Uma das principais consequências dos processos de mineração e beneficiamento do carvão é a elevada produção de rejeitos. Esses materiais retornam às cavas de mineração ocasionando efeitos negativos ao meio ambiente, como a drenagem ácida de mina. Uma alternativa em potencial para esses rejeitos é aplica-los no tratamento de efluentes líquidos como sólidos sorventes. Dentre os principais poluentes aquosos destacam-se os metais pesados e, entre eles, o cromo hexavalente, devido aos seus efeitos carcinogênicos e mutagênicos, sendo altamente prejudicial aos organismos vivos. Neste contexto, o presente trabalho tem como objetivo utilizar o rejeito do beneficiamento do carvão de Moatize (Moçambique) como sólido sorvente para a remoção de cromo hexavalente de águas contaminadas. O sólido foi utilizado em duas granulometrias diferentes: no intervalo entre 0,7 e 1,5 mm (R1) e menor que 0,074 mm (R2). As amostras foram caracterizadas segundo sua massa específica, densidade aparente, área superficial (BET), volume de poros e diâmetro de poros (BJH), ponto de carga zero, composição química (FRX) e mineralógica (DRX). Ensaios experimentais foram realizados a fim de determinar as melhores condições de sorção, onde foram avaliados o efeito do pH, do tempo de residência e da concentração de sorvente As melhores condições encontradas para o sólido R1 foram: pH 2, 10 h de ensaio e concentração de sorvente de 8 g L-1, onde foi obtido 98,6% de remoção de Cr(VI). A maior remoção para o sólido R2 foi de 98,8%, obtida utilizando-se: pH 2, 50 min de ensaio e concentração de sorvente de 10 g L-1. Comparando com o limite previsto pela legislação brasileira CONAMA 430 para despejos industriais as concentrações finais de cromo hexavalente em solução ficaram abaixo do valor máximo estabelecido (0,1 mg L-1). A partir destas condições encontradas, foram construídas isotermas de equilíbrio e os modelos de Langmuir, Freundlich e Sips foram ajustados aos dados experimentais. Para o sólido R1, os modelos de Langmuir e Sips demostraram um bom ajuste, apresentando valores de R2 de 0,897 e 0,907 respectivamente. Já para o sólido R2, o modelo de Sips foi o que melhor representou os dados experimentais, com um R2 de 0,954. Os resultados encontrados indicam que o rejeito de carvão de Moatize pode ser utilizado para o tratamento de águas contaminadas com cromo hexavalente. / One of the main consequences of coal mining and beneficiation process is the large production of waste and by-products. These materials return to the mines generating significant negative impacts to the environment. One of the possible applications for the coal wastes is in the wastewater treatments, where it can be used as a sorbent. Amongst the main water pollutants, heavy metals stand out, especially hexavalent chromium, due to its carcinogenic and mutagenic effects, being highly prejudicial to the living organisms. In this context, the objective of this study is to use coal beneficiation waste from Moatize (Mozambique) as a sorbent to remove hexavalent chromium from aqueous solution. Coal waste was utilized in two different particle sizes: between 0.7 and 1.5 mm and smaller than 0.074 mm. These solids were characterized for their specific weight, bulk density, superficial area (BET), pore volume and diameter (BJH), point of zero charge, chemical composition (XRF) and mineral composition (XRD). Experiments were conducted to determinate the best sorption conditions, were the operating parameters investigated were: solution pH, contact time and sorbent concentration The best conditions for Cr(VI) sorption onto R1 were: pH 2, 10 h and 8 g L-1 of sorbent concentration, were 98.6% removal was obtained. Cr(VI) maximum removal onto R2 of 98.8% was achieved at pH 2, 50 min and 10 g L-1 of sorbent concentration. Comparing with the limit permitted by Brazilian legislation, CONAMA 430, for industrial wastewaters, the final Cr(VI) concentration in water were below the maximum established by law (0.1 mg L-1). From these results, equilibrium isotherms were build and the mathematical models of Langmuir, Freundlich and Sips were fitted to the experimental data. For the R1 sorbent, Langmuir and Sips models fitted better the experiments, with R2 values of 0.897 and 0.907, respectively. Sips model described better the experimental data when the R2 sorbent was used, with a R2 of 0.954. Results showed that Moatize’s coal waste can be utilized for hexavalent chromium wastewater treatment.

Population growth, increasing affluence, and greater access to medicines have led to an increase in active pharmaceutical ingredients (APIs) entering sewerage networks. Wastewater in lower and lower middle-income countries use that use wastewater for irrigation may use untreated or poorly treated wastewater resulting in the potential for greater concentrations of APIs to enter soils in this way. Wastewater re-used for irrigation is currently not included in environmental risk assessments for APIs in soils. The addition of wastewater to soils changes the organic content and can increase the pH of soils, which will have an impact on the fate of any ionisable APIs introduced during the irrigation process. As the input of APIs to soil from wastewater irrigation is not currently included in the risk assessments, this is an area that requires increased attention. A study was undertaken using a modified sorption-desorption batch equilibrium method (OECD 106) to simulate the addition of synthetic wastewater (SWW) to soils compared to a normal OECD 106 study. The APIs studied were ofloxacin, propranolol, naproxen and nevirapine, and represent a range of API physico-chemical properties. These experiments showed that the changes to soil properties (pH and dissolved organic carbon (DOC)) caused by irrigation with SWW can change the fate of APIs in soils. The ionisation state of the API at the altered pH was more important for the positively charged propranolol than it was for the negatively charged naproxen and neutral nevirapine. The Kd and Log Koc increased during the sorption experiment in some cases with SWW. This has implications on the current terrestrial risk assessment where the trigger value for a more detailed soil risk assessment in at Log Koc >4. If the experiment is only performed in 10 mM CaCl2 as is currently required this may lead to unknown risks of APIs in wastewater irrigated soils not being taken into account. Three soil sterilisation or microbial enzyme suppression methods were investigated to identify how successful they were and if there was any impact on the soil physical chemical structure. Gamma irradiation, autoclaving and the addition of 0.2 g L-1 sodium azide were studied. None of the methods successfully sterilised the soils and some changes in soils were identified post-treatment. Autoclaving destroyed the soil structure, turning it into a fine powder and significantly increasing DOC. Sodium azide changed the pH of the loam soil but not the sandy loam soil. Literature suggested that gamma irradiation was the most likely to sterilise the soils with the least amount of disturbance to its physico-chemical properties but increases in DOC were identified in the current study. The changes to soils after sterilisation varied depending on the individual soil properties, indicating that soils should be studied on a case-by-case basis. Irrigation with wastewater provides continuous inputs of chemicals into soils throughout the growing season so it is vital that more work is done to understand the ultimate fate of pollutants in soil as a result. Wastewater has the potential to change the fate of chemicals in soils meaning that current risk assessments may not thoroughly assess all risks involved.

