A indústria cimenteira busca alternativas para economia de recursos no processo produtivo, em especial envolvendo o uso de materiais residuais no cimento, como escórias siderúrgicas. A escória de aciaria, em particular, apresenta composição desfavorável para aplicação in natura, porém há metodologias na literatura de modificação do material para aplicações cimentícias. No entanto, ainda não se encontram avaliações da corrosão de armaduras de aço em compósitos cimentícios com essa adição, seja em meio sólido ou líquido (água de poro). Esse estudo avaliou, através de curvas de polarização e da espectroscopia de impedância eletroquímica (EIE), a resistência à corrosão do aço CA-50 em soluções representativas de águas de poro extraídas por pressão de pastas de cimento com 25 % de escória de aciaria in natura ou modificada por processo pirometalúrgico. Para efeitos comparativos, foi feita também a avaliação do desempenho do aço em meios de águas de poro indicadas na literatura como representativas de cimento Portland comum e de escória de alto forno. O efeito da presença de espécies agressivas na resistência à corrosão do aço foi avaliado adicionando-se 1,0 % de NaCl em massa às soluções estudadas. Nas águas de poro sem 1,0 % de cloreto, o aço CA-50 apresentou-se passivo e não mostrou indícios de corrosão nos ensaios nem de polarização nem de EIE durante 120 h de imersão. Entretanto, os ajustes dos diagramas com circuito elétrico equivalente (CEE) apontaram que as características de proteção da camada passiva formada nas águas de poro de cimento com escória de aciaria foram superiores, resultando em maior resistência à corrosão do aço CA-50 nestes meios. Por sua vez, nos meios com 1,0 % de NaCl, após polarização e EIE até 120 h, o aço sofreu corrosão para as águas de poro de cimento comum e escória de alto forno, porém não corroeu nas águas de poro representativas de cimentos com escórias de aciaria, cujo melhor desempenho foi associado à maior alcalinidade destes meios. A caracterização microestrutural por microscopia eletrônica de varredura após os ensaios de polarização anódica e de imersão mostrou que o principal produto de corrosão formado foi a lepidocrocita (?-FeOOH), comum em ataque do aço por cloretos. / The cement industry seeks alternatives to save resources in production processes, especially involving the use of residual materials in cements, such as slags. Steel slags present unfavorable composition for application as cement additions in natura, but there are methodologies in the literature for modifying this material for commercial application. However, there are no evaluations of the corrosion of steel reinforcements in cementitious composites with steel slags, either in solid or liquid medium (pore water). The present study employed polarization curves and electrochemical impedance spectroscopy (EIS) to evaluate the corrosion resistance of CA-50 steel in pore water solutions representative of cement pastes with 25 % steel slag in natura or modified by a pyrometallurgical process. For comparison purposes, the performance of CA-50 steel in the pore waters indicated in the literature as representatives of Portland cement and blast furnace slag activated with cement were also evaluated. The effect of aggressive species on the corrosion resistance of the steel was assessed by adding 1.0 % NaCl by mass to the pore water solutions. Without 1.0 % chloride addition, CA-50 steel exhibited good performance and showed no evidences of corrosion in all of the investigated media, both in anodic polarization and in EIS tests performed up to 120 h immersion. However, the fitting of the EIS diagrams with equivalent electric circuit (EEC) revealed that the protectiveness of the passive layer formed in pore waters representative of cements with steel slags were superior, indicating better corrosion resistance of CA-50 steel in these media. Conversely, when 1.0 % chloride was added to the pore waters, CA-50 steel presented pitting corrosion, and impedance decreases with immersion in the pore waters representative of pure cement and blast furnace slag, whereas no corrosion was detected by both methodologies in pore waters representatives of cements with steel slags, which superior performance was ascribed to their higher alkalinity. Microstructural characterization by scanning electron microscopy (SEM) after anodic polarization and immersion tests showed that the main corrosion product formed was lepidocrocite (?-FeOOH), usual of chloride attack of steel.

