Blue-green infrastructure have been more lucrative during the last 30 years, since urbanizationbrings more impervious surfaces that increases stormwater runoff volumes. Amongst thedifferent blue-green infrastructures there are e.g., constructed wetlands and swales. Blue-greeninfrastructure means more natural management of the stormwater, such as infiltration. Forinfiltration of water, the hydraulic conductivity is an important parameter, but also the abilityto remove dissolved pollutants. In literature, various studies of filter materials are only testedfor single dissolved pollutants, which might be a disadvantage as this does not represent fieldconditions where metals usually co-exist. Economic costs are also an important parameter,unfortunately not always targeted in research. In this thesis, the efficiency of five different material mixtures for removing typical dissolvedstormwater pollutants: chromium (Cr), copper (Cu), nickel (Ni), phosphorus (P), lead (Pb) andzinc (Zn) were studied. The mixtures were following: 1) crushed rock + soil (RO_SO) 2)crushed rock + soil + LECA 4/10 + biochar (RO_SO_BC_LC4). 3) crushed rock + soil + LECA10/20 + biochar (RO_SO_BC_LC10). 4) Soil (SO). 5) crushed rock + soil + biochar(RO_SO_BC). This study was a part of blue-green investments that is being made in Östersundmunicipality and the use of low-cost materials for stormwater treatment are examined. The study was made using batch equilibrium tests, to determine the sorption capacity fordifferent material mixtures, using dissolved metal- and P-solutions. The measured data werefitted to Freundlich, Langmuir, Temkin, Dubinin-Radushkevich and Redlich-Petersonisotherms. Economic feasibility has also been compared between the material mixtures.Results showed that SO had the best sorption capacity for all metals and P, with rankingPb > Cr > Cu > Ni > Zn for the metals. All material mixtures showed a removal efficiency of79-99%, at the lowest concentration (1mg/L) for the metals and 31-62% for the lowestconcentration of P-single solution (1mg/L). Using additional materials in the mixtures, such asbiochar, slightly improved the sorption capacities of Pb and P. Redlich-Peterson isothermsprovided the best fits to the data. An economic evaluation of the ingoing materials shows thatSO and RO_SO are undoubtedly the most feasible alternatives for removal of targeted metalsand P.

Urban stormwater is today recognized as a significant source of pollution that has contributed to the deterioration of water quality in lakes and streams. Of the pollutants, metals are commonly occurring in stormwater and can cause major damage when released into the receiving waters. A promising treatment method for removing these metals before it reaches the receiving waters is to filter the water in various filter technologies such as catch basin inserts. In this study, the potential of five materials to remove dissolved copper (Cu) and zinc (Zn) from stormwater was investigated. The study was initiated with batch equilibrium tests to assess the sorption capacity of the materials at different metal concentrations relevant for stormwater. This was done in both single and binary batches to investigate whether or not any competitive sorption occurred between the metals. Langmuir, Freundlich and Sips isotherm models were adapted to the obtained data. Through geochemical modelling, it was also possible to investigate whether precipitation of metals was likely. Finally, kinetic studies were conducted to investigate whether the reaction rate of Cu and Zn was relevant in the context of catch basin inserts. The results showed that the biochar had the highest sorption capacity followed by peat, bark, milkweed, and polypropylene. It could also be noted that Cu competed with Zn binding sites at high concentrations and that the sorption capacity of biochar, peat and bark, at concentrations between 50-100 μg/l Cu and 50-500 μg/l Zn, was sufficient to meet the limits set for stormwater emissions. For these sorbents, the reaction rate was also significant. Kinetics tests showed that at an initial concentration of 1,000 μg/l, 83% of the metals were sorbed after 5 minutes and after 10 minutes this number was 93%. Bark and peat also showed low effluent pH and leaching of dissolved organic carbon (DOC). The Langmuir and pseudo-second order equation could be well adapted to the data while geochemical modelling showed that precipitation of