. Tout comme la molécule mère, ces métabolites sont principalement éliminés par l'intermédiaire des fèces. Le tamoxifen a déjà été mesuré dans les effluents de stations d'épuration et dans les eaux naturelles, mais aucune valeur n'a été reportée pour ses métabolites jusqu'à présent. Un autre anticancéreux, également éliminé par voie biliaire et susceptible d'atteindre l'environnement, est l'imatinib. Cette récente molécule a révolutionné le traitement et la survie des patients souffrant de leucémie myéloïde chronique et de tumeur stromales gastrointestinales. Les effets du tamoxifen et de l'imatinib sur plusieurs générations d'organismes aquatiques, tels que les microcrustacés Daphnia, sont inconnus et le 4OHTam et l'endoxifen n'ont même jamais été testés en écotoxicologie. Cette thèse s'est articulée autour de trois objectifs principaux. Premièrement, la sensibilité des D. pulex exposés au tamoxifen, 4OHTam, endoxifen et imatinib a été évaluée par l'intermédiaire de tests aigus et de tests sur deux à quatre générations. La mobilité, la taille, la reproduction, la viabilité et la croissance potentielle de la population ont été relevées au cours de ces expériences. Des tests supplémentaires, à but prospectifs, ont également été réalisés afin d'évaluer 1) la capacité de récupération des daphnies, lorsque leurs descendants ont été placés dans un milieu exempté de tamoxifen ou de 4OHTam, 2) les effets chez les daphnies exposées à une solution contenant de faibles concentration de tamoxifen et de 4OHTam mélangés. Le deuxième objectif a été d'évaluer la stabilité du tamoxifen, 4OHTam et endoxifen dilué dans le milieu des daphnies. Après analyses, les concentrations mesurées ne correspondaient pas aux concentrations nominales (c.-à-d., théoriques) et il a été nécessaire de développer une méthode efficace de prédiction des niveaux d'exposition lors de tests de longue durée réalisés avec ces trois molécules. Finalement, des changements dans l'expression des protéines chez des daphnies exposées au tamoxifen ont été investigués par l'intermédiaire d'expériences écotoxicoprotéomiques avec une approche dite de shot-gun avec une étape de fractionnement des protéines. Les résultats obtenus dans cette thèse montrent que le tamoxifen, le 4OHTam et l'endoxifen induisent des effets indésirables chez les daphnies à des niveaux d'exposition proches ou identiques aux concentrations du tamoxifen mesurées dans l'environnement, c'est-à-dire 0.12 et 0.67 µg/L de tamoxifen. Ces molécules ont induit des effets inhabituels tels que la production de : nouveau-nés anormaux, avec des antennes et des queues déformées, des prématurés et des oeufs avortés. Le tamoxifen fut la molécule la plus toxique pour les D. pulex suivie du 4OHTam, de l'endoxifen et enfin de l'imatinib. Lors des expériences sur plusieurs générations, les concentrations n'ayant statistiquement pas d'effet (c.à.d. NOEC en anglais) sur la taille, la reproduction et la croissance intrinsèque de la population étaient du même ordre de grandeur que les concentrations environnementales du tamoxifen. Par exemple, les NOECs du tamoxifen calculées pour la reproduction étaient de 0.67 et 0.72 µg/L, tandis que celle calculée sur la base des anomalies chez les nouveau-nés était < 0.15 µg/L. Les NOECs du 4OHTam se situaient entre 0.16 et 1.48 µg/L et celles de l'endoxifen pour la croissance intrinsèque de la population, ainsi que pour la reproduction, étaient de 0.4 et 4.3 µg/L, respectivement. Dans l'expérience basée sur la récupération des daphnies, la taille et la reproduction ont diminué bien que la descendance fût placée dans un milieu sans substances chimiques. Les daphnies exposées au mélange de tamoxifen et de 4OHTam ont produit moins de nouveau-nés que les contrôles, alors que ces concentrations n'ont pas induit d'effets lorsque testées individuellement. Finalement, l'imatinib n'a pas montré d'effets sur les deux générations testées. Seule la première génération exposée à la plus haute concentration (626 µg/L) a montré une diminution de la reproduction. Les résultats obtenus lors de l'évaluation de la stabilité du tamoxifen, 4OHTam et endoxifen dans le milieu des daphnies ont souligné l'importance d'utiliser des concentrations mesurées ou prédites en écotoxicologie. En effet, des différences notables entre concentrations nominales et mesurées ont été observées à toutes les concentrations et l'hypothèse d'un phénomène d'adsorption sur le verre des récipients a été posée. De ce fait, il a été nécessaire d'élaborer une méthode prédictive efficace et acceptable, en terme de temps et de coûts. Une régression polynomiale basée sur des concentrations mesurées et nominales a permis de prédire avec efficacité les faibles niveaux d'exposition utilisés lors d'expériences écotoxicologiques à long terme, sur plusieurs générations. Suite aux expériences d'écotoxicoprotéomiques, un total de 3940 protéines ont été identifiées et quantifiées chez des daphnies exposées au tamoxifen. Ce nombre est actuellement la plus large série de données publiées et mises à disposition pour la communauté scientifique. Parmi ces protéines, 189 sont significatives et possiblement reliées à des processus de reproduction et de stress. Sur cette base, nous avons émis l'hypothèse que les individus subissant un stress, lié à l'exposition au tamoxifen, ont utilisé leur énergie de base pour favoriser leur survie plutôt que la reproduction. Enfin, la détermination de bio-marqueurs exprimant des dommages précoces des daphnies exposées au tamoxifen n'a pas abouti en tant que telle, mais des protéines prometteuses, telle que la famille de viellogenin-2 (E9H8K5) et le récepteur à la ryanodine (E9FTU9), ont été exprimées après deux jours d'exposition déjà. Ces protéines pourraient faire l'objet d'investigations écotoxicoprotéomiques futures. Les résultats de cette thèse posent certaines questions quant au risque du tamoxifen, du 4OHTam et de l'endoxifen sur la faune et la flore aquatique et plus particulièrement sur les anticancéreux présents dans l'environnement. Les effets toxiques de ces molécules ont été observés à des concentrations environnementales et sur plusieurs générations. La question de considérer les métabolites, et ainsi les pro-médicaments, en écotoxicologie est soulevée, notamment parce que ces molécules peuvent être plus actives et efficaces que la molécule mère. Les expériences chroniques, sur plusieurs générations sont également à favoriser car elles offrent un meilleur reflet de la réalité environnementale que des essais aigus ou d'une génération. L'utilisation de la protéomique permet d'agrandir les connaissances sur les effets des médicaments à un niveau inférieur de l'organisation biologique et ainsi, de mieux comprendre de potentiels mécanismes d'action ou de déterminer de potentiels biomarqueurs. Finalement, il semble important de discuter de l'opportunité de mesurer les concentrations qui sont testées en écotoxicologie afin de ne pas sous-estimer le risque pour la faune et la flore aquatique.

