Ce travail de thèse est consacré à la caractérisation des propriétés mécaniques de l’interphase pâte de ciment-granulat au cours de l’hydratation et au cours de la dégradation chimique par lixiviation. La microstructure de l'interphase entre la pâte de ciment et les granulats est caractérisée par une porosité supérieure à celle de la pâte de ciment. Cette zone constitue un point de fragilité dans le béton et ses propriétés affectent fortement le comportement mécanique du béton à l’échelle macroscopique et à l’échelle de la structure. Dans ce travail, la résistance de l’interphase pâte de ciment-granulat est analysée expérimentalement à l'échelle locale. Des essais expérimentaux sont réalisés sur des composites constitués de granulats liés par une pâte de ciment portland préparée avec un rapport Eau/Ciment de 0,5. Des dispositifs expérimentaux dédiés ont été conçus et réalisés de manière à être adaptés à la taille et à la forme des échantillons. La forme des échantillons utilisés et les outils expérimentaux développés permettent de solliciter directement l’interphase. A différents stades de l'hydratation, des échantillons de pâte de ciment seule et des composites sont soumis à des essais de compression, de traction et de cisaillement direct. L’étude des propriétés mécaniques de l’interphase pâte de ciment-granulat révèle une faiblesse de cette zone en termes de propriétés mécaniques..Le protocole expérimental mis au point a permis d’étudier les effets du mécanisme de lixiviation du calcium au niveau de l’interphase sur les propriétés mécaniques du béton à l’échelle locale. Compte tenu du temps caractéristique long du phénomène de lixiviation, la mise en situation expérimentale au laboratoire est accélérée en remplaçant l’eau par une solution de nitrate d'ammonium. Afin de quantifier le développement et la cinétique de dégradation au niveau de la liaison cimentée, les fronts de lixiviation du béton sont caractérisés à différents degrés de dégradation en utilisant la phénolphtaléine comme traceur. Des essais mécaniques locaux (compression, traction et cisaillement) sont réalisés sur les composites et sur la pâte de ciment à différents temps de dégradation. L’étude de l’effet de la lixiviation à l’échelle locale montre le rôle important de l’interphase pâte de ciment-granulat lors du processus de dégradation chimique sur les propriétés mécaniques du composite. / In this work, we presents an experimental study to characterize the mechanical properties at the local scale of the cement paste-aggregate interface during hydration and during chemical degradation by leaching.It is generally accepted that the microstructure of the interface between the aggregates and the cement paste is characterized by a higher porosity than that of cement paste. This makes this zone a weak point in the concrete. The particular properties of this zone strongly influence the mechanical behavior of concrete. In this work, the mechanical properties of the cement paste-aggregate composite, are experimentally studied. The experimental tests are performed on composites at classical aggregate scale (one centimeter of section). These composite are composed by and Portland cement paste and aggregate. The cement paste is prepared with a water/cement ratio of 0.5. The shape of the prepared composites makes them convenient for direct tensile and shear tests. At different stages of hydration, we performed direct tensile and shear tests on the composites by means of specific devices. The same tests were carried out on the cement paste in order to compare with composites results. The shape of the prepared composites makes them convenient to characterize the cement paste-aggregate interface. At different stages of hydration, the composites are subjected to compression tests, direct tensile tests or shear tests. The study of the mechanical properties of the cement-aggregates interface revealed that the cement paste-aggregate interface is the weakest zone in the composite.An experimental protocol was developed to study the effects of calcium leaching mechanism at the cement paste-aggregate interface on the mechanical properties of the concrete. As the process of leaching with the deionised water occurs very slowly, the experimental study in the laboratory is accelerated by replacing the water by ammonium nitrate solution. To quantify the development and kinetics of degradation at the cemented bond, the concrete leaching fronts are characterized at different levels of degradation by using phenolphthalein. Local mechanical tests (compression, tensile and shear) are performed on composite and cement paste at different stages of degradation. The experimental results show that there is a leaching effect on the alteration of the mechanical properties at the cement paste-aggregate interface.