Soil is a critical component of the global sulfur (S) cycle acting as source and a sink for various S species and mediating changes of S oxidation states. However, very little is known about the identities of these specific organic and inorganic S containing molecules, especially in Brazilian soils under no-tillage (NT) system. Thus, the objectives of this study were: (i) to report long and medium term effects of the application of lime and up to 12 t ha-1 of phosphogypsum (PG) in samples from two Oxisols collected in field experiments carried out under no-tillage (NT) systems; (ii) to assess the effect of PG application on the amount, form and distribution of organic and inorganic S pools in soils under NT comparing to a natural forest ; (iii) to investigate C, N and S mineralization/immobilization in soil samples affected by plant residues and biochar, thus identifying the major transformations in the S fractions. After 13 years of lime application in a loamy Oxisol, changes in soil acidity and exchangeable Ca2+ ad Mg2+ supply were visible up to 80 cm depth. The effect of PG providing Ca2+ and S-SO4 2- were more pronounced at lower depths. S-SO4 2- distribution in the soil profile was mostly correlated with contents of free dithionite extractable Fe (Fed) and amorphous dithionite extractable Fe minus oxalate extractable Fe (Fed-Feo). There was no effect of lime and PG in maize grain yield, showing that the plants were unable to benefit of the soil ameliorations. An appreciable movement of sulfate to the subsoil was observed in soil samples from a clayey Oxisol, even in a medium-term (after 3.5 years), despite the fact that the soil had presented high SO4 2- adsorption capacity. In this area, PG had positive benefits in cereal crop yield due to the supply of Ca2+ and S-SO4 2-. PG application and changes in landuse practice alters both quantitative (evaluated by the wet-chemical technique) and qualitative (evaluated by means of X-Ray Near Edge Structure - XANES spectroscopy) composition of S functional groups in this wet subtropical Brazilian soil under NT. Compared to the forest site, soils under NT system had lower amounts of organic C, total N and total S Sulfur losses due to cultivation were higher than losses of C and N, and the use of fertilizers containing S seems to be vital for the recovery of S moieties. The dynamics of the plant materials decomposition was mostly governed by the C/S ratio. Sulfur mineralization was driven by the form of S in the starting materials rather than S concentration in the tissue, as revealed by XANES. The incorporation of plant residues and biochar led to an increase in the amount of ester sulfate in the early stage of incubation, which was further mineralized and had a steady decline at the end of evaluation. These findings encourage further investigations of biochar as S source, involving particularly chars produced from different feedstocks and pyrolysis temperatures. / O solo é um componente crítico do ciclo global de enxofre (S), agindo como fonte e dreno das várias espécies de S e mediando mudanças nos seus estados de oxidação. No entanto, pouco se sabe sobre as identidades dos compostos orgânicos e inorgânicos de S, especialmente em solos brasileiros sob plantio direto (PD). Assim, os objetivos deste estudo foram: (i) relatar os efeitos a longo e médio prazo da aplicação de calcário e de até 12 t ha-1 de fosfogesso (FG) em amostras de dois Latossolos coletadas em experimentos de campo realizados sob PD; (ii) avaliar o efeito da aplicação de PG na quantidade, forma e distribuição das frações orgânicas e inorgânicas de S em solos sob PD em comparação com uma floresta natural; (iii) investigar a mineralização/imobilização de C, N e S em amostras de solo afetadas por fontes de resíduos vegetais e biocarvão, identificando as transformações nas frações de S. Após 13 anos de aplicação de calcário em um Latossolo Vermelho distrófico de textura média, foi verificado efeito na correção da acidez do solo e no fornecimento de Mg2+ até 80 cm de profundidade enquanto os efeitos do FG fornecendo Ca2+ e S-SO4 2- foram mais pronunciados em profundidade. A distribuição de S-SO4 2- no perfil deste solo foi correlacionada com o conteúdo de Fe-ditionito (Fed) e Fe-ditionito menos Fe-oxalato (Fed, Feo). Não houve efeito do calcário e do FG na produção de grãos de milho, mostrando que as plantas não puderam se beneficiar das melhorias no solo. Foi observado apreciável movimento de S para o subsolo em amostras de um Latossolo Vermelho distrófico muito argiloso, mesmo em médio prazo (após 3,5 anos), apesar de o solo apresentar alta capacidade de adsorção de sulfato. Nesta área, o FG teve efeitos positivos no rendimento das culturas de cereais, devido ao fornecimento de Ca2+ e S-SO4 2- . A aplicação de FG e as mudanças no uso da terra alteraram tanto a composição quantitativa (avaliada pela técnica de fracionamento químico) quanto qualitativa (avaliada por meio