Evaluation of ammonia volatilization losses by adjusted parameters of a logistic function

The dynamics of N losses in fertilizer by ammonia volatilization is affected by several factors, making investigation of these dynamics more complex. Moreover, some features of the behavior of the variable can lead to deviation from normal distribution, making the main commonly adopted statistical strategies inadequate for data analysis. Thus, the purpose of this study was to evaluate the patterns of cumulative N losses from urea through ammonia volatilization in order to find a more adequate and detailed way of assessing the behavior of the variable. For that reason, changes in patterns of ammonia volatilization losses as a result of applying different combinations of two soil classes [Planossolo and Chernossolo (Typic Albaqualf and Vertic Argiaquolls)] and different rates of urea (50, 100 and 150 kg ha-1 N), in the presence or absence of a urease inhibitor, were evaluated, adopting a 2 × 3 × 2 factorial design with four replications. Univariate and multivariate analysis of variance were performed using the adjusted parameter values of a logistic function as a response variable. The results obtained from multivariate analysis indicated a prominent effect of the soil class factor on the set of parameters, indicating greater relevance of soil adsorption potential on ammonia volatilization losses. Univariate analysis showed that the parameters related to total N losses and rate of volatilization were more affected by soil class and the rate of urea applied. The urease inhibitor affected only the rate and inflection point parameters, decreasing the rate of losses and delaying the beginning of the process, but had no effect on total ammonia losses. Patterns of ammonia volatilization losses provide details on behavior of the variable, details which can be used to develop and adopt more accurate techniques for more efficient use of urea.

Soluble carbon in oxisol under the effect of organic residue rates

The application of organic residues to the soil can increase soluble organic carbon (SOC) and affect the pH and electrolytic conductivity (EC) of the soil. However, the magnitude of these changes depends on the type of residue and the applied dose. This study aimed to evaluate the effect of increasing C rates contained in organic residue on the pH, EC, water-extractable total carbon (WETC), water-extractable organic carbon (WEOC), and water-extractable inorganic carbon (WEIC) in soil treated with manure (chicken, swine, and quail), sawdust, coffee husk, and sewage sludge. The levels of total C (TC- KH2PO4), organic carbon (OC- KH2PO4), and inorganic C (IC- KH2PO4) extractable by a 0.1 mol L-1 KH2PO4 solution were also quantified in soil under the effect of increasing rates of chicken and quail manures. The following rates of organic residue C were applied to a dystrophic Red Latosol (Oxisol) sample: 0, 2,000, 5,000, 10,000, and 20,000 mg kg-1. The addition of organic residues to the soil increased pH, except in the case of sewage sludge, which acidified the soil. The acidity correction potential of chicken and quail manure was highest, dependent on the manure rate applied; regardless of the dose used, sawdust barely alters the soil pH. At all tested rates, the EC of the soil treated with swine manure, coffee husk, and sawdust remained below 2.0 dS m-1, which is a critical level for salinity-sensitive crops. However, the application of chicken or quail manure and sewage sludge at certain rates increased the EC to values above this threshold level. Highest levels of WETC, WEOC, and WEIC were obtained when chicken and quail manure and coffee husk were applied to the Oxisol. The quantities of SOC extracted by KH2PO4 were higher than the quantities extracted by water, demonstrating the ability of soil to adsorb C into its colloids.