Herbicidas aplicados nos sistemas de cana-de-açúcar, diretamente no solo ou sobre palha, ficam disponíveis a fenômenos de transporte, retenção e transformação. Nesse contexto, o objetivo desse trabalho foiavaliar a lixiviação e sorção de herbicidas residuais em solos com diferentes características físicoquímicas e em palha de cana-de-açúcar. Para tal, foram realizados quatro experimentos. O primeiro relativo à lixiviação, através da metodologia de bioensaios, seguindo o esquema fatorial 8 x 2 x 2, em delineamento inteiramente casualizado, com quatro repetições, sendo oito profundidades do perfil do solo, dois períodos de seca (0 e 30 dias após a aplicação dos tratamentos - DAT) e duas quantidades de palha, esse fatorial foi adotado de forma individual para os herbicidas amicarbazone (1225 g i.a. ha-1 ); imazapic (147 g i.a ha- 1 ), sulfentrazone (800 g i.a ha-1 ) e tebuthiuron (900 g i.a ha-1 ). Os herbicidas foram aplicados no topo de colunas de solo montadas em tubos de PVC com 0 e 10 t ha-1 de palha, esses tratamentos foram submetidos aos três diferentes períodos de seca (0 e 30 DATs), ao final dessas épocas foi realizada uma simulação de chuva de 30 mm e realizada a semeadura de Cucumis sativus (planta bioindicadora), as avaliações de fitoxicidade foram efetuadas aos 7, 10 e 15 dias após a emergencia - DAE, aos 15 DAE foramrealizadas as avaliações de massa seca e altura da parte aérea das plantas. O segundo experimento consistiu na determinação de coeficientes de adsorção e dessorção (Kd e Koc) em 15 solos com diferentes características físico-químicas, para os herbicidas indaziflam, imazapic e amicarbazone. Foi utilizada a metodologia de herbicidas rádio marcados com C14, aplicou-se cinco diferentes concentrações dos herbicidas frios (0,125, 0,25, 0,50, 0,75 e 1,00 ppm), associados aos diferentes solos e herbicidas rádio marcados nas concentrações de 0,24 KBq de indaziflam, 0,26 KBq de imazapic ou 0,20 KBq de amicarbazone, de forma individual em cada unidade experimental. A concentração dos herbicidas rádio marcados presentes no sobrenadante foi determinada por espectroscopia de cintilação líquida (LSS) e por diferença entre a quantidade inicialmente aplicada e a presente na solução do solo, determinando-se adsorção. Através do mesmo processo também foi avaliada a dessorção dos herbicidas em quatro dias de análise. O terceiro experimento avaliou a adsorção de indaziflam, imazapic e amicarbazone em palha de cana-de-açúcar. Um estudo típico e equilíbrio em lotes foi conduzido para determinar adsorção e dessorção em diferentes concentrações dos herbicidas. A palha de cana-de-açúcar (0,27 g) foi combinada com três concentrações dos herbicidas (0,125, 0,5 e 1 ppm) mais os herbicidas radiomarcados nas seguintes quantidades: 0,24 KBq de indaziflam, 0,26 KBq imazapic e 0,20 KBq de amicarbazone. Após o estabelecimento do equilíbrio que foi de 24 horas para os três herbicidas, foi determinada a quantidade de herbicida adsorvida na palha de cana-de-açucar. Após a analise da adsorção, a solução presente nas unidades experimentais foi descartada e reposta por uma solução de cloreto de cálcio, e a dessorção foi então analisada após 24 horas, durante o período de um dia para amicarbazone, cinco dias para indaziflam, e não foi realizada analise de dessorção para o herbicida imazapic.Um quarto experimento, abordou a intercepção de herbicidas pela palha de cana-de-açúcar mediante a simulação de chuvas em diferentes precipitações (3, 6, 12 e 24 mm). Os herbicidas foram aplicados em duas quantidades de palha de cana-de-açúcar, as quais foram espalhadas de forma uniforme sobre uma tela de aço inoxidável (5 t ha-1 e 10 t ha-1), em seguida, essa tela foi colocada sobre um recipiente de vidro. As simulações de chuva ocorreram aos 0 horas, 24 horas e sete dias após a aplicação dos tratamentos. Para o herbicida amicarbazone aos 0 DAT sem palha, a lixiviação do herbicida amicarbazone foi notada ate os 25 cm, sendo os efeitos fitotoxicos mais expressivos observados nos primeiros 15 cm, já nas aplicações de 30 DAT, nos tratamentos com palha e sem palha a lixiviação foi notada até os 10 cm, com maior fitotoxicidade nos primeiros 5 cm. Na lixiviação tebuthiuron e imazapic e sulfentrazone a permanência do produto sobre a palha de cana-de-açúcar durante 30 DAT tornou a lixiviação desses herbicidas menor. Para o herbicida sulfentrazone a presença de palha imapctou de maneira mais expressiva na lixiviação desse herbicida que o perido de seca. Para imazapic e amicarbazone, os valores de Kd foram baixos devido à sua alta solubilidade em água; no entanto, a adsorção de imazapic foi fortemente influenciada pelo pH do solo, e para amicarbazone a adsorção e dessorção foi influenciada pela matéria orgânica e pH dos solos. Para indaziflam, Kd foi correlacionado negativamente com o teor de argila, mas foi positivamente correlacionado com a matéria orgânica. A adsorção de indaziflam foi superior a 80% em todas as concentrações, enquanto que a adsorção imazapic foi inferior a 7% em todas as concentrações. A adsorção de amicarbazone foi inferior a 20% em todas as concentrações. A dessorção de indaziflam foi de 30%, 28,5% e 27,5% a 0,125, 0,5 e 1 ppm, respectivamente, após 5 dias. A dessorção máxima para amicarbazone foi observada a 1 ppm com 11%. Para o indaziflam, após um período de sete dias após a aplicação dos herbicidas sobre a palha de cana-de-açúcar simulou-se uma precipitação de 24 mm resultando na remoção de apenas 25% do herbicida interceptado. Para o herbicida imazapic a palha de cana-de-açúcar não apresentou uma barreira de expressiva para interceptação desse produto. Dessa forma, as características dos herbicidas, como a solubilidade em água e Kow, podem ser utilizadas para determinar a sua dinâmica em sistemas de produção de cana-de-açúcar, sendo