Reducing the rates of greenhouse gas (GHG) emissions is critical in combatting global climate change. Carbon dioxide (CO2) and methane (CH4) are the two most important carbon-based GHGs, for their atmospheric warming potential. Wetlands such as the Florida Everglades play major roles in the global carbon cycle, as varying hydrologic conditions lead to differential production rates of these two GHGs. This study measured CO2 and CH4 emissions in a re-created Everglades ridge-and-slough wetland, where water levels were controlled to reflect natural flood patterns. As expected, lower elevations were flooded longer and produced more CH4, while higher elevations produced more CO2. Since CH4 has a relatively high global warming potential, CO2 production would need to be 70 times that of CH4, to balance their GHG output. The average ratio of CO2 to CH4 across elevations was 22.0 (mol:mol), indicating that future water management within wetlands should consider GHG production potential.

No description available.

Die Festigkeitssteigerung von Betonen unter hohen Belastungsgeschwindigkeiten ist seit über 100 Jahren im Fokus der Forschung. Bisher konnten bereits eine Vielzahl von möglichen Er-klärungen dieser Festigkeitssteigerung benannt werden, wobei die Heterogenität des Betons im Allgemeinen als eine wesentliche Ursache angenommen werden kann. Die Heterogenität des Betons resultiert aus den im Zementstein eingebetteten Zuschlägen, aber auch durch da-rin eingeschlossene Luft- und Wasserporen, welche Hauptgegenstand dieser Arbeit sind. Es wurde untersucht, inwieweit vorhandenes Porenwasser die Festigkeitssteigerung von Be-ton unter hohen Belastungsgeschwindigkeiten beeinflusst. Auf Basis von experimentellen Ver-suchen im Split-HOPKINSON-Bar an verschiedenen Normalbetonen konnte gezeigt werden, dass vorhandenes Porenwasser die statische und dynamische Betondruckfestigkeit in gleicher Weise signifikant reduziert. Diese Abnahme der Betondruckfestigkeit kann als unabhängig von der Belastungsgeschwindigkeit angesehen werden. Des Weiteren wurden numerische Untersuchungen zum Einfluss von Poren auf die Ausbrei-tung von Belastungswellen durchgeführt. Dabei rückten sowohl das globale Wellenausbrei-tungsverhalten in einer porendurchsetzten Struktur als auch die lokale Wellenbrechung an ei-ner Einzelpore, sowie das Porenmedium (Luft oder Wasser) in den Fokus. Es konnte gezeigt werden, dass vorhandene Poren die Wellenausbreitungsgeschwindigkeit reduzieren und dass das Verhältnis aus Porengröße zur Belastungswellenlänge einen wesentlichen Einflussfaktor für die transiente Spannungsverteilung im Porenbereich darstellt. Insbesondere konnte mit ab-nehmender Belastungswellenlänge eine Reduzierung der örtlichen Kerbspannungen am Po-renrand beobachtet werden, woraus festigkeitssteigernde Effekte resultieren können.

The doctoral thesis deals with usage of gel techniques for in situ measurement of bioavailable metals in soils and sediments. The DGT technique was applied to soil samples from the localities of Zlín, Tuřany and Chrlice for estimation of bioavailable metals in soils. These soils were amended by sewage sludges in years 1980-1987. The experiment using diffusive gels with different pore size, APA and RG gels, has shown that the DGT can be used for assessment of trace metal soil complexes - small inorganic and larger organic. The results obtained by DGT measurements were approximately up to two orders of magnitude lower than metal concentrations obtained by leaching with sodium nitrate. The leaching with sodium nitrate does not provide true reflection of metal availability to plant root system and soil microorganisms and the DGT technique seems to be a better predictor of metal bioavailability. Only small differences between undisturbed and homogenized soil samples were found out by application of DGT to soil samples from localities of Veverská Bítýška and Ostrovačice. The undisturbed soil is not homogenous and the DGT unit gives information only about the part of the soil which is in direct contact with the unit. The procedure with soil slurry can be recommended for the characterization of large soil areas and estimation of bioavailable metals in soils. Gel techniques were also used for the study of processes occuring in sediments. Mercury species and other metals were analysed in surface water, pore water and sediments collected from two sampling sites in the Dele River in northern France. This river had been polluted during the last century by the activity of Métaleurop factory, which dealt with metal ore treatment. The application of DGT technique using two specific ion-exchange resins, Chelex-100 and Duolite GT-73, provided assessment of mercury in sediment pore water. DGT and DET techniques together with centrifugation provided also high resolution depth profiles of Fe, Mn, Zn, Pb, Cr and Cd in pore water. It is not possible to determine which sampling site was more contaminated. Only small differences in mercury species and metal content were observed between sampling sites. The Dele River can be classified as contaminated river according to total mercury content in sediments and as slightly contaminated river from the point of view of methylmercury content. Correlations between mercury species and sulphide content confirm that total mercury and sulphide content count among factors influencing the mercury release to pore water and controlling processes of methylation and demethylation. Only low toxicity of sediment slurries was found out by the bioluminiscence test with Vibrio fischeri. The results of doctoral thesis demonstrate gel techniques as a very good tool in environmental analysis.