da espectroscopia de raios-X próxima à borda de absorção - XANES) dos grupos funcionais de S em um solo subtropical da região úmida sob PD. Em comparação com o PD, os solos sob floresta apresentaram maior conteúdo de C orgânico, N e S total. As perdas de S devido ao cultivo foram superiores às perdas de C e N, e o uso de fertilizantes sulfatados parece ser vital para a recuperação do S do solo. A dinâmica de decomposição dos materiais vegetais foi principalmente regida pela razão C/S. A mineralização de enxofre foi impulsionada pela forma de S nos materiais iniciais, e não pela concentração S no tecido, conforme revelado por XANES. A incorporação de resíduos vegetais e biocarvão levou ao aumento nos ésteres de sulfato na fase inicial de incubação, fração posteriormente mineralizada, apresentando declínio no final da avaliação. Estas descobertas incentivam mais investigações do biocarvão como fonte de S, envolvendo carvões produzidos a partir de diferentes matérias-primas e temperaturas de pirólise.

Magister Scientiae - MSc (Dept. of Chemistry) / Fly ash and AMD samples were characterised by standard analytical methods for selection of the test materials. Active treatment by means of mixing fly ash with AMD in beakers and a large tank at pre-determined ratios have shown that fly ash is capable of neutralising AMD and increasing the pH beyond neutral values, which optimises the removal of heavy metals and ions. The trend was: the more fly ash added the quicker was the reaction time and higher the pH values achieved. Iron was reduced by as much 99 % in beaker scale experiments via Fe(OH)3 precipitation at pH values >4.0. A 99 % decrease in aluminium concentration was observed which was attributed to the precipitation of primarily gibbsite and various other mineral phases at pH values >5.5. As the pH increases, sulphate is adsorbed via Fe(OH)3 and gypsum precipitation at elevated pH. Sulphate attenuation with fly ash was excellent, achieving 98 % attenuation with beaker scale experiments and 1:1 fly ash:AMD ratio. Sulphate attenuation with fly ash was comparable to membrane and ion exchange systems and exceeded the performance of limestone treatment. Except for the larger volumes of fly ash needed to neutralise the AMD, fly ash proved to be a feasible and cost efficient alternative to limestone treatment. Fly ash produced competing results to limestone concerning acidity removal and sulphate attenuation. The comparison highlighted the advantages of utilising fly ash in comparison to limestone and demonstrated its cost effectiveness. The results of this study have shown that fly ash could be successfully applied for the neutralisation of acid mine drainage (AMD) and effectively attenuate the sulphate load in the treated water. The critical parameters to this technology are the variations of chemical composition and mineralogy of fly ash, which could influence the pH, contact time of the neutralisation reaction, and the same is true if the AMD quality varies. / South Africa

O presente trabalho mostra a investigação da influência da temperatura sobre a absorção de SO2 por calcários na combustão de carvão mineral em reator de leito fluidizado atmosférico. Introduz-se bateladas de carvão no reator fluidizado com ar pré-aquecido a temperaturas entre 700 e 900ºC, e a combustão se desenvolve produzindo gases contendo SO2. Bateladas de calcário são injetadas para absorção do SO2. Considera-se duas situações distintas: injeção simultânea de carvão e calcário e injeção defasada. Na primeira situação investiga-se sulfatação direta, enquanto na segunda estuda-se sulfatação com o calcário previamente calcinado. Utiliza-se um carvão energético CE4500 procedente de Criciúma-SC, e dois tipos de calcário : um calcítico procedente de Itaú-MG, outro dolomítico de Ipeúna-SP. Os resultados mostram absorção de SO2 mais eficiente quando os calcários são previamente calcinados. As máximas conversões são observadas em temperaturas em torno de 800ºC. / This work shows the investigation about the influence of temperature on the absorption of SO2 by limestones in atmospheric bubbling fluidized bed combustion of mineral coal. Batches of coal are introduced into the reactor fluidized by air pre-heated at temperatures between 700 and 900ºC, and the combustion develops producing gases containing SO2. Batches of limestone are injected for sulfur absorption. Two distinct situations are considered: simultaneous and non-simultaneous injection of coal and limestone. In the first situation direct sulfation is investigated, while in the second situation sulfation is carried out by pre-calcined limestone. A CE4500 energetic coal from Criciúma-SC is used, alongside with two types of limestone : a calcitic limestone from Itaú-MG, and a dolomite from Ipeúna-SP. The results show that tha absorption of SO2 is more efficient for limestones previously calcined. The maximum conversions were observed for temperatures around 800ºC.