que os atributos lixiviação, sorção em palha e em solo, podem direcionar a uma predileção do comportamento agronômico e destino ambiental de herbicidas residuais. Dessa forma, pode-se concluir que a presença de palha na superfície do solo atrelada aos diferentes períodos de seca pode afetar a mobilidade desses herbicidas no ambiente. Conclui-se que as cracteristicas físico-quimicas dos herbicidas associadas com os atributos do solo podem direcionar a dinâmica de adsorção e dessorção dos herbicidas. As características dos herbicidas, como a solubilidade em água e Kow, podem ser utilizadas para determinar a dificuldade de remoção dos herbicidas em palha de cana-de-açucar. / Herbicides applied to sugar cane systems, directly on the soils our by residues, are available to transport, retention and transformation phenomenon. In this context, the objective of this work was to evaluate the leaching and sorption of residual herbicides in soils with different physicochemical characteristics and in sugarcane residues. Four experiments were carried out. The first, was based on the bioassay methodology, followed the 8 x 2 x 2 factorial scheme, in a completely randomized design, with four replications, eight depths of the soil profile, two dry periods (0 and 30 days after application of the treatments (DAT) and two quantities of residues, this factorial was adopted individually for the herbicides amicarbazone (1225 g ia ha-1); imazapic (147 g i.a ha-1), sulfentrazone (800 g i.a ha-1) and tebuthiuron (900 g i.a ha-1). The herbicides were applied to the top of soil columns mounted in PVC tubes with 0 and 10 t ha-1 of straw, these treatments were submitted to the three different periods of dry (0 and 30 DATs), at the end of those times a 30 mm rainfall simulation and Cucumis sativus sowing (bioindicator plant), phytotoxicity (7, 10 and 15 DAE), dry mass and shoot height were evaluated. It was noted that the greatest phytotoxicity of the herbicide amicarbazone was in the 0-5 cm layer. And that periods of drought and straw decreased the mobility of this herbicide in the columns. In leaching tebuthiuron, imazapic and sulfentrazone the permanence of the product on the sugarcane straw during 30 DAT made the leaching of this herbicide minor. Thus, it can be concluded that the presence of straw on the soil surface coupled to the different periods of drought can affect the mobility of these herbicides in the environment. The second experiment consisted in the determination of coeficivity of adosorption and desorption (Kd and Koc) in 16 soils with different physicochemical characteristics, for the herbicides indaziflam, imazapic and amicarbazone. The C14- labeled radio-herbicide methodology was used to apply five different concentrations of the cold herbicides (0.125, 0.25, 0.50, 0.75 and 1.00 ppm), associated with the different soils and herbicides radio -marked at the concentrations of 0.24 KBq of indaziflam, 0.26 KBq of imazapic or 0.20 KBq of amicarbazone, individually in each experimental unit. The concentration of radiolabelled herbicides present in the supernatant was determined by liquid scintillation spectroscopy (LSS) and by difference between the amount initially applied and the present in the soil solution, determining adsorption. Through the same process the herbicide desorption was also evaluated in four days of analysis For imazapic and amicarbazone, Kd values were low due to their high solubility in water; however, the adsorption of imazapic was strongly influenced by the pH of the soil, and for amicarbazone the adsorption and desorption was influenced by the organic matter and pH of the soils. For indaziflam, Kd was negatively correlated with clay content but was positively correlated with organic matter. The third experiment evaluated the adsorption of indaziflam, imazapic and amicarbazone in sugarcane straw. A typical study and batch equilibrium was conducted to determine adsorption and desorption at different concentrations of the herbicides. Sugarcane residues (0.27 g) was combined with three concentrations of the herbicides (0.125, 0.5 and 1 ppm) plus 0.24 KBq of indaziflam, 0.26 KBq imazapic or 0.20 KBq of labeled amicarbazone radio. The adsorption of indaziflam, imazapic and amicarbazone was evaluated 24, 48 and 120 hours, respectively, after the contact of sugarcane residues. Indaziflam adsorption was greater than 80% at all concentrations, while imazapic adsorption was below 7% at all concentrations. The adsorption of amicarbazone was less than 20% at all concentrations. Indaziflam desorption was 30%, 28.5% and 27.5% at 0.125, 0.5 and 1 ppm, respectively, after 5 days. Maximum desorption for amicarbazone was observed at 1 ppm with 11%. The desorption for imazapic was not determined due to the low initial adsorption. A fourth experiment, addressed the interception of herbicides by sugarcane straw through simulated rainfall in various amounts of precipitation (3, 6, 12 and 24 mm). Two amounts of sugarcane straw were uniformly spread over a stainless steel screen (5 t ha-1 and 10 t ha-1), then the screen was placed on a Pyrex® pan. The rain simulations occurred at 0 hr, 24 hrs and seven days after the treatments were applied. For indaziflam, a period of seven days after application of the herbicides on the sugarcane straw was simulated a precipitation of 24 mm resulting in the removal of only 25% of the adsorbed herbicide. For the herbicide imazapic the sugarcane straw did not present an expressive barrier to interception of this product. Thus, the characteristics of the herbicides, such as water solubility and Kow, can be used to determine their dynamics in sugarcane production systems, and the leaching, straw sorption and soil attributes can a predilection for agronomic behavior and environmental fate of residual herbicides.