metals was unlikely. This suggests that chemical adsorption may be the mechanism that largely accounted for the removal of Cu and Zn. The results of this study can hardly be used to estimate the field performance of stormwater filters, but can be used as a basis for comparing and selecting sorbents for subsequent column tests. / I denna studie undersöktes potentialen för fem material att avskilja löst koppar (Cu) och zink (Zn) från dagvatten. Studien inleddes med skaktest för att testa sorptionsförmågan hos materialen vid olika metallkoncentrationer relevant för dagvatten. Detta gjordes i både singel och binära test för att undersöka om någon konkurrerande sorption skedde mellan metallerna. Langmuirs, Freundlichs och Sips isotermmodeller anpassades även till resultatet. Genom geokemisk modellering var det även möjlig att undersöka om utfällning av metaller var sannolik. Till sist gjordes kinetiska studier för att undersöka om reaktionshastigheten för sorption av Cu och Zn till filtermaterialen var relevanta i ett brunnsfiltersammanhang. Resultaten visar att biokol hade den största sorptionsförmågan följt av torv, bark, sidenört och polypropylen. Det kunde även konstateras att koppar konkurrerade om sorptionsplatser för zink vid högre koncentrationer och att sorptionskapaciteten för biokol, torv och bark, vid koncentrationer mellan 50-100 µg/l Cu och 50-500 µg/l Zn, är tillräckligt hög för att uppfylla gränsvärdena för utsläpp av dagvatten. För dessa sorbenter var reaktionshastigheten betydande. Kinetiktesten visade att vid en initial koncentration på 1,000 µg/L var 83% av metallerna sorberade efter 5 minuter och efter 10 minuter var denna siffra uppe i 93%. Bark and torv uppvisade även ett lågt uppmätt pH och lakade löst organisk kol (DOC). Langmuir och pseudo-andra ordningens ekvation kunde anpassas väl till datat samtidigt som den geokemiska modelleringen visade att utfällning av metaller var osannolikt. Detta antyder att kemisk adsorption kan vara den mekanism som till störst del stod för avskiljningen av Cu och Zn. Studien kan inte fastställa något om filtermaterialens fältprestanda, men kan användas som underlag för att jämföra och att välja sorbenter för efterföljande kolumntester. / Formas project 2016-75

O conhecido histórico de contaminação por passivos da mineração de galena (PbS) da região do Vale do Ribeira (SP) faz com que seja de grande importância o estudo da adsorção de Pb com a finalidade de determinar a capacidade de sorção de materiais inconsolidados do município de Eldorado Paulista (SP) para serem empregados como barreira selante na contenção da lixiviação de metais por resíduos de mineração (com destaque para o Pb). O objetivo do presente trabalho foi avaliar a adsorção de Pb por meio de ensaios de equilíbrio em lote. Para realizar tal objetivo, foram coletadas 4 amostras de materiais inconsolidados (3 transportados e 1 residual) no município de Eldorado Paulista, anteriormente caracterizadas. Foram realizados ensaios de caracterização dos materiais (MO, \'delta\'pH, compactação e permeabilidade) visando determinar as principais características que influenciam na retenção de metais, assim como ensaios de equilíbrio em lote para avaliar a capacidade de adsorção de Pb. O ensaio BET foi realizado com amostras triplicatas dos 4 solos, empregando concentrações iniciais de Pb aproximadas de 30, 60, 90 e 120 mg L-1, massa de solo de 20 g, tempo de contato de 24 horas e razão massa/solução de 1/5. Com os resultados obtidos foram confeccionadas isotermas de sorção segundo os modelos Linear, de Freundlich e Langmuir I e II. Os resultados indicaram que os materiais inconsolidados transportados T2 e T3 são os mais adequados para o emprego em barreira selante para contenção de Pb, sendo suas capacidades de adsorção influenciadas, principalmente, pelo teor de óxidos de ferro e fração argila. As melhores sorções foram obtidas para os solos T2 e T3 para concentrações iniciais aproximadas entre 30 e 120 mg L-1. Desta forma, conclui-se que o ensaio BET foi adequado para determinação da adsorção por metais. / The known history of contamination by galena (PbS) mining liabilities from Ribeira Valley region (SP) provides importance to the Pb adsorption study in order to determine the sorption by unconsolidated materials from Eldorado Paulista city (SP) to be employed as liners to contain metals leaching derived from mining (with emphasis on Pb). The objective of the current