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The tobacco production system in Rio Grande do Sul state is mainly developed in small farms, using shallow soils in steep slope. In these areas rivers are born forming small watersheds. The areas are fragilized by use of inappropriate tillage systems causing soil degradation. To compensate this, new areas are included in the production system, after deforestation and not following environmental legislations rules. In order to maintain yield of the degraded areas is needed high fertilization rates and agrochemical application, following a technology package recommended by tobacco industry. Adding to this the fact, that tobacco has a low efficiency of nutrient use. The objective of this study, was monitored the nitrate concentration of soil solution in several soil management and use and in two domestic well used for drinking water. The study was carried out at Arroio Lino watershed, located in Nova Boemia district of Agudo county, state of Rio Grande do Sul. The area of the watershed presents high steepness and it prevails Entisols and mollisols.The soil solution was extracted with tension lysimeters equipped with ceramic porous cup installed at rooting depth (0,15 or 0,2 m) and below this depth (0,3 or 0,5 m), after the main rains happened during the tobacco cycle.The precipitation data were obtained from an automated meteorological station installed at central part of watershed. In 2004/2005 agricultural year, the nitrate concentration was measured in lysimeters installed in a soil management experiment, in an Entisol, including tobacco no-tillage (NT), minimum tillage (MT) and conventional tillage (CT). In 2005/2006 agricultural year, the nitrate concentration was measured in five transects distributed in several places of the watershed, including tobacco plantation, forest and grass field. Two domestic wells located at lower position of landscape were monitored to nitrate concentration. One of those was located at a position which had above it 15 m stripe of forest and after had tobacco plantation, and the other had no tobacco plantation at position above it. At the points of each transect was evaluated bulk density, soil porosity, saturated hydraulic conductivity and soil water retention curve. The soil tillage systems experiment showed higher value of nitrate concentration after starter fertilization application and decreased along of plant cycle, with content varying from 8 to 226 mg L-1. The highest concentration was observed at MT and lowest at NT. The average nitrate concentration in the rooting zone (0,2 m) was 75 for PD, 95 for MT and 49 mg L-1 for CT. Below the rooting zone, the average was 58 for NT, 108 for MT and 36 mg L-1 for CT. The soil in the transects presented low bulk density, low water storage, high porosity and high saturated hydraulic conductivity. The nitrate reached depths bellow rooting zone and its concentration was higher at tobacco plantation than at forest and grass field, reaching values as high as 80 mg L-1 in tobacco plantation. The well located below tobacco plantation had higher nitrate concentration, overcoming the critical limit of 10 mg L-1 in some periods. / A fumicultura no Rio Grande do Sul é desenvolvida em propriedades familiares em regiões ecologicamente frágeis, com solos rasos e alta declividade. Nessas regiões nascem rios e ocorre a formação de pequenas bacias hidrográficas. As áreas são fragilizadas por sistemas de manejo do solo impróprios para aquelas condições e, para manter a capacidade produtiva, recebem anualmente altas doses de fertilizantes e agrotóxicos, seguindo-se um pacote tecnológico difundido pelas agroindústrias fumageiras, que desconsidera as condições ambientais e os atributos do solo. O objetivo deste trabalho foi monitorar a concentração de nitrato na solução do solo, sob diferentes condições de uso e manejo, e na água de duas fontes usadas para o abastecimento doméstico, e relacioná-las com a influência antrópica. O estudo foi conduzido na microbacia hidrografia do Arroio Lino, localizada no distrito de Nova Boêmia, Agudo-RS. A área da microbacia apresenta alta declividade e nela predominam Neossolos e Chernossolos. A solução do solo foi extraída com lisímetros de tensão com cápsulas porosas na região da zona radicular do fumo (0,15 a 0,20 m) e abaixo dessa (0,30 a 0,50 m), logo após as principais chuvas ocorridas durante o ciclo do fumo. Os dados de precipitação foram obtidos de uma micro-estação meteorológica automatizada instalada na microbacia. Na safra de 2004/2005, os lisímetros foram instalados num experimento, sob Neossolo Litólico, com sistemas de manejo para a implantação da cultura do fumo, sendo monitorado o sistema plantio direto (PD), cultivo mínimo (CM) e preparo convencional (PC). Na safra de 2005/2006, os lisímetros foram instalados em cinco transeções distribuídos na paisagem, abrangendo lavouras de fumo, mata e campo nativo. As duas fontes monitoradas estavam localizadas na encosta, sendo que uma delas apresentava uma faixa de 15 m de mata na sua volta e, acima dessa, era cultivado fumo. A outra fonte estava protegida pela mata e não apresentava influência antrópica nas suas proximidades. Nos pontos de cada transeção, avaliaram-se a densidade do solo, porosidade do solo, condutividade hidráulica saturada e curva de retenção de água. Nos sistemas de manejo do solo os teores de nitrato variaram de 8 a 226 mg L-1 e foram maiores após a adubação de base e decresceram ao longo do ciclo. Os níveis mais altos foram obtidos no CM e os menores no PD. Os teores médios de nitrato na zona radicular foram de 75 no PD, 95 no CM e 49 mg L-1 no PC. Abaixo da zona radicular os teores médios foram de 58 no PD, 108 no CM e 36 mg L-1 de nitrato no PC. O solo nas transeções apresentou baixa densidade, baixa capacidade de armazenamento de água, alta porosidade e alta condutividade hidráulica saturada. O nitrato atingiu profundidades abaixo da zona de exploração radicular (0,5m). Os teores de nitrato foram superiores nas lavouras em relação ao campo e à mata nativa, atingindo 80 mg L-1 nas áreas com fumo. A fonte (poço) que se encontrava abaixo das lavouras de fumo teve maiores concentrações de nitrato, superando o limite crítico de 10 mg L-1 em alguns períodos.