As indústrias de papel e celulose geram enormes quantidades de cinzas de caldeira todos os anos. A disposição final dessas cinzas em aterros costumava ser prática comum, porém a sua utilização em solos florestais e agrícolas merece consideração devido ao seu potencial de corrigir a acidez e de fertilizar os solos, minimizando assim a pressão sobre sua forma de descarte no ambiente. No entanto, o uso desse resíduo pode afetar diretamente a dinâmica de pesticidas no solo, além de adicionar metais pesados. Desta forma, o presente trabalho avaliou o efeito de três cinzas de biomassa florestal (C-1, C-11 e C-27) na fertilidade e na sorção do herbicida imazetapir em três solos com atributos físico-químicos distintos (RQd, LVd e LVAd). Além das três cinzas, calcário e o controle compuseram os tratamentos, os quais foram incubados por três meses. Posteriormente, estudos de sorção do herbicida imazetapir foram realizados nos diferentes tratamentos. As cinzas C-11 e C-27 aumentarem o valor do pH dos solos e os teores de macroelementos, mas reduziram os teores de microelementos catiônicos. A C-1 mostrou ser boa fonte de K para os solos. Nenhuma cinza mostrou-se limitante quanto ao teor de metais pesados. De forma geral, o imazetapir apresentou baixo potencial de sorção nos solos e seus respectivos tratamentos (Kd < 1,8 L kg-1). A C-11 e a C-27 reduziram enquanto que a C-1 aumentou o potencial de sorção do imazetapir nos solos, o que foi devido às alterações nos valores de pH do solo. A sorção foi ligeiramente maior no solo com maiores teores de argila e carbono orgânico (LVd), enquanto a dessorção foi maior no solo de teores intermediários (LVAd). Houve histerese em todos os solos, sugerindo irreversibilidade de parte do herbicida sorvido. / The pulp and paper industries generate huge amounts of wood ash every year. The ashes disposals in landfills used to be a common practice, but their use in agricultural and forest soils deserves special attention due to their potential to neutralize acidity and to fertilize soils, thus decreasing pressure about their environmental disposal. However, the use of this residue may directly impact the dynamic of pesticides as well as add heavy metals to the soils. Therefore, this study evaluated the effects of three wood ashes (C-1 , C-11, and C-27 ) in the fertility and sorption of imazethapyr in three soils (RQd, LVd, LVAd), with contrasting physical-chemical attributes. Besides the ashes, lime and control treatments were added, all of them incubated for three months. Afterwards, batch sorption isotherms for imazethapyr were performed for all treatments. The C-11 and C-27 enhanced soil-pH and macroelement contents, but decreased cationic microelement contents. The C-1 was a good source of K to the soils. There is little risk of contamination by heavy metals. Overall, imazethapyr sorption was low in all soils and their respective treatments (Kd < 1,8 L kg-1). The C-11 and the C-27 decreased whereas C-1 enhanced sorption of imazethapyr to the soils, most likely due to changes in soil-pH. Sorption was slightly higher in the soil with higher clay and organic carbon contents (LVd) whereas desorption was higher in the soil with intermediate values (LVAd). There was hysteresis, suggesting irreversibility during sorption/desorption processes.

Herbicidas aplicados nos sistemas de cana-de-açúcar, diretamente no solo ou sobre palha, ficam disponíveis a fenômenos de transporte, retenção e transformação. Nesse contexto, o objetivo desse trabalho foiavaliar a lixiviação e sorção de herbicidas residuais em solos com diferentes características físicoquímicas e em palha de cana-de-açúcar. Para tal, foram realizados quatro experimentos. O primeiro relativo à lixiviação, através da metodologia de bioensaios, seguindo o esquema fatorial 8 x 2 x 2, em delineamento inteiramente casualizado, com quatro repetições, sendo oito profundidades do perfil do solo, dois períodos de seca (0 e 30 dias após a aplicação dos tratamentos - DAT) e duas quantidades de palha, esse fatorial foi adotado de forma individual para os herbicidas amicarbazone (1225 g i.a. ha-1 ); imazapic (147 g i.a ha- 1 ), sulfentrazone (800 g i.a ha-1 ) e tebuthiuron (900 g i.a ha-1 ). Os herbicidas foram aplicados no topo de colunas de solo montadas em tubos de PVC com 0 e 10 t ha-1 de palha, esses tratamentos foram submetidos aos três diferentes períodos de seca (0 e 30 DATs), ao final dessas épocas foi realizada uma simulação de chuva de 30 mm e realizada a semeadura de Cucumis sativus (planta bioindicadora), as avaliações de fitoxicidade foram efetuadas aos 7, 10 e 15 dias após a emergencia - DAE, aos 15 DAE foramrealizadas as avaliações de massa seca e altura da parte aérea das plantas. O segundo experimento consistiu na determinação de coeficientes de adsorção e dessorção (Kd e Koc) em 15 solos com diferentes características físico-químicas, para os herbicidas indaziflam, imazapic e amicarbazone. Foi utilizada a metodologia de herbicidas rádio marcados com C14, aplicou-se cinco diferentes concentrações dos herbicidas frios (0,125, 0,25, 0,50, 0,75 e 1,00 ppm), associados aos diferentes solos e herbicidas rádio marcados nas concentrações de 0,24 KBq de indaziflam, 0,26 KBq de imazapic ou 0,20 KBq de amicarbazone, de forma individual em cada unidade experimental. A concentração dos herbicidas rádio marcados presentes no sobrenadante foi determinada por espectroscopia de cintilação líquida (LSS) e por diferença entre a quantidade inicialmente aplicada e a presente na solução do solo, determinando-se adsorção. Através do mesmo processo também foi avaliada a dessorção dos herbicidas em quatro dias de análise. O terceiro experimento avaliou a adsorção de indaziflam, imazapic e amicarbazone em palha de cana-de-açúcar. Um estudo típico e equilíbrio em lotes foi conduzido para determinar adsorção e dessorção em diferentes concentrações dos herbicidas. A palha de cana-de-açúcar (0,27 g) foi combinada com três concentrações dos herbicidas (0,125, 0,5 e 1 ppm) mais os herbicidas radiomarcados nas seguintes quantidades: 0,24 KBq de indaziflam, 0,26 KBq imazapic e 0,20 KBq de amicarbazone. Após o estabelecimento do equilíbrio que foi de 24 horas para os três herbicidas, foi determinada a quantidade de herbicida adsorvida na palha de cana-de-açucar. Após a analise da adsorção, a solução presente nas unidades experimentais