Soil is a critical component of the global sulfur (S) cycle acting as source and a sink for various S species and mediating changes of S oxidation states. However, very little is known about the identities of these specific organic and inorganic S containing molecules, especially in Brazilian soils under no-tillage (NT) system. Thus, the objectives of this study were: (i) to report long and medium term effects of the application of lime and up to 12 t ha-1 of phosphogypsum (PG) in samples from two Oxisols collected in field experiments carried out under no-tillage (NT) systems; (ii) to assess the effect of PG application on the amount, form and distribution of organic and inorganic S pools in soils under NT comparing to a natural forest ; (iii) to investigate C, N and S mineralization/immobilization in soil samples affected by plant residues and biochar, thus identifying the major transformations in the S fractions. After 13 years of lime application in a loamy Oxisol, changes in soil acidity and exchangeable Ca2+ ad Mg2+ supply were visible up to 80 cm depth. The effect of PG providing Ca2+ and S-SO4 2- were more pronounced at lower depths. S-SO4 2- distribution in the soil profile was mostly correlated with contents of free dithionite extractable Fe (Fed) and amorphous dithionite extractable Fe minus oxalate extractable Fe (Fed-Feo). There was no effect of lime and PG in maize grain yield, showing that the plants were unable to benefit of the soil ameliorations. An appreciable movement of sulfate to the subsoil was observed in soil samples from a clayey Oxisol, even in a medium-term (after 3.5 years), despite the fact that the soil had presented high SO4 2- adsorption capacity. In this area, PG had positive benefits in cereal crop yield due to the supply of Ca2+ and S-SO4 2-. PG application and changes in landuse practice alters both quantitative (evaluated by the wet-chemical technique) and qualitative (evaluated by means of X-Ray Near Edge Structure - XANES spectroscopy) composition of S functional groups in this wet subtropical Brazilian soil under NT. Compared to the forest site, soils under NT system had lower amounts of organic C, total N and total S Sulfur losses due to cultivation were higher than losses of C and N, and the use of fertilizers containing S seems to be vital for the recovery of S moieties. The dynamics of the plant materials decomposition was mostly governed by the C/S ratio. Sulfur mineralization was driven by the form of S in the starting materials rather than S concentration in the tissue, as revealed by XANES. The incorporation of plant residues and biochar led to an increase in the amount of ester sulfate in the early stage of incubation, which was further mineralized and had a steady decline at the end of evaluation. These findings encourage further investigations of biochar as S source, involving particularly chars produced from different feedstocks and pyrolysis temperatures. / O solo é um componente crítico do ciclo global de enxofre (S), agindo como fonte e dreno das várias espécies de S e mediando mudanças nos seus estados de oxidação. No entanto, pouco se sabe sobre as identidades dos compostos orgânicos e inorgânicos de S, especialmente em solos brasileiros sob plantio direto (PD). Assim, os objetivos deste estudo foram: (i) relatar os efeitos a longo e médio prazo da aplicação de calcário e de até 12 t ha-1 de fosfogesso (FG) em amostras de dois Latossolos coletadas em experimentos de campo realizados sob PD; (ii) avaliar o efeito da aplicação de PG na quantidade, forma e distribuição das frações orgânicas e inorgânicas de S em solos sob PD em comparação com uma floresta natural; (iii) investigar a mineralização/imobilização de C, N e S em amostras de solo afetadas por fontes de resíduos vegetais e biocarvão, identificando as transformações nas frações de S. Após 13 anos de aplicação de calcário em um Latossolo Vermelho distrófico de textura média, foi verificado efeito na correção da acidez do solo e no fornecimento de Mg2+ até 80 cm de profundidade enquanto os efeitos do FG fornecendo Ca2+ e S-SO4 2- foram mais pronunciados em profundidade. A distribuição de S-SO4 2- no perfil deste solo foi correlacionada com o conteúdo de Fe-ditionito (Fed) e Fe-ditionito menos Fe-oxalato (Fed, Feo). Não houve efeito do calcário e do FG na produção de grãos de milho, mostrando que as plantas não puderam se beneficiar das