The aim of this diploma thesis was to clarify the differences among three different ponds (Bolevecký, Třemošenský, Šídlovský) situated in Pilsen. All of the above mentioned ponds are recreational areas where Bolevecký pond is best known for his water quality improvements since 2006 (after application of Fe and Al - colagulants and also fish - stock changes). The main difference was based on the growth of submersed water plants. The macrophytes were growing slowly or not at all in Bolevecký pond. There was a huge expansion of macrophytes (mainly Myriophyllum spicatum species) in Třemošenský and Šídlovský ponds therefore the water plants must be regulated during summer seasons by mechanical harvesting. The water in all three ponds proves the same qualities but the differences may be found in the nutrient composition of sediments. The fractionation analysis (the founders Psenner and Puczsko) confirmed the fact that all localities are poor in phosphorus however the differences were found in content of iron. The increased content of iron was observed in sediments of Šídlovksý and Třemošenský ponds (mainly in BD fraction - the iron was unstable under redox potential changes). The result of this analysis proves that phosphorus is potentially more available for macrophytes in sediments of Třemošenský and Šídlovský...

O Complexo Billings é o maior reservatório de água da Região Metropolitana de São Paulo. Devido a sua importância estratégica e à degradação da qualidade de suas águas e sedimentos, a represa foi e continua sendo alvo de muitas pesquisas. No entanto, os valores-guia da qualidade de sedimentos (VGQS) adotados pelas normas nacionais vigentes, usualmente aplicados nestes estudos, baseiam-se na abordagem canadense Threshold Effect Level/Probable Effect Level (TEL/PEL), e sua interpretação quanto aos efeitos tóxicos podem divergir dos países que as originaram. O objetivo deste trabalho foi avaliar o potencial tóxico de contaminantes orgânicos e inorgânicos na água e nos sedimentos do reservatório Billings por meio da utilização de diferentes VGQS empíricos e teóricos e ensaios ecotoxicológicos. Uma abordagem multi-tarefas foi conduzida através de avaliações em campo e em laboratório envolvendo extensas caracterizações químicas, físicas e toxicológicas ao longo de dez pontos do reservatório. Em cada local, os parâmetros de qualidade da água superficial foram monitorados in situ. Amostras de sedimento integral, água intersticial e superficial foram coletadas para a avaliação das propriedades físicas e químicas nestes locais, como granulometria e carbono orgânico total (COT). Os teores de sulfetos volatilizáveis por acidificação (SVA) e os metais extraídos simultaneamente (MES) foram obtidos nas amostras de sedimento integral, assim como as concentrações totais de metais (Cd, Cr, Cu, Fe, Mn, Ni, Pb e Zn) e contaminantes orgânicos (pesticidas organoclorados e hidrocarbonetos aromáticos polinucleares). Os contaminantes foram então comparados a diferentes linhas de evidências (LDE), dentre elas VGQS empíricos (TEL/PEL, LEL/SEL e VRR), VGQS baseados na teoria do Equilíbrio de Partição (EqP) e ensaios ecotoxicológicos com as espécies Daphnia magna e Hyalella azteca em água superficial e sedimento integral, respectivamente. As concentrações de metais nas águas superficial e intersticial do reservatório foram relativamente baixas e ausentes de efeitos crônicos ou agudos pelos ensaios ecotoxicológicos. Os teores de SVA foram superiores aos de MES quando normatizados pela fração COT. Embora a LDE baseada em EqP tenha sugerido a ausência de toxicidade nos sedimentos do reservatório Billings, a mesma ocorreu nos pontos Braço do Rio Grande e Barragem de Pedreira. Os resultados dos ensaios ecotoxicológicos demonstraram efeitos agudos para Hyalella azteca, com sobrevivência dos organismos de 32,5 ± 6,57% e 45 ± 5,77% nos pontos Braço do Rio Grande e Barragem de Pedreira, respectivamente. Efeitos crônicos também foram observados para a espécie H. azteca em ambos os pontos. Os valores de biomassa individuais dos anfípodas foram afetadas quando comparadas ao Controle (0,072 ± 0,01 mg), com valores de 