Iron oxides and quality of organic matter in sugarcane harvesting systems

Improvements in working conditions, sustainable production, and competitiveness have led to substantial changes in sugarcane harvesting systems. Such changes have altered a number of soil properties, including iron oxides and organic matter, as well as some chemical properties, such as the maximum P adsorption capacity of the soil. The aim of this study was to characterize the relationship between iron oxides and the quality of organic matter in sugarcane harvesting systems. For that purpose, two 1 ha plots in mechanically and manually harvested fields were used to obtain soil samples from the 0.00-0.25 m soil layer at 126 different points. The mineralogical, chemical, and physical results were subjected to descriptive statistical analyses, such as the mean comparison test, as well as to multivariate statistical and principal component analyses. Multivariate tests allowed soil properties to be classified in two different groups according to the harvesting method: manual harvest with the burning of residual cane, and mechanical harvest without burning. The mechanical harvesting system was found to enhance pedoenvironmental conditions, leading to changes in the crystallinity of iron oxides, an increase in the humification of organic matter, and a relative decrease in phosphorus adsorption in this area compared to the manual harvesting system.

Quantification of permanent and variable charges in reference soils of the State of Pernambuco, Brazil

The electrical charges in soil particles are divided into structural or permanent charges and variable charges. Permanent charges develop on the soil particle surface by isomorphic substitution. Variable charges arise from dissociation and association of protons (H+), protonation or deprotonation, and specific adsorption of cations and anions. The aim of this study was to quantify the permanent charges and variable charges of Reference Soils of the State of Pernambuco, Brazil. To do so, 24 subsurface profiles from different regions (nine in the Zona da Mata, eight in the Agreste, and seven in the Sertão) were sampled, representing approximately 80 % of the total area of the state. Measurements were performed using cesium chloride solution. Determination was made of the permanent charges and the charges in regard to the hydroxyl functional groups through selective ion exchange of Cs+ by Li+ and Cs+ by NH4+, respectively. All the soils analyzed exhibited variable cation exchange capacity, with proportions from 0.16 to 0.60 and an average of 0.40 when related to total cation exchange capacity.

Phosphorus availability in oxidic soils treated with lime and silicate applications

Based on the assumption that silicate application can raise soil P availability for crops, the aim of this research was to compare the effect of silicate application on soil P desorption with that of liming, in evaluations based on two extractors and plant growth. The experiment was carried out in randomized blocks with four replications, in a 3 × 3 × 5 factorial design, in which three soil types, three P rates, and four soil acidity correctives were evaluated in 180 experimental plots. Trials were performed in a greenhouse using corn plants in 20-dm³ pots. Three P rates (0, 50 and 150 mg dm-3) were applied in the form of powder triple superphosphate and the soil was incubated for 90 days. After this period, soil samples were collected for routine chemical analysis and P content determination by the extraction methods resin, Mehlich-1 and remaining P. Based on the results, acidity correctives were applied at rates calculated for base saturation increased to 70 %, with subsequent incubation for 60 more days, when P content was determined again. The acidity correctives consisted of: dolomitic lime, steelmaking slag, ladle furnace slag, and wollastonite. Therefore, our results showed that slags raised the soil P content more than lime, suggesting a positive correlation between P and Si in soil. Silicon did not affect the extractor choice since both Mehlich-1 and resin had the same behavior regarding extracted P when silicon was applied to the soil. For all evaluated plant parameters, there was significant interaction between P rates and correctives; highest values were obtained with silicate.

Long-range-interactions induced ordered structures in deposition processes

We present a new model of sequential adsorption in which the adsorbing particles experience dipolar interactions. We show that in the presence of these long-range interactions, highly ordered structures in the adsorbed layer may be induced at low temperatures. The new phenomenology is manifest through significant variations of the pair correlation function and the jamming limit, with respect to the case of noninteracting particles. Our study could be relevant in understanding the adsorption of magnetic colloidal particles in the presence of a magnetic field.

Influence of hydrodynamic interactions on the adsoption process of large particles

We have studied the adsorption process of non-Brownian particles on a line. Our work differs from previously proposed models in that we have incorporated hydrodynamic interactions between the incoming particles and the preadsorbed particles as well as the surface. We then numerically analyze the effect of these interactions on quantities related to the adsorption process. Comparing our model to the ballistic deposition model (BM) shows a significant discrepancy in the pair correlation function. These results can explain some differences between recent experiments and BM predictions. Finally, the limitations of the applicability of BM are addressed.