Leaching is one of the major processes occurring when organic litter is decomposed and is often completed within a few days when litter enters aquatic environments. It is important that leaching is addressed when studying microbial and invertebrate decomposition rates in order to avoid overestimations. The traditional litter bag method that has been used to measure decomposition rates in both terrestrial and aquatic environments has in recent years been challenged by the new and widely adopted tea bag index (TBI). Both methods, however, fail to bring a standardized methodology for separating and recognizing weight losses of litter due to leaching and biotic decomposition. Through a field experiment in two streams with different water discharge, this study has focused on exploring the leaching phase and post-leaching phase of the tea products used in TBI. The results unveiled that 20% of rooibos tea’s and 44% of green tea’s initial weight was lost to leaching within three days (72 hours) of the experiment. After the 72nd hour, both teas remained in a stabilized phase until the end of the experiment (120 hours). Water discharge had no significant effect on neither of the tea-weights during or after the leaching phase. This study recommends that weight loss through the leaching phase are taken into account in future studies and advocate the development of an updated TBI protocol where leaching losses are recognized. If not, overestimations of active decomposition rates will be made and may result in compromised conclusions. / Urlakning är en av de viktigaste processerna som uppstår vid nedbrytning av organiskt material och är ofta slutfört inom några dagar när materialet befinner sig i vattenmiljöer. Det är viktigt att den urlakade massan beräknas när studier fokuserade på nedbrytningshastigeter av mikrober och evertebrater genomförs, detta för att undvika en överestimering av den biotiska aktiviteten. Den traditionella metoden, där torkade växtdelar i påsar, har använts för att mäta nedbrytningshastigheter i både mark- och vattenmiljöer har under de senaste åren utmanats av det nya och allmänt accepterade tepåse-indexet (TBI). Båda metoderna misslyckas dock med att implementera en standardiserad metodik för att separera och uppskatta materialets viktförluster genom urlakning och biotisk nedbrytning. Genom ett fältexperiment i två vattendrag med olika vattenföring har denna studie fokuserat på att undersöka urlakningsfasen och den stabiliserade perioden efter urlakningen hos teprodukterna som används i TBI. Resultaten avslöjade att 20% av rooibos tes och 44% av grönt tes ursprungliga vikt förloras genom urlakning inom tre dagar (72 timmar) av experimentet. Efter den 72:a timmen förblev båda teerna i en stabiliserad fas till slutet av experimentet (120 timmar). Vattenflöde hade ingen signifikant effekt på någon av tetypernas vikter, varken för perioden under eller efter urlakningsfasen. Denna studie rekommenderar att viktminskning genom urlakningsfasen beaktas i framtida studier och förespråkar utvecklingen av ett uppdaterat TBI-protokoll för att inkludera urlakningens påverkan. Om inte, kommer överskattningar av aktiva nedbrytningshastigheter att göras och kan leda till äventyrade slutsatser.

Konstgräsplaner kan beaktas som en betydande utsläppskälla av mikroplaster. Fyllnadsmaterialet som används på konstgräsplaner kallas granulat och går under definitionen mikroplast. De som används främst på den svenska marknaden är SBR, TPE, EPDM och R-EPDM. Granulatet sprids främst via dagvattnet från konstgräsplaner som då riskerar att hamna i närliggande vattendrag. Tidigare studier har påvisat att granulatet kan urlaka toxiska ämnen som riskerar att förorena vattendragen. Vattenlevande organismer kan misstolka små partiklar som föda, vilket kan ge konsekvenser som bland annat förstoppning och svält. Ämnena som kan urlaka tillhör samlingsnamnet miljögifter och är stabila, toxiska, reproduktionsstörande och ackumulerande. Syftet med denna studie är att ge en beskrivning av vilka fyllnadsmaterial som används på konstgräsplaner i Gävle och undersöka hur dessa partiklar kan spridas samt identifiera åtgärdsförslag för att minska spridningen. Syftet är också att redovisa konstgräsplanernas dagvattenutlopp och vattendragens status för att redogöra för den potentiella miljöpåverkan som granulatet kan ge upphov till. Metoderna som använts i arbetet är litteraturstudie, personlig kommunikation, fältobservationer, kartsystem och figurer samt vattenprov.   Gavlefastigheter äger fem konstgräsplaner i Gävle kommun, vilka är Träffen IP, Gavlevallen, Nynäs IP, Sörby IP och Andersberg. På dessa planer används SBR- TPE- och R-EPDM-granulat. På planområdet förekommer dagvattenbrunnar och granulatet kan spridas till dessa genom ytavrinning vid höga regnflöden, snöplogning och smältvatten samt att spelarna får med sig partiklarna från planen. De flesta planer har dräneringssystem kopplat till dagvattenledningar som kan sprida urlakande ämnen till vattendrag. Dagvattenledningarna har utlopp i Testeboån, Bäckebrobäcken, Gavleån och Hemlingbybäcken. Granulatets fysikaliska egenskaper är en betydande roll om partikeln sedimenterar till botten eller om den kan transporteras med vattendraget. De konstgräsplaner som främst är i behov av åtgärder för att minska spridningen av granulat är Sörby, Anderberg och Nynäs.   