0,032 ± 0,01 mg e 0,031 ± 0,01 mg no Braço do Rio Grande e Barragem de Pedreira, respectivamente. A utilização dos VGQS empíricos TEL/PEL e os Valores de Referência Regionais demonstraram ser eficazes para predição de efeitos tóxicos, visto que as concentrações dos metais Cu, Cr, Ni, e Zn presentes nos sedimentos superaram o limiar PEL em vários pontos do reservatório, indicando uma alta probabilidade de efeitos adversos à biota, comprovada pelos ensaios ecotoxicológicos. As concentrações dos pesticidas organoclorados mirex e DDT encontram-se acima de TEL, enquanto o DDE, mais persistente, demonstrou uma alta probabilidade de ocorrência de efeitos tóxicos (acima de PEL). Embora o EqP não tenha sido eficaz na predição dos efeitos tóxicos, foi imprescindível para compreender a dinâmica dos metais no reservatório, visto que os elevados teores de sulfetos e COT demonstram ser os responsáveis pelo equilíbrio dos metais neste ambiente. Dessa forma, a combinação de VGQS empíricos e teóricos pode - de maneira não regulatória - ser considerada uma solução efetiva e de baixo-custo para a tomada de decisão sobre locais passivos de contaminação. / The Billings Complex is the largest water-storage facility in the São Paulo Metropolitan Region. Due to its strategic importance and the deterioration in its water quality over time, the Billings reservoir was and remains subject of many researches. However, the sediment quality guidelines (SQGs) adopted in Brazil and usually applied in these studies are based on the Canadian Threshold Effect Level/Probable Effect Level (TEL/PEL) and may not suitably predict ecotoxicological effects. The aim of this study was to evaluate the toxicity of organic and inorganic compounds in the overlying water, pore water and bedded sediments of the Billings reservoir through several SQGs and toxicological tests. A laboratory and field assessment was conducted involving extensive physical, chemical, and toxicological characterizations within ten stations of the Billings reservoir. At each sampling station, water quality parameters (pH, redox, DO, conductivity, turbidity, and temperature) were measured in depth (intervals of 1 meter). Bedded surface sediment, sediment pore water, and overlying water were collected to assess the physical and chemical properties at these sites, such as particle size and total organic carbon (TOC). Sediment samples were analyzed for acid volatile sulfides (AVS) and simultaneously extractable metals (SEM), total metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) and organic contaminants (organochlorine pesticides and semivolatile organic compounds). Empirical (TEL/PEL, RRV, and LEL/SEL) and mechanistic (AVS/SEM) SQGs approaches were applied and compared with 10-d toxicity tests with Daphnia magna and Hyalella azteca for overlying water and bedded sediment, respectively. Metals in the overlying and pore water were at a relatively low concentrations and absent of chronic or acute effects. AVS concentrations was greater then SEM in every station of the reservoir, therefore suggesting the absence of toxicity. However, Hyalella azteca post-exposure survival was affected in both Rio Grande branch and Pedreira Dam stations (32,5 ± 6,57% and 45 ± 5,77%, respectively). Relative growth rates were also affected in both Rio Grande branch and Pedreira Dam stations (0,032 ± 0,01 mg and 0,031 ± 0,01 mg) when compared to Control (0,072 ± 0,01 mg). Empirical (TEL/PEL, RRV, and LEL/SEL) guidelines were more suitable for toxicity prediction. Several stations exhibit metal concentrations for Cu, Cr, Ni, and Zn higher than the Canadian PEL adopted in Brazil. Organic compounds such as mirex and DDT were above TEL. Persistent DDT metabolite p,p\'-DDE were above PEL in both Rio Grande branch and Pedreira Dam stations. Although EqP was not suitable for toxicity prediction, it was important for understanding the role of sulfides and TOC for metal contamination in the reservoir. Therefore, the adoption of both empirically and mechanistic SQGs for sediment quality assessments can provide a more accurate and low cost alternative for sediment management decisions.