melhorias no solo. Foi observado apreciável movimento de S para o subsolo em amostras de um Latossolo Vermelho distrófico muito argiloso, mesmo em médio prazo (após 3,5 anos), apesar de o solo apresentar alta capacidade de adsorção de sulfato. Nesta área, o FG teve efeitos positivos no rendimento das culturas de cereais, devido ao fornecimento de Ca2+ e S-SO4 2- . A aplicação de FG e as mudanças no uso da terra alteraram tanto a composição quantitativa (avaliada pela técnica de fracionamento químico) quanto qualitativa (avaliada por meio da espectroscopia de raios-X próxima à borda de absorção - XANES) dos grupos funcionais de S em um solo subtropical da região úmida sob PD. Em comparação com o PD, os solos sob floresta apresentaram maior conteúdo de C orgânico, N e S total. As perdas de S devido ao cultivo foram superiores às perdas de C e N, e o uso de fertilizantes sulfatados parece ser vital para a recuperação do S do solo. A dinâmica de decomposição dos materiais vegetais foi principalmente regida pela razão C/S. A mineralização de enxofre foi impulsionada pela forma de S nos materiais iniciais, e não pela concentração S no tecido, conforme revelado por XANES. A incorporação de resíduos vegetais e biocarvão levou ao aumento nos ésteres de sulfato na fase inicial de incubação, fração posteriormente mineralizada, apresentando declínio no final da avaliação. Estas descobertas incentivam mais investigações do biocarvão como fonte de S, envolvendo carvões produzidos a partir de diferentes matérias-primas e temperaturas de pirólise.

The San Bernardino Mountains are well known for their rich mining history, especially, gold in the mid-1800s and the current mining of one of the world’s largest deposits of high purity limestone. The purpose of this study was to compile new, current, and historical data of the major economic resources that are present and mining that has gone on in the San Bernardino Mountains. It is estimated that historical mining of the Holcomb Valley recovered $457,660,000 of gold or about 350,000 troy ounces based on samples collected for this study and 2013 gold price. The current major geologic resource is the limestone deposits on the north slope of the San Bernardino Mountains. Presently, there are three operators: Omya, Specialty Minerals, and Mitsubishi Cement. The San Bernardino Mountains are well known for skarn gold deposits. New work indicates that the placer gold from Holcomb Valley is often of very high purity. Placer gold samples were analyzed using the scanning electron microscope and energy dispersive x-ray spectra to determine the purity of the gold. Rim and core analysis of the placer gold was used to determine if the gold was transported from its source and to give an estimate of transportation distance. Results show some of the placer gold of Holcomb Valley has been rounded and flattened by weathering and transportation with increased gold purity in the rims while other gold grains still sustain their octahedral crystalline structure. Rims range in gold purity from 84.26% to 100%, with core gold purity ranging from 79.51% to 99.79%. Gold samples were weighed, photographed, measured, and classified by shape, angularity and texture, to assess the effects of transportation. Gold weights where used to calculate an economic value of gold. Geographic Information System “GIS” was used to visually display geology, historical and current mine locations, locations of samples used in this study, and to help calculate the volume of the Holcomb Valley TsE rock unit, which is where the placer gold is deposited. Sediment sample 15 from TsE had the lowest gold value of .002 ounces per cubic yard. This value is inferred to represent the amount of gold remaining after mining. Based on this assumption and the estimated volume of TsE at 50,027,000 cubic yards, the estimated total weight of gold remaining in the deposit is about 100,000 troy ounces, with a dollar value of about $130,760,000, using gold values for 2013. Sample 17 had the highest gold value, with .014 ounces per cubic yard. This is inferred to represent the concentration of placer gold deposits within parts of Holcomb Valley that have never been mined. This yields a total weight of the deposit of roughly 700,000 troy ounces, with an estimated value of $915,320,000 using gold prices for 2013. The gold values were calculated using November 7, 2013 gold spot price of $1,307.60.