Vattendragens statusklassning uppnår ej god kemisk status och ämnen som förekommer i förhöjda halter varierar beroende på vattendrag. Enligt tidigare studier kan flera av dessa ämnen urlaka från granulatet, vilket innebär att det finns en risk för ett tillskott av dessa ämnen om spridning sker. / Artificial turfs have been shown to be a significant source of microplastics. The filling material used on artificial turf is called granules and are under the definition microplastic. There are different kinds of granules on the Swedish market, these are SBR, TPE, EPDM and R-EPDM. The granules spread mainly through stormwater from artificial turf, which may then end up in nearby streams. Previous studies have shown that the granules can release toxic substances that risk contaminating the water. Aquatic organisms can misinterpret microscopic particles as food, which can cause consequences such as constipation and starvation. The substances that may leach from the granules belongs to the collective name environmental toxins and are stable, toxic, reproductive and accumulative.   The purpose of this study is to provide a description of the filling material that are used in artificial turfs in Gävle, investigate how these granules can spread and then identify suggestions to reduce the spread. The purpose is also to present the artificial turf's stormwateroutlets and water status to describe the potential environmental impact that the granulate may cause. The methods used in this work are literature studies, personal communication, field observations, map systems and figures and water samples.   Gavlefastigheter owns five artificial turfs in the municipality of Gävle which are Träffen IP, Gavlevallen, Nynäs IP, Sörby IP and Andersberg. These turfs use SBR- TPE and R-EPDM granules. There are open water wells on every turf area and granules can spread to these by surface water at intensive rain, snow plowing and meltwater and with the players when they leave the turf. Most turfs have drainage systems connected to stormwater pipelines that can spread leachable substances to water. The water pipelines have outlets in Testeboriver, Bäckebrostream, Gavleriver and Hemlingbystream. The physical properties of the granules have a significant effect if the particle sinks to the bottom or if it is transported along with the water. The artificial turfs that are primarily in need of taking actions to reduce the spread of granules are Sörby, Anderberg and Nynäs.   The waters do not achieve good chemical status and substances that occur at high concentrations varies depending on the kind of water. According to previous studies, several of these substances may leach from the granules which means that there is a risk of a contribution of these substances if spreading occurs.

Due to the increasing usage of Sn in different electronics, such as solders and in touchscreens, together with Boliden Rönnskärs increased intake of electronic waste as a secondaryraw material, a Zn-containing product called Zn-clinker has increasing amounts of Sn. TheZn-clinker is shipped to Boliden Zn-smelter in Odda, where the Zn-clinker is mixed in withcalcine (roasted concentrate) and leached in several steps. Since Zn-clinker is a product froma halogen removal in a clinker-furnace, the feed material (Mixed Oxide), for this furnace, wasalso investigated since there are plans to replace clinkering with soda-washing in the future.Most of the Sn ends up in the leaching residue which then is deposited in the mountaincaverns close by the Boliden Odda smelter. Boliden is studying the possibility to recoverPb/Ag and Sn content from the leaching residue and create a valuable by-product. Bystudying how the leaching of Sn behaves, together with a characterization of the materials, thefollowing question should be answered: “During which sulphuric acid leaching conditions, ofZn-clinker and Mixed Oxide, is the leaching of Sn minimized?” The leaching results for Zn-clinker showed that 8-10% Sn will leach out, despite changingtemperature, redox potential, time and pH. A characterization of the material with SEM-EDSand XRD-analysis was also conducted to see if Sn could be identified in any phases in thematerials. The studies provided enough evidence that Zn2SnO4 could be concluded to be themain phase in the leaching residue for Zn-clinker, a form that would not leach underconditions presented in this project. However, 8-10% of the Sn will come together with Feand when Fe leach out, so does Sn. The leaching results for Mixed Oxide pointed towards that different phases from them foundin Zn-clinker was present. Sn losses varied between 10-20% but raised to 47% whentemperature was changed to 80 °C during leaching. The SEM-EDS analysis showed that theidentified Sn-phases contained more Sn than in Zn-clinker and together with the leachingresults, a conclusion that Sn would mainly be found as SnO2 or SnO in the Mixed Oxide, butthere is still uncertainty about the distributions of these forms. Unfortunately half of the As leached out during the soda-washing for Mixed Oxide, creating aleachate with Cl, F and As that need to be taken care of. This could be challenging andpresenting a costly side-project for the route different from the Zn-clinker route used today.Another observation was that PbCO3 formed during the soda-washing, a phase that willconsume more sulphuric acid during leaching.