Sediment quality guidelines (SQGs) or values (SQVs) are used to assess the potential risk of contaminants in sediment to aquatic organisms, specifically benthic invertebrates. The objectives of this research were to evaluate SQGs derived specifically for use by the uranium industry in Canada, propose alternative SQVs for use at uranium operations in northern Saskatchewan using a novel approach, and investigate the potentially bioavailable fractions of metals in sediment which could become an alternative measurement to the typically used total metal concentrations. The screening-level concentration (SLC) approach has been used in Ontario, Canada, to derive lowest effect levels (LELs) and severe effect levels for use as SQGs. This approach was adopted by the Canadian Nuclear Safety Commission (CNSC) to set guidelines for metals (As, Cr, Cu, Pb, Mo, Ni, Se, U, and V) and radionuclides (Ra-226, Pb-210, and Po-210) in sediment at northern Saskatchewan uranium mining and milling operations. The SLC approach is based on total metal and radionuclide concentrations in sediment, and corresponding benthic invertebrate community composition data for a specific sampling site. In this study, sediment chemistry (total metals and radionuclides) and benthic community data from northern Saskatchewan uranium operations were compiled and examined. Results indicated that the CNSC-derived SQGs had limited relationships to observed effects, or lack thereof, on benthic invertebrate communities near uranium operations in Saskatchewan. On a general basis, the correct alignment of at least one LEL exceedence at an effect site was observed 95% of the time, but on an element-specific basis many of the elements had concentrations at effect sites below their LELs. Furthermore, concentrations of the evaluated elements exceeded at least one LEL at 60% of the no-effect sites. The high number of exceedences of LELs at reference and no-effect sites (false-positives) calls to question the appropriateness of the CNSC-derived SQGs. To address the deficiencies of the SLC approach, a new approach was developed to derive alternative metal SQVs for the uranium industry in northern Saskatchewan that was based on the use of reference and no-effect site field data. Three different sets of NE values were derived using combinations of benthic invertebrate community effect criteria (abundance, richness, evenness, Bray-Curtis index). Additionally, reference (REF) values were derived based solely on sediment metal concentrations from reference sites. In general, NE values derived using abundance, richness, and evenness (NE1 and NE2 values) were found to be higher than the NE values derived using all four metrics (NE3 values). Derived NE values for Cr, Cu, Pb, and V did not change with the incorporation of additional effects criteria due to a lack of influence from the uranium operations on these metal concentrations (i.e., they were generally present at or near background levels). However, a gradient of exposure concentrations was apparent for As, Mo, Ni, Se, and U in sediment which allowed for acceptable exposure levels of these metals in sediment to be defined. The findings from this assessment proposed a set of new, alternate SQVs for use at the uranium industry in northern Saskatchewan. Often, only total metals concentrations are measured in the evaluation of contaminated sediment. However, this measure may over-estimate metal exposure to benthic invertebrates. Using sediment cores collected from near the Rabbit Lake and Key Lake uranium operations, along with a series of mixed-sediments (contaminated and reference sediment), metal bioaccumulation experiments using Chironomus dilutus were conducted in the laboratory. Metal concentrations in extracts from single extractions with either potassium phosphate or hydrochloric acid on wet and dried sediment, pore-water, and whole-sediment were used to evaluate metal bioaccumulation in test organisms. Depending on the metal, pore-water isolated using peepers generally exhibited the best relationship with tissue metal concentrations. Based on this finding, it is suggested that pore-water sampling using peepers (an in-situ dialysis device) be added to environmental sampling programs at Saskatchewan uranium operations so that sediment metal availability to benthic invertebrates can be better assessed. With the eventual development of a larger pore-water metals dataset, SQGs based on pore-water metals concentrations could likely be derived as an alternative to existing SQGs based on total metal concentrations in sediment.