Orientador: Edson Lazarini / Resumo: No cerrado, o Sistema Plantio Direto assume importância devido ao não revolvimento do solo, utilizar culturas de cobertura e preconizar rotação de culturas. Em área experimental no município de Selvíria – MS implantou-se o sistema plantio direto no ano agrícola 2000/01, com o objetivo de avaliar os tratamentos com diferentes modos e épocas de aplicação de calcário, culturas de cobertura e doses de N, no comportamento das culturas de milho e soja. Os resultados abordados neste trabalho, referem-se aos anos agrícolas 2015/16, 2016/2017 e 2017/18, quando utilizou-se o milho como cultura principal, o milheto e a Crotalaria juncea como culturas de cobertura, diferentes doses de calcário aplicadas durante os anos anteriores, complementadas com a reaplicação de calcário na presença e ou ausência de gesso e doses de N em cobertura. A área experimental pertence a UNESP – Campus de Ilha Solteira, sendo o solo classificado como LATOSSOLO VERMELHO distrófico com textura argilosa. O delineamento experimental utilizado foi o em blocos casualizados com os tratamentos disposto em esquema fatorial. O calcário foi aplicado em 2001, 2007 e 2012, perfazendo um total de (T1) 4,66; (T2) 6,90; (T3) 5,47; (T4) 6,11 e (T5) 0,81 t ha-1. No ano de 2016, foi realizado uma nova reaplicação de calcário, aplicando respectivamente nos tratamentos, 2,26; 4,52; 2,26; 4,52 e 0 t ha-1, acrescido para os tratamentos T3 e T4, 1,7 t ha-1 de gesso. As plantas de cobertura forma mantidas e as doses de N utilizadas a... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In the Cerrado region, the no-tillage system assumes importance because of no soil tillage, use of cover crops and crop rotation. In an experimental area in Selvíria county, Mato Grosso do Sul State, Brazil, the no-tillage system was implemented in the agricultural year 2000/01, aiming to evaluate the treatments with different modes and times of application of limestone, cover crops and N rates, on the behavior of corn and soybean crops. The results to be presented in this work refer to the agricultural years 2015/16, 2016/2017 and 2017/18, when maize was used as the main crop, millet and Crotalaria juncea as cover crops, different doses of limestone applied during the previous years, complemented by the reapplication of limestone in the presence and / or absence of gypsum and N rates in topdressing. The experimental area of UNESP - Ilha Solteira Campus has soil classified as dystrophic Red Latosol with clay texture. The experimental design was a randomized complete block with treatments arranged in a factorial scheme. Limestone was applied in 2001, 2007 and 2012, totaling (T1) 4.66; (T2) 6.90; (T3) 5.47; (T4) 6.11 and (T5) 0.81 t ha-1. In 2016, a new limestone reapplication was performed, applying respectively 2.26; 4.52; 2.26; 4.52 and 0 t ha-1, plus for treatments T3 and T4, 1.7 t ha-1 of gypsum. The cover crops were maintained and the doses of N used annually were 0, 90 and 180 kg ha-1, using urea as source. Evaluations were based on corn nutritional status, corn agronomi... (Complete abstract click electronic access below) / Mestre

Indian Key Historic State Park is a small island located on the Atlantic Ocean side of the Florida Keys, near Islamorada. Before it was bought by the state of Florida in 1970, Indian Key had been the setting for a number of historically significant activities. The most well known of these is the 1840 raid on the people and buildings that made up a small wrecking village, established on the island by Jacob Housman in the early 1830s. The limestone foundations of these structures are the main attraction to today's visitor to the park. There is more to the story of Indian Key, though, than the Housman period and the structural remains left behind from this stage of the island's history. Almost immediately after the near destruction of the island in 1840, the Florida Squadron of the Navy took over, constructing their own buildings, and re-using some of the previously constructed foundations. This cycle of rebuilding and re-use continued for another hundred years, with families and fishers trying to inhabit and profit from Indian Key. The focus of this thesis is to examine the foundations and associated archaeological features of Indian Key in order to determine better periods of use and re-use for the buildings that have been identified through archaeological investigations. This research was conducted in order to examine the site's architecture through an archaeological perspective; it is by no means an attempt at a complete architectural study of the site. Rather, it is an effort to examine the entire island of Indian Key, by focusing on the history of the buildings that helped make it an important piece of Florida's past.