Fundação de Amparo a Pesquisa no Estado do Rio Grande do Sul / Technological development and intensive marketing support the growth of demand for electrical and electronic equipment (EEE), which have as a primary component printed circuit boards (PCBs). These devices have become obsolete in a shorter period of time, then residual PCBs become a problem, requiring recycling. The PCBs are composed of ceramic, polymers and metals, especially copper, metal present in the highest percentage. In addition they contain toxic substances such as brominated flame retardants and heavy metals. So the PCBs represent a problem and an opportunity at the same time, they require proper treatment and they are composed for materials with economic value. Therefore the aim of this study was to evaluate the application of supercritical CO2 and co-solvents in the recovery of copper and polymers from mobile phone PCBs, for the development of a more efficient and environmentally friendly recycling process. The study involved the mechanical processing of PCBs separated from discarded mobile phones; the characterization of PCBs; copper recovery using the CO2 supercritical leaching and H2O2 and H2SO4 as cosolvents, this method was conducted comparatively with leaching at atmospheric pressure using H2O2 and H2SO4 as leaching agents; Electrowinning of copper supercritical leached; and recovering the polymer fraction contained in the PCBs, using ethanol as cosolvent. The results indicated that mechanical processing in two milling, carried out in a hammer mill and knives mill were important for the reduction of PCBs to particle diameter less than 2 mm. From the leaching with aqua regia, it was determined that the PCBs containing 34.83 wt% copper. The characterization steps have demonstrated that PCBs are composed of 64.02% of metal, 20.51% of ceramics and 15.47% of polymers. The results showed that the supercritical leaching is 9 times faster than the atmospheric leaching. About 90% of copper was extracted from PCBs in 20 min of supercritical leaching, employing a solid:liquid ratio of 1:20, 20% (v/v) H2O2 and H2SO4 (2.5M). From the electrowinning, performed in a current density of 250 A / m², the copper metal form was recovered with 95.97% purity, reaching a current efficiency of 99%. It was extracted 69.53% of the polymers present in the PCBs using supercritical CO2 and ethanol co-solvent at 170 ° C and 7.5 MPa. Therefore the application of supercritical CO2 and co-solvents is a promising method and efficient to PCBs recycling. / O desenvolvimento tecnológico e marketing intenso propiciam o crescimento da demanda por equipamentos elétricos e eletrônicos (EEE), os quais apresentam como componente primário as placas de circuito impresso (PCIs). Como esses equipamentos vêm se tornando obsoletos em um menor intervalo de tempo, as PCIs residuais tornam-se um problema, necessitando de reciclagem. As PCIs são compostas por cerâmicos, polímeros e metais, com destaque para o cobre, metal presente em maior percentual, além de conterem substâncias tóxicas como os retardantes de chama bromados e os metais pesados. De modo que as PCIs representam um problema e uma oportunidade ao mesmo tempo, pois requerem tratamento adequado e são compostas por materiais com valor econômico agregado. Diante disso, o objetivo deste trabalho foi avaliar a aplicação de CO2 supercrítico na presença de cosolventes para a recuperação do cobre e na remoção dos polímeros de PCIs de celulares, visando o desenvolvimento de um processo de reciclagem mais eficiente e ambientalmente aceitável. O estudo compreendeu o processamento mecânico das PCIs separadas manualmente de celulares descartados; a caracterização das PCIs; a recuperação do cobre a partir da lixiviação com CO2 supercrítico e H2O2 e H2SO4 como cosolventes, realizada de forma comparativa com a lixiviação à pressão atmosférica utilizando H2O2 e H2SO4 como agentes lixiviantes; a eletro-obtenção do cobre lixiviado supercriticamente; e a recuperação da fração polimérica contida nas PCIs, empregando etanol como cosolvente. Os resultados obtidos no processamento mecânico indicaram que as duas moagens, realizadas em moinho de martelos, seguido de facas, foram importantes para a redução das PCIs a partículas de diâmetro inferior a 2 mm. A partir das lixiviações com água régia, determinou-se que as PCIs contêm 34,83% em massa de cobre. As etapas de caracterização demonstraram que as PCIs são compostas por 64,02% de metais, 20,51% de cerâmicos e 15,47% de polímeros. Os resultados mostraram que a lixivação supercrítica é 9 vezes mais rápida do que a lixiviação à pressão atmosférica. Extraiu-se, em 20 minutos de lixiviação supercrítica, cerca de 90% do cobre contido nas PCIs, empregando uma razão sólido:líquido de 1:20, 20% (v/v) de H2O2 e H2SO4 (2,5M). A partir da eletro-obtenção, realizada em uma densidade de corrente de 250 A/m², recuperou-se o cobre na forma de depósito metálico com 95,97% de pureza, alcançando uma eficiência de corrente de 99%. Extraiu-se 69,53% dos polímeros presentes nas PCIs, a partir de CO2 supercrítico modificado com etanol, a 170°C e 7,5 MPa. Portanto a aplicação de CO2 supercrítico na presença de cosolventes é um método promissor e eficiente à reciclagem das PCIs.