work was assess the Pb adsorption by Batch Equilibrium Tests. To accomplish this objective, 4 unconsolidated materials samples were collected in Eldorado Paulista, previously characterized. Characterization tests were performed (MO, \'delta\'pH, compaction and permeability) to determine the main characteristics that influence the retention of metals, and Batch Equilibrium Tests to assess soils capacities of Pb adsorption. BET was performed with triplicate samples of the 4 materials, applying initial Pb concentrations around 30, 60, 90 and 120 mg L-1, mass of soil about 20 g, mass/solution rate of 1/5 and 24 hours of contact time. the results provide sorption isotherms modeled by Linear, Freundlich and Langmuir I and II equations. The results indicated that unconsolidated materials T2 and T3 are the best suited for use in liners to retain Pb, and their sorption capacities are mainly influenced by iron oxides content and clay content. Best sorption were obtained to soils T2 and T3 with initial concentrations about 30 to 120 mg L-1. Thus, it is concluded that BET is appropriated to determine metals adsorption.

O conhecido histórico de contaminação por passivos da mineração de galena (PbS) da região do Vale do Ribeira (SP) faz com que seja de grande importância o estudo da adsorção de Pb com a finalidade de determinar a capacidade de sorção de materiais inconsolidados do município de Eldorado Paulista (SP) para serem empregados como barreira selante na contenção da lixiviação de metais por resíduos de mineração (com destaque para o Pb). O objetivo do presente trabalho foi avaliar a adsorção de Pb por meio de ensaios de equilíbrio em lote. Para realizar tal objetivo, foram coletadas 4 amostras de materiais inconsolidados (3 transportados e 1 residual) no município de Eldorado Paulista, anteriormente caracterizadas. Foram realizados ensaios de caracterização dos materiais (MO, \'delta\'pH, compactação e permeabilidade) visando determinar as principais características que influenciam na retenção de metais, assim como ensaios de equilíbrio em lote para avaliar a capacidade de adsorção de Pb. O ensaio BET foi realizado com amostras triplicatas dos 4 solos, empregando concentrações iniciais de Pb aproximadas de 30, 60, 90 e 120 mg L-1, massa de solo de 20 g, tempo de contato de 24 horas e razão massa/solução de 1/5. Com os resultados obtidos foram confeccionadas isotermas de sorção segundo os modelos Linear, de Freundlich e Langmuir I e II. Os resultados indicaram que os materiais inconsolidados transportados T2 e T3 são os mais adequados para o emprego em barreira selante para contenção de Pb, sendo suas capacidades de adsorção influenciadas, principalmente, pelo teor de óxidos de ferro e fração argila. As melhores sorções foram obtidas para os solos T2 e T3 para concentrações iniciais aproximadas entre 30 e 120 mg L-1. Desta forma, conclui-se que o ensaio BET foi adequado para determinação da adsorção por metais. / The known history of contamination by galena (PbS) mining liabilities from Ribeira Valley region (SP) provides importance to the Pb adsorption study in order to determine the sorption by unconsolidated materials from Eldorado Paulista city (SP) to be employed as liners to contain metals leaching derived from mining (with emphasis on Pb). The objective of the current work was assess the Pb adsorption by Batch Equilibrium Tests. To accomplish this objective, 4 unconsolidated materials samples were collected in Eldorado Paulista, previously characterized. Characterization tests were performed (MO, \'delta\'pH, compaction and permeability) to determine the main characteristics that influence the retention of metals, and Batch Equilibrium Tests to assess soils capacities of Pb adsorption. BET was performed with triplicate samples of the 4 materials, applying initial Pb concentrations around 30, 60, 90 and 120 mg L-1, mass of soil about 20 g, mass/solution rate of 1/5 and 24 hours of contact time. the results provide sorption isotherms modeled by Linear, Freundlich and Langmuir I and II equations. The results indicated that unconsolidated materials T2 and T3 are the best suited for use in liners to retain Pb, and their sorption capacities are mainly influenced by iron oxides content and clay content. Best sorption were obtained to soils T2 and T3 with initial concentrations about 30 to 120 mg L-1. Thus, it is concluded that BET is appropriated to determine metals adsorption.