<p>Fly ash and AMD samples were characterised by standard analytical methods for selection of the test materials. Active treatment by means of mixing fly ash with AMD in beakers and a large tank at pre-determined ratios have shown that fly ash is capable of neutralising AMD and increasing the pH beyond neutral values, which optimises the removal of heavy metals and ions. The trend was: the more fly ash added the quicker was the reaction time and higher the pH values achieved. Iron was reduced by as much 99 % in beaker scale experiments via Fe(OH)3 precipitation at pH values &gt / 4.0. A 99 % decrease in aluminium concentration was observed which was attributed to the precipitation of primarily gibbsite and various other mineral phases at pH values &gt / 5.5. As the pH increases, sulphate is adsorbed via Fe(OH)3 and gypsum precipitation at elevated pH. Sulphate attenuation with fly ash was excellent, achieving 98 % attenuation with beaker scale experiments and 1:1 fly ash:AMD ratio. Sulphate attenuation with fly ash was comparable to membrane and ion exchange systems and exceeded the performance of limestone treatment. Except for the larger volumes of fly ash needed to neutralise the AMD, fly ash proved to be a feasible and cost efficient alternative to limestone treatment. Fly ash produced competing results to limestone concerning acidity removal and sulphate attenuation. The comparison highlighted the advantages of utilising fly ash in comparison to limestone and demonstrated its cost effectiveness. The results of this study have shown that fly ash could be successfully applied for the neutralisation of acid mine drainage (AMD) and effectively attenuate the sulphate load in the treated water. The critical parameters to this technology are the variations of chemical composition and mineralogy of fly ash, which could influence the pH, contact time of the neutralisation reaction, and the same is true if the AMD quality varies.</p>

The 1990s has seen an increased awareness of possible environmental effects of corrosion-induced metal release from outdoor constructions. Considerable efforts have been initiated to perform critical assessments of possible risks of selected metals. Gaps of knowledge have been identified and research investigations started. This doctoral thesis is the result of an interdisciplinary research effort in which scientific insight into corrosion, soil chemistry and ecotoxicology has been integrated. The work comprises atmospheric exposure of pure metals and commercial materials for outdoor use. The focus is on release of four metals, copper, zinc, chromium and nickel. Their chemical speciation and bioavailable fraction in metal runoff were determined, both at the release moment and after environmental interaction with, e.g., soil and limestone. Total metal concentrations in runoff are influenced both by material properties (e.g., corrosion product solubility, and specific surface area) and by exposure parameters (e.g., rain volume, intensity, contact time and pollutants). Long-term runoff rates of copper, zinc, chromium and nickel were based on exposures (4-8 years) at standardized conditions (45o inclination facing south) in Stockholm, Sweden. Runoff rates for pure copper range from 1.2 to 1.5 g m-2 yr-1, depending on year. At the copper release moment the potential environmental effect was evaluated using 72 hours growth inhibition test with the green algae Raphidocelis subcapitata. This resulted in a mean value of 15 μg L-1 causing a 50% growth reduction (EC50). Long-term runoff rates for pure zinc range from 1.9 to 2.5 g m-2 yr-1. A considerable variation in average annual runoff rates (0.07-2.5 mg zinc m2yr-1) was observed between different investigated commercial zinc-based materials. An average 72 hour (EC50) value of 69 μg L-1 towards Raphidocelis