foi descartada e reposta por uma solução de cloreto de cálcio, e a dessorção foi então analisada após 24 horas, durante o período de um dia para amicarbazone, cinco dias para indaziflam, e não foi realizada analise de dessorção para o herbicida imazapic.Um quarto experimento, abordou a intercepção de herbicidas pela palha de cana-de-açúcar mediante a simulação de chuvas em diferentes precipitações (3, 6, 12 e 24 mm). Os herbicidas foram aplicados em duas quantidades de palha de cana-de-açúcar, as quais foram espalhadas de forma uniforme sobre uma tela de aço inoxidável (5 t ha-1 e 10 t ha-1), em seguida, essa tela foi colocada sobre um recipiente de vidro. As simulações de chuva ocorreram aos 0 horas, 24 horas e sete dias após a aplicação dos tratamentos. Para o herbicida amicarbazone aos 0 DAT sem palha, a lixiviação do herbicida amicarbazone foi notada ate os 25 cm, sendo os efeitos fitotoxicos mais expressivos observados nos primeiros 15 cm, já nas aplicações de 30 DAT, nos tratamentos com palha e sem palha a lixiviação foi notada até os 10 cm, com maior fitotoxicidade nos primeiros 5 cm. Na lixiviação tebuthiuron e imazapic e sulfentrazone a permanência do produto sobre a palha de cana-de-açúcar durante 30 DAT tornou a lixiviação desses herbicidas menor. Para o herbicida sulfentrazone a presença de palha imapctou de maneira mais expressiva na lixiviação desse herbicida que o perido de seca. Para imazapic e amicarbazone, os valores de Kd foram baixos devido à sua alta solubilidade em água; no entanto, a adsorção de imazapic foi fortemente influenciada pelo pH do solo, e para amicarbazone a adsorção e dessorção foi influenciada pela matéria orgânica e pH dos solos. Para indaziflam, Kd foi correlacionado negativamente com o teor de argila, mas foi positivamente correlacionado com a matéria orgânica. A adsorção de indaziflam foi superior a 80% em todas as concentrações, enquanto que a adsorção imazapic foi inferior a 7% em todas as concentrações. A adsorção de amicarbazone foi inferior a 20% em todas as concentrações. A dessorção de indaziflam foi de 30%, 28,5% e 27,5% a 0,125, 0,5 e 1 ppm, respectivamente, após 5 dias. A dessorção máxima para amicarbazone foi observada a 1 ppm com 11%. Para o indaziflam, após um período de sete dias após a aplicação dos herbicidas sobre a palha de cana-de-açúcar simulou-se uma precipitação de 24 mm resultando na remoção de apenas 25% do herbicida interceptado. Para o herbicida imazapic a palha de cana-de-açúcar não apresentou uma barreira de expressiva para interceptação desse produto. Dessa forma, as características dos herbicidas, como a solubilidade em água e Kow, podem ser utilizadas para determinar a sua dinâmica em sistemas de produção de cana-de-açúcar, sendo que os atributos lixiviação, sorção em palha e em solo, podem direcionar a uma predileção do comportamento agronômico e destino ambiental de herbicidas residuais. Dessa forma, pode-se concluir que a presença de palha na superfície do solo atrelada aos diferentes períodos de seca pode afetar a mobilidade desses herbicidas no ambiente. Conclui-se que as cracteristicas físico-quimicas dos herbicidas associadas com os atributos do solo podem direcionar a dinâmica de adsorção e dessorção dos herbicidas. As características dos herbicidas, como a solubilidade em água e Kow, podem ser utilizadas para determinar a dificuldade de remoção dos herbicidas em palha de cana-de-açucar. / Herbicides applied to sugar cane systems, directly on the soils our by residues, are available to transport, retention and transformation phenomenon. In this context, the objective of this work was to evaluate the leaching and sorption of residual herbicides in soils with different physicochemical characteristics and in sugarcane residues. Four experiments were carried out. The first, was based on the bioassay methodology, followed the 8 x 2 x 2 factorial scheme, in a completely randomized design, with four replications, eight depths of the soil profile, two dry periods (0 and 30 days after application of the treatments (DAT) and two quantities of residues, this factorial was adopted individually for the herbicides amicarbazone (1225 g ia ha-1); imazapic (147 g i.a ha-1), sulfentrazone (800 g i.a ha-1) and tebuthiuron (900 g i.a ha-1). The herbicides were applied to the top of soil columns mounted in PVC tubes with 0 and 10 t ha-1 of straw, these treatments were submitted to the three different periods of dry (0 and 30 DATs), at the end of those times a 30 mm rainfall simulation and Cucumis sativus sowing (bioindicator plant), phytotoxicity (7, 10 and 15 DAE), dry mass and shoot height were evaluated. It was noted that the greatest phytotoxicity of the herbicide amicarbazone was in the 0-5 cm layer. And that periods of drought and straw decreased the mobility of this herbicide in the columns. In leaching tebuthiuron, imazapic and sulfentrazone the permanence of the product on the sugarcane straw during 30 DAT made the leaching of this herbicide minor. Thus, it can be concluded that the presence of straw on the soil surface coupled to the different periods of drought can affect the mobility of these herbicides in the environment. The second experiment consisted in the determination of coeficivity of adosorption and desorption (Kd and Koc) in 16 soils with different physicochemical characteristics, for the herbicides indaziflam, imazapic and amicarbazone. The C14- labeled radio-herbicide methodology was used to apply five different concentrations of the cold herbicides (0.125, 0.25, 0.50, 0.75 and 1.00 ppm), associated with the different soils and herbicides radio -marked at the concentrations of 0.24 KBq of indaziflam, 0.26 KBq of imazapic or 0.20 KBq of amicarbazone, individually in each experimental unit. The concentration of radiolabelled herbicides present in the supernatant was determined by liquid scintillation spectroscopy (LSS) and by difference between the amount initially applied and the present in the soil solution, determining adsorption. Through the same process the herbicide desorption was also evaluated in four days of analysis For imazapic and amicarbazone, Kd values were low due to their high solubility in water; however, the adsorption of imazapic was strongly influenced by the pH of the soil, and for amicarbazone the adsorption and desorption was influenced by the organic matter and pH of the