Made available in DSpace on 2016-06-02T18:55:26Z (GMT). No. of bitstreams: 1 5571.pdf: 3484455 bytes, checksum: 718ef33aa55e8e1b4e4f22c374cbf1a9 (MD5) Previous issue date: 2013-08-12 / Vinasse is a liquid effluent with a high organic load and it has significant concentrations of Nitrate (NO3 -) and Potassium (K⁺). It is of great interest for the sugarcane sector by reducing costs in fertilizer application. According to the technical regulation P4.231 of CETESB, the impasse in the usage of vinasse in fertigation leads the search toward new alternatives for the effluent usage and treatment. This study investigated the mobility of NO₃ and K⁺ at different depths of Oxisol and the changes in soil electrical conductivity (ECs) in the layer next to the water table. Additionally, this work evaluated whether the rate and period of vinasse application established by the technical regulation P4.231 are appropriate to minimize the risk of soil and groundwater contamination, also evaluate the residual effects of vinasse in soil columns after 6 months monitoring, in order to contribute to the improvement of P4.231. The study was conducted in 15 x 170 cm PVC columns (diameter x height). The column packing was done in order to reproduce the profile of Oxisol, mainly on the thickness and density of the layers collected. Extractors of soil solution were installed at depths of 50 cm and 100 cm from the top of the columns. In the base of the column, a drain was placed at 50 cm to collect the leached. TDR (Time Domain Reflectometer) probes were installed at 120 cm to monitor soil moisture and ECs. After 15 days of saturation with distilled water, the columns received the application of vinasse in nature (V), vinasse in nature subjected to chemical treatment (Q), vinasse in nature subjected to biological treatment (B) and concentrated vinasse (C) at dose calculated by the P4.231 (1) and at duplicated dose calculated (2). The columns were subjected to a simulated rainfall based on the behavior of the rainfall in the region of Araras, SP. After collecting the solution at 50 and 100 cm and leached at 150 cm, determinations of NO3 - contents, by the method of brucine, and K+, by flame photometry, were made every 15 days for 5 months. Significant differences were observed in the levels of NO3 - and K+ in solution attributed to time, depth, type and dose of vinasse. After 45 days of the application of V1, V2, Q1, Q2, B1, B2 vinasses, the NO3 - had leached through the layer until 100 cm. The adsorption of NO3 - , which occurred in the layer until 100 cm, delayed but not prevented ion leaching to a deeper layers than 100 cm, from the 90 days, independent of the type and dose of vinasse. All vinasses, after 105 days, resulted in levels of NO3 - from 3 to 4 times greater than the maximum allowed value for the quality of groundwater (10 mg L-1). At the layer until 50 cm, all the vinasses promoted changes in the K+ solution after 30 days of application, but the application of Q2, C1, C2, and specifically B2, resulted in higher rate of K+ solution. In the layer until 50 cm, a decrease in the levels of K+ in solution was observed from 90 days. Unlike what happened with NO3 -, K+ was absorbed by surface soil layers and its leaching was avoided. Regardless of the type and dose of vinasse, there was an increase in ECs until the 15th week after application, without compromising the quality of the water. The application of vinasses in nature treated chemically and biologically resulted in higher values of ECs. The use of vinasse in nature, at the rate calculated by P4.231, resulted in lower values of NO3 - and K+ in solution, regardless of depth, thus it is recommended that the standard P4.231 should be used only for the application of vinasse in nature. It is suitable to incorporate the levels of NO3 - in the equation in order to calculate the dose of vinasse by P4.231, since the NO3 - had reached the layer at 100 cm in 45 days, i.e., an incompatible period of time with the adequate development of the sugarcane root system, allowing the leaching of NO3 - out of the root zone of influence. In general through the analysis of soil column percolation after 6 months of monitoring, it was possible to verify a residual effect of vinasse, considering all types and doses, in soil samples for the parameters Na+, K+ , and Fe3+. The K+ was retained in the 0 to 50 cm in the percolation columns. Conversely Na+, showed the highest concentrations in the depths of 80-130 cm, showing their greatest potential leaching compared to K+. / A vinhaça é um efluente