subcapitata was found for runoff water from zinc-based materials. Long-term runoff rates from stainless steel of grade 304 and 316 range from 0.23 to 0.30 chromium and 0.28 to 0.52 nickel mg m-2 yr-1, with corresponding concentrations in the runoff at the release moment far below reported ecotoxic concentrations for chromium and nickel. Two predictive runoff rate models were successfully developed for transforming copper runoff rate data from Stockholm to other exposure sites. One model is based on rain pH, yearly precipitation and building geometry, and the other on average annual SO2 concentration, yearly precipitation and building geometry. In addition to total metal concentration, adequate effect assessments also require information on chemical speciation of the released metal and its bioavailability. Metal chemical speciation in runoff was determined experimentally through an ion selective electrode (for copper), and also modelled with the Windermere Humic Aquatic model (WHAM (V)). Bioavailability assessments were generated through bioassay tests. At the moment of metal release, all methods show that the majority (60-99%) of the metal in runoff exists in its most bioavailable form, the hydrated metal ion. During subsequent environmental entry the metal undergoes major reductions in concentration and bioavailability. This was evidenced by model column studies of the capacity of soil to retain and immobilize the metal in runoff water, and by model and field column studies of the capacity of limestone to retain copper. The retention by soil of all metals investigated is very high (96-99.8%) until each materials retention capacity is reached. Limestone also exhibits a substantial capacity (5- 47%) to retain copper. The capacity is significantly increased by increased amount and decreased fraction of limestone particles. Any outer or inner surface with significant retention ability and with low possibility of subsequent mobilization is an excellent candidate for neutralizing metal release and its potential ecotoxic effects. This was demonstrated through computer modelling (WHAM(V)) and biosensor tests (Biomet™), which showed the most bioavailable and ecotoxic metal species to be reduced during passage through soil and limestone. Predictions based on the computer model HYDRUS-1D suggest a time-period of between 4 and 8000 years, depending on runoff water and soil characteristics, before saturation in soil retention capacity of copper and zinc is reached. A significant fraction of the retained metal is extractable towards the strong complexing agent EDTA, indicating possible future mobilisation. It is also available for plant uptake, as shown by DGT- (Diffuse Gradients in Thin films-) analysis of copper and zinc in soil. The data generated, presented and discussed are all believed to be important for risk assessment work related to corrosion-induced metal release from outdoor constructions. As evidenced from this doctoral thesis, such work requires a complete set of data on annual runoff rates, concentrations, chemical speciation and bioavailability and its changes during environmental entry, together with knowledge on, e.g., type of material, service life of coating, building geometry, and dewatering system. / QC 20100901

The influence of supplementary materials such as slag, metakaolin and limestone in steam-cured ternary and quaternary cement blends on physical and chemical hydration mechanisms was studied by analyzing the evolution of non-evaporable water content, hydration products and compressive strength. The role of limestone in hydration reactions of cement was also investigated. These properties were studied through the use of differential thermal and thermogravimetric analyses, as well as the loss-on-ignition, X-ray diffraction and compressive strength tests at 1, 3, 7, and 28 days. Research findings revealed that it is possible to replace up to 40% cement with other materials and still achieve compressive strengths similar to mixtures with a 25% cement replacement at 0.34 w/b ratio. Additionally, ternary limestone mixtures exhibited superior mechanical properties to ternary metakaolin mixtures. Lastly, limestone powder was determined to behave as inert filler, accelerating hydration at early ages through heterogeneous nucleation.