soils. For indaziflam, Kd was negatively correlated with clay content but was positively correlated with organic matter. The third experiment evaluated the adsorption of indaziflam, imazapic and amicarbazone in sugarcane straw. A typical study and batch equilibrium was conducted to determine adsorption and desorption at different concentrations of the herbicides. Sugarcane residues (0.27 g) was combined with three concentrations of the herbicides (0.125, 0.5 and 1 ppm) plus 0.24 KBq of indaziflam, 0.26 KBq imazapic or 0.20 KBq of labeled amicarbazone radio. The adsorption of indaziflam, imazapic and amicarbazone was evaluated 24, 48 and 120 hours, respectively, after the contact of sugarcane residues. Indaziflam adsorption was greater than 80% at all concentrations, while imazapic adsorption was below 7% at all concentrations. The adsorption of amicarbazone was less than 20% at all concentrations. Indaziflam desorption was 30%, 28.5% and 27.5% at 0.125, 0.5 and 1 ppm, respectively, after 5 days. Maximum desorption for amicarbazone was observed at 1 ppm with 11%. The desorption for imazapic was not determined due to the low initial adsorption. A fourth experiment, addressed the interception of herbicides by sugarcane straw through simulated rainfall in various amounts of precipitation (3, 6, 12 and 24 mm). Two amounts of sugarcane straw were uniformly spread over a stainless steel screen (5 t ha-1 and 10 t ha-1), then the screen was placed on a Pyrex&reg; pan. The rain simulations occurred at 0 hr, 24 hrs and seven days after the treatments were applied. For indaziflam, a period of seven days after application of the herbicides on the sugarcane straw was simulated a precipitation of 24 mm resulting in the removal of only 25% of the adsorbed herbicide. For the herbicide imazapic the sugarcane straw did not present an expressive barrier to interception of this product. Thus, the characteristics of the herbicides, such as water solubility and Kow, can be used to determine their dynamics in sugarcane production systems, and the leaching, straw sorption and soil attributes can a predilection for agronomic behavior and environmental fate of residual herbicides.

Dans le contexte des futurs stockages des matières nucléaires en couches géologiques profondes, le transfert desélénium 79 des eaux de nappes vers la biosphère, par le biais de l'irrigation, est un des scenarii envisagés parl'ANDRA. Le sol servirait alors d'interface entre la géosphère et la biosphère.Le modèle actuellement utilisé pour évaluer la mobilité de nombreux éléments dans le sol repose sur une représentationsimple de leur distribution entre la quantité adsorbée sur le sol et la quantité restante en solution (modèleKd), considérée comme instantanée, réversible et linéaire avec la concentration de contamination. Ce modèleprésente des lacunes vis-à-vis du sélénium puisque ce dernier peut être présent sous différents états redoxqui contrôlent sa mobilité et dont les cinétiques de transformation entre ces états sont peu connues (Se(-II), Se(0),Se(IV) et Se(VI)).Dans le but d'améliorer les prédictions faites sur la mobilité du sélénium dans un sol, le séléniate (Se(VI)), qui estla forme la plus mobile, a été utilisé pour étudier ses interactions vis-à-vis de deux sols différents (sol B et sol R).Un modèle cinétique, alternatif au modèle Kd, a été développé pour décrire l'évolution des stocks de Se(VI) ensolution, en considérant une fraction de sélénium associée au sol de façon réversible (potentiellement mobile) etune fraction stabilisée sur le sol (fixée pseudo-irréversiblement). Ce modèle intègre des cinétiques de stabilisationbiotique et abiotique sur le sol, et une cinétique de réduction en solution.Afin d'acquérir les paramètres des modèles, des expériences en batchs et en réacteurs à flux ouvert avecl'utilisation de sacs à dialyse ont été réalisées. L'acquisition des paramètres a permis de confronter les modèlescinétiques et Kd dans différents scenarii réalistes de contamination (chronique ou séquentielle) d'un sol de surfacepar du 79Se(VI).De plus, les mécanismes de sorption du Se(VI) au sein des deux sols ont été évalués en batch avec l'ajout de compétiteursspécifiques vis-à-vis de certains sites pouvant sorber ce dernier (acides humiques et carbonates de calcium).Ceci a été complété avec l'étude de la sorption du Se(VI) sur des phases pures commerciales (silice, hydroxyded'aluminium, goethite, bentonite, carbonate de calcium et acides humiques) ou extraites d'un sol (substanceshumiques), pour différentes concentrations en Se(VI) (10-8, 10-6 et/ou 10-3 mol/L), de l'impact de l'ajout dephases pures réactives, dans les sols, sur la sorption du Se(VI).Il a été montré que le Se(VI) était sorbé sous la forme de complexes de sphères externes (CSE) au sein du sol Rpour des concentrations inférieures à 10-6 mol/L, tandis que dans le sol B, la majorité était sorbée sous la formesde complexes de sphère internes (CSI). La formation de CSE étant réversible et instantanée, l'utilisation du modèleKd était donc suffisante pour décrire la sorption du Se(VI) au sein du sol R, dans les expériences en réacteursà flux ouvert.A contrario, pour le sol B, il a été montré que le modèle Kd, contrairement au modèle cinétique, présentait deslacunes pour décrire la sorption pseudo-irréversible du Se(VI), engendrée par la formation de CSI.Il a été montré que les mécanismes biotiques étaient majoritaires au sein du sol B, en raison de l'apport de nutrimentspour les microorganismes, par l'utilisation de sacs à dialyse en cellulose régénérée. Cependant les mécanismesabiotiques ont aussi eu lieux au sein du sol B.14/256Les études sur les phases pures ont montré que seuls l'hydroxyde d'aluminium (pH 5,2 et 8) et la goethite (pH 5,2)pouvaient sorber le Se(VI) respectivement de manière pseudo-irréversible et réversible (pour [Se(VI)] < 10-6mol/L).Enfin, il a été montré que l'ajout de certaines phases pures (goethite et hydroxyde d'aluminium) au sein des deuxsols, pouvait entrainer une augmentation ou une diminution de la sorption du Se(VI) par rapport à celle attendue(additivité réactionnelle). Les interactions solide/solide directes et/ou indirectes, (la plus connue étant le coating)peuvent être à l'origine de la difficulté d'évaluation, de manière générique, de la sorption du Se(VI) au sein dusol, connaissant seulement sa composition élémentaire.