Na região do Vale do Ribeira, os resíduos provenientes do beneficiamento e fundição do minério de chumbo (Pb) foram lançados por décadas no rio Ribeira de Iguape ou depositados diretamente na superfície do solo, sem qualquer proteção, constituindo fontes de contaminação do solo e das águas por metais potencialmente tóxicos. O uso do solo local na construção de barreira selante para impermeabilização e retenção dos contaminantes representa uma alternativa para o controle desse tipo de contaminação. Por isso é importante estudar os solos da região, sua capacidade de retenção de metais potencialmente tóxicos, e alternativas de baixo custo para melhorar suas propriedades físicas e químicas. A adição de matéria orgânica é um caminho para aumentar a retenção de cátions. Assim, a presente pesquisa visou verificar se um solo residual proveniente de Eldorado Paulista, no Vale do Ribeira, apresenta características favoráveis para o emprego como barreira selante na disposição de resíduos de mineração desta região; bem como analisar a melhoria da sua capacidade de adsorção de Pb e cádmio (Cd), quando misturado com turfa, um material orgânico com elevada capacidade de retenção de metais e de baixo custo, em proporções de 10 e 20% (m/m). Foram realizados ensaios de caracterização para determinação das propriedades físicas, químicas e mineralógicas do solo. Para avaliação da capacidade de adsorção de Pb e Cd pelo solo e pelas misturas solo-turfa, foram realizados ensaios de equilíbrio em lote. O solo estudado é um solo residual argiloso, cuja fração argilosa é predominantemente composta por caulinita. Ele apresenta alguns pontos favoráveis para que seja utilizado como barreira selante na retenção de cátions metálicos, como granulometria predominantemente fina (54,5% de argila), índice de plasticidade adequado (25,1%), meio oxidante (Eh = +333 mV), predomínio de cargas negativas na superfície dos coloides (ΔpH = -0,9 e PESN = 3,6) e baixa condutividade hidráulica quando compactado (na ordem de 10-9 m/s). Por outro lado, algumas características são menos interessantes para a retenção de metais, como baixa capacidade de troca catiônica (41,4 mmolc/dm3), baixo teor de matéria orgânica (9 g/kg) e pH ácido (4,6). A adição de turfa em proporções de 10 e 20% (m/m) ao solo aumentou o teor de matéria orgânica em 4,3 vezes e 6,4 vezes, respectivamente. A CTC também aumentou, variando de 41,4 mmolc/dm3 para o solo a 101,7 mmolc/dm3 para a mistura com 10% de turfa, e ainda a 143,1 mmolc/dm3 para a mistura com 20% de turfa. Não foram observadas mudanças de pH. Observou-se também a melhoria da capacidade de adsorção de Pb e Cd. O solo residual natural apresentou eficiência de remoção de Pb de 54% a 100% para concentrações iniciais de 22 a 232 mg/L deste metal. A mistura com maior teor de turfa (20%) removeu 95,3% a 100% do Pb para concentrações iniciais de 31 a 267 mg/L. O coeficiente de distribuição Kd aumentou de 4,57 cm3/g (para o solo natural) até 58,57 cm3/g (para a mistura com 20% de turfa). O Kf aumentou de 75,75 a 508,86 cm3/g e o KL aumentou de 0,0276 a 0,4118 cm3/g, devido a adição de turfa em 20%. Em relação ao Cd, o solo natural apresentou eficiência de remoção de 30,5 a 72,1% para concentrações iniciais de 17 a 170 mg/L. A mistura com 20% de turfa aumentou a eficiência de 54,9 a 88,9% para concentrações iniciais de 20 a 150 mg/L de Cd. O coeficiente Kd foi de 1,56 cm3/g para o solo natural a 6,42 cm3/g para a mistura com maior proporção de turfa. O Kf foi de 30,06 a 63,88 cm3/g, e o KL foi de 0,0301 a 0,0483 cm3/g. Concluiu-se que a adição de turfa ao solo nas proporções de 10 e 20% contribuiu para a melhoria das propriedades associadas a retenção de cátions metálicos e favoreceu a melhor adsorção de Pb e