líquido com alta carga orgânica e que possui importantes concentrações de nitrato (NO₃ ) e de potássio (K+), de grande interesse para o setor sucroenergético por reduzir os custos com a aplicação de fertilizantes. Impasses para o uso da vinhaça na fertirrigação, conforme a Norma Técnica P4.231 da CETESB, levam a busca de novas alternativas de uso e de tratamento do efluente. Este trabalho objetivou estudar a mobilidade de NO₃ e de K+ em diferentes profundidades de um LATOSSOLO VERMELHO Eutrófico (LVe), verificar alterações da condutividade elétrica do solo (CEs) na camada próxima ao lençol freático, avaliar se a taxa e o período de aplicação de vinhaça estabelecidos pela P4.231 estão adequados para a minimização do risco de contaminação do solo e da água subterrânea, avaliar os efeitos residuais da vinhaça no solo das colunas após 6 meses de monitoramento, além de contribuir para o aprimoramento da P4.231. O estudo foi conduzido em colunas de PVC de 150 mm de , por 170 cm de altura. O empacotamento da coluna foi feito de maneira a reproduzir o perfil de 1,5 m de um LVe, principalmente quanto à espessura e à densidade das camadas coletadas. Foram instalados extratores de solução do solo do solo, nas profundidades de 50 cm e de 100 cm a partir do topo das colunas. Na base da coluna, a 150 cm, foi colocado um dreno para coleta do lixiviado. Sondas de TDR foram instaladas a 120 cm para monitoramento da umidade volumétrica e da CEs. Após 15 dias da saturação com água destilada, as colunas receberam a aplicação de vinhaça in natura (V), vinhaça in natura submetida a tratamento químico (Q), vinhaça in natura submetida a tratamento biológico (B) e vinhaça concentrada (C), em doses equivalentes à calculada pela norma P4.231 (1) e ao dobro da calculada (2). As colunas foram submetidas a simulação da chuva com base no comportamento pluviométrico da região de Araras-SP. Após a coleta das soluções, a 50 e a 100 cm, a cada 15 dias, e do lixiviado, a 150 cm, semanalmente, foram feitas determinações dos teores de NO3 -, pelo método da brucina, e de K+, por fotometria de chama, durante 5 meses. Foram observadas diferenças significativas nos teores de NO3 - e de K+ em solução do solo atribuídas ao tempo, à profundidade e ao tipo e dose de vinhaça. Após 45 dias da aplicação de V1, V2, Q1, Q2, B1 e B2, o NO3 - lixiviou para a camada até 100 cm. A adsorção de NO3 -, que ocorreu na camada até 100 cm, retardou mas não impediu a lixiviação do íon para camadas mais profundas do que 100 cm, a partir dos 90 dias, independente do tipo e da dose de vinhaça. Todos os tratamentos com vinhaça, após 105 dias, resultaram em teores de NO3 - 3 a 4 vezes maiores no lixiviado do que o valor máximo permitido para a qualidade das águas subterrâneas (10 mg L-1). Na camada até 50 cm, todos os tratamentos com vinhaça promoveram alterações nos teores de K+ em solução do solo aos 30 dias da aplicação, mas a aplicação de Q2, C1, C2 e, principalmente, de B2, resultaram nos maiores de K+ em solução do solo. Foi observado diminuição dos teores de K+ em solução do solo a partir dos 90 dias na camada até 50 cm. Ao contrário do que aconteceu com o NO3 -, o K+ foi adsorvido nas camadas superficiais e sua lixiviação foi evitada. Independentemente do tipo e da dose da vinhaça, houve aumento da CEs até a 15ª semana após a aplicação, mas sem comprometimento da qualidade da água. A aplicação das vinhaças in natura tratadas química e biologicamente resultaram nos maiores valores de CEs. A utilização de vinhaça in natura, na taxa calculada pela norma P4.231 da CETESB, resultou nos menores valores de NO3 - e de K+ em solução do solo, independentemente da profundidade, desta forma recomenda-se que a norma P4.231 deve ser usada somente para aplicação de vinhaça in natura. É indicada a incorporação dos teores de NO3 - na equação de cálculo da dose de vinhaça da norma P4.231, uma vez que o NO3 - alcançou a camada até 100 cm em 45 dias, ou seja, período de tempo incompatível com o adequado desenvolvimento radicular da cana-de-açúcar e que permite a lixiviação do NO3 - para fora da zona de influência das raízes. Em geral, através das análises de solo das colunas de percolação após 6 meses de monitoramento, pode-se verificar um efeito residual da vinhaça , considerando todos os tipos e doses, nas amostras de solo para os parâmetros Na+, K+, e Fe3+. O K+ ficou retido na camada de 0 a 50 cm das colunas de percolação. De forma contrária, o Na+ apresentou as maiores concentrações nas profundidades de 80 a 130 cm, evidenciando seu maior potencial de lixiviação em relação ao K+.