Le fil conducteur des recherches que j'ai effectuées depuis 1995 est la compréhension de la réactivité de surface des oxy-hydroxydes métalliques et de son implication dans les processus de sorption et d'adhésion. J'ai débuté ces recherches par une thèse sur l'étude des interactions des ions iodure avec plusieurs composés du cuivre (oxydes, carbonates et sulfures) par des méthodes spectroscopiques (XPS, Raman) et électrochimiques pour caractériser les composés formés. L'application de ces recherches au stockage souterrain des déchets radioactifs (l'iode étant un vecteur potentiel de contamination) a justifié leur financement par l'ANDRA. Ces premiers travaux m'ont dévoilé l'étendue des études nécessaires à l'avancée des connaissances dans le domaine des interfaces oxydes/solution. Mon embauche au CNRS m'a permis de mettre en œuvre un programme de recherche basé sur une approche multiéchelle (des colloïdes aux substrats massifs) et multitechnique (caractérisation en masse et en surface). Dans une première étape, j'ai utilisé des solides de référence pour améliorer les méthodes de caractérisation acido-basiques et les modèles de complexation de surface. La plate-forme expérimentale du CECM, laboratoire spécialisé dans les matériaux, a permis de réaliser une caractérisation approfondie des solides, au-delà des analyses réalisées habituellement par des chercheurs n'ayant pas un accès direct à ces moyens analytiques (MET, XRD, ATG, XPS,...). J'ai ainsi mis en évidence l'instabilité de la surface de l'alumine gamma en solution, alors que ce composé était utilisé depuis plusieurs dizaines d'années comme un solide de référence. Aidé d'un stagiaire, j'ai synthétisé un hydroxyde d'aluminium (bayerite) avec différentes morphologies pour prendre en compte la cristallographie sur la réactivité de surface, en accord avec les modèles les plus récents. La sorption des anions reste une problématique importante pour le stockage souterrain des déchets radioactifs puisqu'ils seraient les principaux vecteurs de contamination dans la géosphère. Avec une doctorante, nous avons travaillé sur le système sélénite/hématite pour aboutir à la publication de la première étude approfondie sur la sorption de cette espèce anionique du sélénium sur ce minéral. A cette occasion, la nécessité de disposer d'informations spectroscopiques en présence de solution m'a conduit à développer un système permettant de réaliser des spectres infrarouges en mode ATR (réflexion totale atténuée). J'ai ainsi analysé plusieurs systèmes (sulfate, carbonate, uranyle/hématite, uranyle/rutile,...) pour lesquels j'ai obtenu la spéciation des espèces sorbées, notamment en distinguant les complexes de sphère interne et externe. Ces expériences m'ont permis de publier la première étude française avec ce moyen d'investigation de la sorption. Ces études ont été suivies par un séjour de près d'un an à EDF R&D, résultat de la volonté de cette entreprise de développer ses activités de recherche sur la réactivité des produits de corrosion colloïdaux dans les circuits de refroidissement des réacteurs à eau pressurisée (REP), et de mon souhait de renforcer ma connaissance du milieu industriel et de la recherche finalisée. De retour dans un laboratoire CNRS, j'ai appliqué mes compétences sur la sorption aux phénomènes d'adhésion, de la mise en place d'essais en laboratoire jusqu'à l'analyse des retours d'expérience des centrales nucléaires. De manière étonnante, les interactions entre particules colloïdales et matériaux de structure ont fait l'objet de peu d'études, à l'inverse des systèmes modèles (latex/verre, mica,...) dont les conditions expérimentales sont très éloignées des applications. En parallèle à mes activités dédiées à la sorption, j'ai alors porté mes efforts sur cette thématique. Un premier volet a été consacré à la caractérisation acido-basique des matériaux, colloïdaux ou massifs, avec acquisition d'instruments commerciaux ou développement de méthodes originales de mesure de l'adhésion. Cette approche a permis de dégager les processus majeurs à la base de la déposition des particules (interactions électrostatiques et hydrodynamique). La caractérisation de la réactivité des produits de corrosion colloïdaux envers les ion dissous (sulfate, nickel,...) ainsi que la détermination du point de charge nulle ont été réalisées en conditions simplifiés (température ambiante) jusqu'aux conditions industrielles (320°C, présence d'hydrogène).

In Belgium, the Boom Clay is currently studied as the reference host formation for the disposal of high-level and long-lived radioactive waste. In case of direct disposal of spent fuel, uranium isotopes are important contributors along with their daughters to the dose rate at very long term. Therefore, it is essential to study the migration of uranium in the host formation. The present work contributes to improve the knowledge of uranium speciation in the Boom Clay, U(IV) versus U(VI), and of the mechanisms controlling the uranium mobility such as solubility, sorption and complexation by organic matter. The information necessary to interpret the migration behaviour is derived from the study of naturally occurring uranium in the rock and from laboratory experiments conducted under conditions representative for the Boom Clay. Uranium naturally present in the Boom Clay is concentrated in detrital heavy minerals and in authigenic iron(II)-bearing minerals such as siderite and glauconite. Despite its reducing capacity, pyrite is surprisingly depleted in uranium relative to the mean content. Furthermore, uranium is also associated with the surfaces of clay minerals. The clayey fraction contains about 4 ppm uranium and is the main contributor to the total uranium content of the Boom Clay since it constitutes up to 60 wt. % of the rock. The correlation observed on the field between uranium and organic matter suggests that uranium is reduced, likely during the early diagenesis process of bacterially-mediated sulphate reduction. If hexavalent oxidation state of uranium predominates as predicted by geochemical calculations based on the most recent thermodynamic data of the Nuclear Energy Agency (NEA), less than 5% of uranium is complexed by humic acids in the Boom Clay pore water. The U(VI) speciation is dominated by the inorganic carbonate complexes, merely UO2(CO3)34-. The conditional constant determined for the complexation of U(VI) by humic acids under in situ Boom Clay conditions is log exp = 12.4. However, experimental studies show that UO2(CO3)34- is reduced by interaction with pyrite, the main reducing mineral present in the rock, and precipitates as a mixed oxide of U(IV)/U(VI), i.e. UO2+x. Moreover, electromigration experiments suggest that U(VI) is not stable in the Boom Clay: U(VI) is reduced and precipitates as U(IV) oxy-hydroxides. The experimentally measured solubility of U(IV) amorphous oxide, UO2(am), in Boom Clay pore water is about 10 8 mol•l 1. This solubility value is not increased by complexation of U(IV) with dissolved organic matter. The dominant effect of organic matter on the dissolution of UO2(am) is the stabilisation of U(IV) real colloids which increase the uranium concentration by three orders of magnitude. However, the mobility of these colloids is expected to be very limited because of the compaction level of the Boom Clay and its ultra-filtrating feature. The diffusive transport of dissolved uranium is furthermore retarded by significant sorption onto clay minerals. In conclusion, the presence of organic matter in the Boom Clay has no negative effect on the uranium retention which is dominated by the solubility and sorption of U(IV) species