Cd. / In the Ribeira Valley region, in Brazil, mining waste originated from lead ore beneficiation and smelting was launched for decades in the Ribeira de Iguape river or deposited directly on the soil surface near this river, without any protection. This created sources of soil and water contamination by potentially toxic metals. The use of local soil for construction of sealant barriers aiming to waterproof and retain the contaminants represents an alternative to control this type of contamination. It is important to study the region soils, their capacity of retention of potentially toxic metals, and low cost alternatives to improve their physical and chemical properties. The addition of organic matter to the soil is an alternative to increase cation retention. Therefore, the purpose of this research was to verify if a residual soil collected in the Eldorado Paulista municipality, in the Ribeira Valley, presents suitable characteristics to be used as a sealant barrier for mining waste disposal; and to assess the improvement of its adsorption capacity of lead and cadmium, when mixed with peat (an organic material with high metal retention capacity, and low cost), in proportions of 10 and 20% (w/w). Characterization tests were carried out to determine the physical, chemical and mineralogical properties of the soil. For the evaluation of the adsorption capacity of lead and cadmium by the soil and soil-peat mixtures, batch equilibrium tests were performed. The studied soil is a clayey residual soil. Its clayey fraction is predominantly composed of kaolinite. It presents some favorable characteristics to be used as a sealant barrier for retention of metallic cations, such as: predominance of fines (54.5% clay), suitable plasticity index (25.1%), oxidizing medium (Eh = +333 mV), predominance of negative charges on the surface of the colloidal particles (ΔpH = -0.9 and PZSE = 3.6) and low hydraulic conductivity when compacted, which reached the order of 10-9 m/s. However, some soil properties are less suitable for metal retention, such as low cation exchange capacity (41.4 mmolc/dm3), low organic matter content (9 g/kg) and low pH (4.6). The addition of peat to the soil in proportions of 10 and 20% (w/w) increased the organic matter content by 4.3 times and 6.4 times, respectively. CTC also increased. It ranged from 41.4 mmolc/dm3 (natural soil) to 107.7 mmolc/dm3 (mixture with 10% peat) and to 143.1 mmolc/dm3 (mixture with 20% of peat). No changes in pH were observed. It was also noticed the improvement of the adsorption capacity of lead and cadmium. The lead removal efficiency of the natural residual soil was from 54% to 100% at initial concentrations from 22 to 232 mg/L of this metal. The mixture with higher peat content (20%) removed 95.3% to 100% of the lead at initial concentrations from 31 to 267 mg/L. The distribution coefficient Kd increased from 4.57 cm3/g (for the natural soil) to 58.57 cm3/g (for the mixture with 20% of peat). The Kf increased from 75.75 to 508.86 cm3/g and the KL increased from 0.0276 to 0.4118 cm3/g, due to the addition of peat in 20%. With regard to cadmium, the natural soil removed 30.5 to 72.1% of this metal for initial concentrations of 17 to 170 mg/L. The mixture with 20% of peat increased the Cd removal efficiency to 54.9 to 88.9% at initial concentrations from 20 to 150 mg/L. Kd was 1.56 cm3/g for the natural soil and increased to 6.42 cm3/g for the mixture with the highest content of peat. Kf increased from 30.06 to 63.88 cm3/g, and the KL increased from 0.0301 to 0.0483 cm3/g. It was concluded that the addition of peat to the soil in proportions of 10 and 20% caused improvement of properties related with metalic cation retention and favored Pb and Cd adsorption.