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CAPES / O uso de coberturas vegetais é uma estratégia fundamental para o manejo de plantas daninhas na região Sul do Brasil. Em áreas com elevadas infestações de plantas daninhas, é crescente a utilização de herbicidas, que aumentam os custos de produção das lavouras e a contaminação ambiental. A aveia preta e a mucuna possuem características contrastantes quanto à velocidade de decomposição dos resíduos e capacidade de mobilização do nitrogênio do solo, proporcionando resultados distintos de supressão de plantas daninhas ao longo do tempo e, portanto, demandando estratégias distintas de manejo antes, durante e após a implantação da cultura do milho. O objetivo geral do experimento foi avaliar a dinâmica ambiental do herbicida atrazina, os resultados sobre o rendimento de grãos do milho e eficiência de controle de plantas daninhas, considerando áreas com distintos históricos de utilização de cobertura morta, distintos níveis de palha e do herbicida. Para isso foram realizadas duas etapas de experimentos: na primeira etapa, foram implantados dois experimentos com a cultura do milho, um com utilização de aveia preta e outro com mucuna preta como espécies de cobertura de solo. O delineamento utilizado em ambos os experimentos a campo foi o de blocos ao acaso, com quatro repetições. O fator A foi constituído de quatro níveis de palha (0, 0,75x, 1,5x e 3x) e o fator B foi constituído por quatro doses do herbicida atrazina (0, 2100, 4200 e 8400 g i.a. ha-1). Amostras de solo foram coletadas para realização de bioensaios em casa de vegetação para avaliação da persistência. A avaliação de lixiviação de atrazina foi efetuada por cromatografia, por meio de amostras coletadas ao longo do perfil do solo.No experimento a campo, avaliou-se a densidade de plantas daninhas, massa da parte aérea verde, massa da parte aérea seca e o rendimento de grãos de milho. Nos bioensaios, as principais variáveis avaliadas foram estatura efitotoxicidade. Na segunda etapa, foram coletados solos com diferentes históricos de cultivo de cultura de cobertura e os estudos de mineralização e sorção, ambos com com 14C-atrazina, foram conduzidos em laboratório. O delineamento utilizado foi inteiramente casualizado, com quatro repetições. Os resultados obtidos a partir do experimento a campo, indicam que o uso de elevados níveis de palha sobre o solo, de forma isolada, não são eficientes para controlar as espécies daninhas e queelevados níveis de palha de mucuna preta sobre o solo reduzem o potencial produtivo do milho. Os bioensaios demonstraram que quantidades elevadas de palha de aveia preta impedem a passagem da atrazina até o solo, sendoa influência do nível de palha sobre a disponibilidade do herbicida detectada até 12 dias após a aplicação. A meia-vida da atrazina aplicada sobre a palha de aveia variou de 7 a 14 dias após a aplicação, enquanto que a meia-vida da atrazina aplicada sobre a palha de mucuna varia de 5 a 14 dias após a aplicação. Níveis crescentes de palha de aveia preta sobre o solo apresentam capacidade de redução da lixiviação de atrazina no perfil, porém esse efeito não foi comprovado com a utilização de palha de mucuna preta, porque o herbicida não foi detectado no perfil do solo, aos 21 dias após a aplicação.As análises cromatográficas indicam que a atrazina se concentra mais próximo à superfície do solo independentemente do volume de palha, não sendo detectada em profundidade superior a 8 cm. A mineralização acumulada da 14C-atrazina aplicada a solos com V. sativa é superior se comparada a solos com S. cereale ou solos com ausência de cultura de cobertura. O coeficiente de sorção da atrazina é superior quando o herbicida é aplicado à palha do que ao solo. / The use of cover crops is a fundamental strategy to the weed management in Southern Brazil. In highly infested areas, the herbicides use is increasing, which increases the costs of the crops production as well as the environmental contamination. Oat and velvet bean plants havecontrasting characteristics regarding to residues decomposition speed and the capacity to immobilize Nitrogen in the soil, providing distinct results of weeds suppression throughout the time, and therefore, requiring distinct management strategies before, during, and after the corn crop establishment. The general objective of the experiment was to evaluate the environmental dynamics of the herbicide atrazine, the corn grain yield, and the efficiency of the weed control, considering areas with distinct history regarding the use of mulching, levels of straw and rates of atrazine. For this, the experiment was carried out in two parts: in the first part, two trials with the corn crop were established, one using oat and the other using velvet bean as cover crops. The experimental design used for both field trials was randomized complete blocks arrangement with four replications. The factor A was constituted by four levels of straw (0; 0.75x; 1.5x; 3x) and the factor B was constituted by four rates of the herbicide atrazine (0; 2100; 4200; 8400 g a i. ha-1). Soil samples were collected for greenhouse trialsto determine the persistence. Atrazine leaching evaluation was performed by chromatography using samples collected over the soil profile.In the field, the weed density, the fresh and dry weight and the yield of the corn were evaluated. In the greenhouse trials, the main variables evaluated were plant height and injury caused by the herbicide toxicity. In the second part, soils with distinct covering history were sampled, and the mineralization and sorption studies, both with 14C-atrazine, were conducted in the laboratory. The experimental design was randomized complete blocks arrangement with four replications. The results from the field experiment show that the high levels of straw above ground, isolated, were not efficient to control completely the weeds, and that high levels of velvet bean`s straw decreased the corn potential yield. The greenhouse trials showed that high levels of oat straw prevent the scape of atrazine to soil, this effect of oat straw upon the herbicide availability on soil was detected up to 12 days after spraying. The half-life of atrazine sprayed over oat straw varied from 7 to 14 days after spraying, while the half-life of atrazine sprayed over velvet bean varied from 5 to 14 days after spraying. Increasing oat straw levels presents the capacity to reduce the lixiviation of atrazine in the soil profile, however, this effect was not verified when using velvet bean straw, because the herbicide was not detected in the soil profile, at 21 days after spraying. The chromatographic analysis indicate thatthe atrazine concentrates closer to the soil surface regardless of amount of straw, not being detected deeper than 8 cm in the soil. The accumulated mineralization of 14C-arazine sprayed over V. sativa is superior if compared to soils with S. cereale or non-covered soils. The sorption coefficient of atrazine is superior when sprayed over straw than over the soil.