Sediment quality guidelines (SQGs) or values (SQVs) are used to assess the potential risk of contaminants in sediment to aquatic organisms, specifically benthic invertebrates. The objectives of this research were to evaluate SQGs derived specifically for use by the uranium industry in Canada, propose alternative SQVs for use at uranium operations in northern Saskatchewan using a novel approach, and investigate the potentially bioavailable fractions of metals in sediment which could become an alternative measurement to the typically used total metal concentrations. The screening-level concentration (SLC) approach has been used in Ontario, Canada, to derive lowest effect levels (LELs) and severe effect levels for use as SQGs. This approach was adopted by the Canadian Nuclear Safety Commission (CNSC) to set guidelines for metals (As, Cr, Cu, Pb, Mo, Ni, Se, U, and V) and radionuclides (Ra-226, Pb-210, and Po-210) in sediment at northern Saskatchewan uranium mining and milling operations. The SLC approach is based on total metal and radionuclide concentrations in sediment, and corresponding benthic invertebrate community composition data for a specific sampling site. In this study, sediment chemistry (total metals and radionuclides) and benthic community data from northern Saskatchewan uranium operations were compiled and examined. Results indicated that the CNSC-derived SQGs had limited relationships to observed effects, or lack thereof, on benthic invertebrate communities near uranium operations in Saskatchewan. On a general basis, the correct alignment of at least one LEL exceedence at an effect site was observed 95% of the time, but on an element-specific basis many of the elements had concentrations at effect sites below their LELs. Furthermore, concentrations of the evaluated elements exceeded at least one LEL at 60% of the no-effect sites. The high number of exceedences of LELs at reference and no-effect sites (false-positives) calls to question the appropriateness of the CNSC-derived SQGs. To address the deficiencies of the SLC approach, a new approach was developed to derive alternative metal SQVs for the uranium industry in northern Saskatchewan that was based on the use of reference and no-effect site field data. Three different sets of NE values were derived using combinations of benthic invertebrate community effect criteria (abundance, richness, evenness, Bray-Curtis index). Additionally, reference (REF) values were derived based solely on sediment metal concentrations from reference sites. In general, NE values derived using abundance, richness, and evenness (NE1 and NE2 values) were found to be higher than the NE values derived using all four metrics (NE3 values). Derived NE values for Cr, Cu, Pb, and V did not change with the incorporation of additional effects criteria due to a lack of influence from the uranium operations on these metal concentrations (i.e., they were generally present at or near background levels). However, a gradient of exposure concentrations was apparent for As, Mo, Ni, Se, and U in sediment which allowed for acceptable exposure levels of these metals in sediment to be defined. The findings from this assessment proposed a set of new, alternate SQVs for use at the uranium industry in northern Saskatchewan. Often, only total metals concentrations are measured in the evaluation of contaminated sediment. However, this measure may over-estimate metal exposure to benthic invertebrates. Using sediment cores collected from near the Rabbit Lake and Key Lake uranium operations, along with a series of mixed-sediments (contaminated and reference sediment), metal bioaccumulation experiments using Chironomus dilutus were conducted in the laboratory. Metal concentrations in extracts from single extractions with either potassium phosphate or hydrochloric acid on wet and dried sediment, pore-water, and whole-sediment were used to evaluate metal bioaccumulation in test organisms. Depending on the metal, pore-water isolated using peepers generally exhibited the best relationship with tissue metal concentrations. Based on this finding, it is suggested that pore-water sampling using peepers (an in-situ dialysis device) be added to environmental sampling programs at Saskatchewan uranium operations so that sediment metal availability to benthic invertebrates can be better assessed. With the eventual development of a larger pore-water metals dataset, SQGs based on pore-water metals concentrations could likely be derived as an alternative to existing SQGs based on total metal concentrations in sediment.

This thesis analyses the governing equation of elastic wave propagation by the finite difference method , and considered absorbing boundary condition and the material damping to simulate behavior of wave propagation. Otherwise, we combined with the mechanics of the soil pore water pressure raised by shear stress effected repeatedly and the soil property is changed by water pressure effected to simulate physical phenomenon in half-space, and probe into the soil liquefaction process during different force types. Using the developed numerical wave propagation model probe into reducing vibration by dug trench and filler trench, and analyzed data by 1/3 octave band method. This thesis discuss with reducing vibration effect by different trench disposed¡Bdifferent filler material property, complex filler, and extending the force source pile length.