To achieve predictive capability for complex environmental systems with coagulation and arsenic sorption, a unified improved coagulation model coupled with arsenic sorption was developed. A unified coagulation model coupled with arsenic sorption was achieved by the following steps: (1) an improved discretized population balance equation (PBE) was developed to obtain the exact solution of conventional coagulation, (2) the improved PBE was extended to an adjustable geometric size interval having higher numerical stability, accuracy, and computational efficiency than existing models for fractal aggregate coagulation that includes agglomeration and fragmentation, (3) a surface complexation equilibrium model and a sorption kinetic model was introduced to predict arsenic sorption behavior onto hydrous metal oxide surfaces, and (4) an improved discretized PBE was coupled with arsenic sorption kinetics and equilibrium models by aid of collision efficiency ?? depending on surface charge (potential) on the hydrous metal oxide particles, colliding particle size ratio, and fluid strain-rate in applied flow system. The collision efficiency ?? into the improved (r,r)ij(r,r)ijdiscretized coagulation model for fractal aggregate yielded a unified improved coagulation model coupled with arsenic sorption kinetics and the equilibrium model. Thus, an improved unified coagulation model could provide high statistical accuracy, numerical stability, and computational efficiency to enhance predictive capability for behavior of arsenic sorption and fractal colloid particle aggregation and break-up, simultaneously. From the investigation, it is anticipated that the unified coagulation model coupled with arsenic sorption kinetics and equilibrium will provide a more complete understanding of the arsenic removal mechanism and its application to water/wastewater treatment. Further, this coupled model can be applied to other water and wastewater treatment systems combined with sorption and filtration processes. These combined processes can be optimized by the coupled model that was developed in this study. By simulating the arsenic sorption and particle size distribution as a pretreatment before filtration (sand filtration or membrane filtration), the overall arsenic removal efficiency and operation cost can be estimated.

In Sweden, among other countries, a deep multi-barrier geological repository, KBS-3, is planned for the burial of nuclear waste. One of the barriers is identified as the grantic bedrock itself and in this environment chlorite is present at surfaces in fracture zones. This thesis is focused on characterisation of chlorite samples and studies of their dissolution and sorption behaviour, in order to verify chlorites capacity to retard possible radionuclide migration in the case of leaking canisters. Chlorite dissolution of has been studied in the pH interval 2-12, and as expected the dissolution is highest at acidic pH and at most alkaline pH, whereas dissolution is lowest at near neutral pH values. Chemical and physical properties of chlorites clearly influence the dissolution rates, and at steady-state dissolution rates in the interval 10-12 ‑ 10-13 mol g-1 s-1 was observed. Sorption studies were performed since Ni(II) is one of the important activation products in spent nuclear fuel and sorption data on minerals like chlorite are lacking. Ni(II) sorption onto chlorite was studied using batch technique as a function of; pH, concentration of Ni(II), ionic strength and solid concentrations. As expected, the sorption of Ni(II) onto chlorite was pH dependent, but not ionic strength dependent, with a sorption maximum at pH ~ 8, and with a Kd of ~ 103 cm3/g. This confirms that the Ni(II) sorption onto chlorite is primarily acting through surface complexation. The acid-base properties were determined by titrations and described by a non-electrostatical surface complexation model in FITEQL. Further, the sorption results were fit with a 2-pK NEM model and three surface complexes, Chl_OHNi2+, Chl_OHNi(OH)+ and Chl_OHNi(OH)2, gave the best fit using FITEQL. / Sverige är ett av de länder som planerar ett geologiskt slutförvar kallad KBS-3, bestående av ett antal barriärer, för placering utav det använda kärnbränslet. En av dessa barriärer är identifierad som själva berggrunden där det tilltänkta förvaret kommer att byggas och i denna miljö förekommer klorit på granitytor i sprickzoner. Denna doktorsavhandling karakteriserar kloriter och studerar deras upplösnings- och sorptionsbeetende, för att kunna bestämma huruvida kloriter är utav betydelse som naturlig barriär för eventuell radionuklidtransport från det använda kärnbränslet. Upplösning av klorit har undersökts i pH intervallet 2-12 och graden av upplösningen är som förväntat högst vid sura respektive mest basiska pH och lägst där pH är neutralt. Denna studie bekräftar att den kemiska sammansättning och de fysikaliska egenskaper hos kloriterna påverkar upplösningshastigheterna och vid steady‑state har upplösningshastighet bestämts till 10-12 ‑ 10-13 mol g-1 s-1. Sorptionsstudier genomfördes då Ni(II) är en viktig aktiveringsprodukt och data rörande Ni(II) sorption till klorit saknas. Ni(II) sorption till klorit har studerats i; varierande pH, olika initiala Ni(II) koncentrationen, olika jonstyrka och olika fastfas förhållanden där individuella satser i serie har nyttjats. Som förväntat är sorptionen av Ni(II) till klorit pH beroende men inte jonstyrkeberoende och ett sorpions maximum observerades vid pH ~ 8, med ett Kd‑värde på ~ 103 cm3/g. Från detta dras slutsatsen att sorptionen av Ni(II) till klorit sker mestadels genom ytkomplexering. Syra-bas egenskaperna hos kloriterna bestämdes genom titreringar och bekrevs med en icke‑elektrostatisk modell i FITEQL. Vidare har passning av sorptionsresultaten utförts med en 2-pK NEM-modell och tre ytkomplex, Chl_OHNi2+, Chl_OHNi(OH)+ och Chl_OHNi(OH)2, vilket gav den bästa passningen av data med FITEQL. / QC 20100819