Neste trabalho avaliou-se o desempenho de um reator anaeróbio operado em batelada seqüencial e contendo biomassa imobilizada (ASBBR) em espuma de poliuretano quando submetido a diferentes tempos de alimentação e cargas orgânicas volumétricas, além da aplicação de cargas de choque orgânicas. O reator, com mistura por recirculação da fase líquida e mantido à 30 ± 1 ºC, tratou soro de queijo reconstituído e possuiu 2,5 L de volume reacional. Os resultados mostraram que o tempo de alimentação utilizado exerceu maior influência sobre o desempenho do reator para maiores valores de carga orgânica volumétrica. Durante a operação com carga orgânica volumétrica de 3 gDQO/L.d, a alteração do tempo de alimentação não influenciou na eficiência de remoção de matéria orgânica filtrada, que foi de 98%. Sob carregamento orgânico volumétrico de 6 gDQO/L.d, verificou-se tendência de queda daquela variável para maiores tempos de enchimento: 99, 98 e 97%, para tempos de alimentação de 2, 4 e 6 horas, respectivamente. Na operação com carga orgânica volumétrica de 12 gDQO/L.d, o aumento do tempo de alimentação resultou em queda mais significativa da eficiência de remoção de matéria orgânica filtrada: 97, 95 e 93%, para tempos de alimentação de 2, 4 e 6 horas, respectivamente. Em todas as condições, a aplicação de cargas de choque de 24 gDQO/L.d causaram o aumento da concentração de ácidos no efluente. No entanto, apesar desse aumento, o reator retomou rapidamente sua estabilidade, sendo a alcalinidade otimizada ao afluente suficiente para manter o pH próximo do neutro durante toda a operação. Independente da carga orgânica volumétrica aplicada, a operação com tempo de alimentação de 2 horas foi aquela que proporcionou maior estabilidade e menor suscetibilidade do processo às cargas de choque orgânicas. / This work assessed the performance of an anaerobic sequencing batch reactor containing immobilized biomass (ASBBR) on polyurethane foam when submitted to different feeding times, volumetric loading rate and organic shock loads. The reactor, in which mixing occurred by recirculating the liquid phase, contained 2,5 L reaction medium and was maintained at 30 ± 1 ºC for treating reconstituted cheese whey. Results showed that the effect of feeding time on reactor performance was more pronounced at higher volumetric loading rates. During operation at volumetric loading rate of 3 gDQO/L.d, changing feeding time did not affect filtered organic matter removal efficiency, which amounted to 98%. At volumetric loading rate of 6 gDQO/L.d, removal efficiency showed a tendency to drop at higher feeding times: 99, 98 and 97%, for feeding times of 2, 4 and 6 hours, respectively. At volumetric loading rate of 12 gDQO/L.d, increase in feeding time resulted in a more significant drop in filtered organic matter removal efficiency: 97, 95 and 93%, for feeding times of 2, 4 and 6 hours, respectively. Application of shock loads of 24 gDQO/L.d caused increase in acids concentration in the effluent, at all conditions. However, despite this increase, the reactor readily regained stability and optimized alkalinity supplementation to the influent was sufficient to maintain near neutral pH during the entire operation. Regardless of applied volumetric loading, operation with feeding time of 2 hours was which yielded maximum stability and reduced susceptibility of the process to organic shock loads.

>Magister Scientiae - MSc / Chemical speciation and the evaluation of species distribution is the key to understanding the potential of brines to form scale or corrode the water circuit as well as the potential of mobility and release trends of the pollutants into the environment. It is important to identify highly soluble free ions in water chemistry because toxicity of ions is related to mobility and consequently bioavailability. The chemical composition, character and chemical speciation modelling of saline effluents (brines) at Tutuka Power Station and Sasol Synthetic Fuels Complex in Secunda were studied. The form in which chemical species exist (chemical speciation) and the physical and chemical interactions of species in saline effluents at these two study sites is not fully understood. This study investigated how pH, temperature, alkalinity and chemical composition influenced chemical speciation, species distribution, scale forming and corrosion potentials of the different saline effluent streams at the two sites using computer programs PHREEQC and Aq.QA. Characterizations of the results were presented in Stiff and Piper diagrams generated by the Aq.QA computer software. Chemical speciation modelling of the brines showed that scale-forming minerals aragonite, calcite, hematite, anhydrite and gypsum have positive saturation indices between 0 and 20 in mine water, RO brine at Tutuka and Sasol Secunda, EDR brine at Sasol Secunda and VC brine at Tutuka Power Station. The water types at Tutuka Power Station were found to be mainly Na-S04 water types and those at Sasol Secunda were a mixture of Na-Cl and Na-S04 water types. Water treatment chemicals playa major role in increase were absent in the intake water. It was found that Sasol Secunda water streams are much more heavily contaminated than Tutuka water streams. The study also found that the mine water utilised at Sasol Secunda is two-fold more polluted than the mine water utilised at Tutuka although these sites are a mere 40 km apart. The sodium adsorption ratios showed that all the saline effluent streams at Tutuka and Sasol Secunda were unsuitable for irrigation, except for desalination product waters. Chemical speciation showed that the predominant species in the most concentrated saline effluent (VC brine) at Tutuka were the free cr ion at approximately 100 % with very minute quantities of FeCI+ and ZnCI+ and the predominant sodium species were the free Na+ ion which existed at 85 %. Magnesium species had the predominant form as the ionic compound MgS04 at 73 % and the carbonates were mainly in the form of NaC03- (53 %), HC03- (28 %) and CO{(7 %). The most concentrated brine analysed at Sasol Secunda was the TRO brine. PHREEQC did not predict the precipitation of CaC03 from the TRO brine at Sasol Secunda. The most abundant calcium species were Ca2+(59 %) ions and CaS04 (40 %). The brine was at a pH of 5.76 with dissolved CO2 at 73 % of the carbonate species. Trace elements were evaluated and the toxic trace elements varied from 0.07 mg/L (As) to 26.75 mg/L (Sr) at Sasol Secunda. At Tutuka Power Station the toxic trace elements in brines varied from 0.02 mg/L (As/Se) to 16.85 mg/L (Sr). Sr and B were found to be the most highly concentrated toxic elements. The major and trace ion chemistry, alkalinity, pH, sodium adsorption ratios, change in concentration of the water streams and the brine chemical composition after contact with ash was also evaluated. When saline effluents at Tutuka Power Station and Sasol Secunda are combined with ash, pH, Ca content and alkalinity of the resulting solution increased. The chemical composition of saline effluents can be influenced by the ingress of CO2 from the atmosphere. The study shows conclusively that brine composition and concentration is highly variable at these South African power utilities and processes such as RO, contact with ash and C02 ingress can have an impact upon the overall brine quality. Aq.QA was found to be a more accurate tool for classifying waters according to dominant ions than Stiff diagrams but Stiff diagrams still have the superior advantage of being a mapping tool to easily identify samples of similar composition as well as quickly identify what has been added or what has been removed from a water stream. Chemical speciation could identify effluent streams where C02 dissolution had taken place.

Sinking Creek, located in upper east Tennessee, is on the 303(d) list for not meeting minimum water quality standards for recreation. A Total Maximum Daily Load (TMDL) for fecal coliforms was developed. The purpose of this study was to investigate the use of water quality parameters to identify areas that contribute to the fecal coliform loading. Concentrations of nitrate-N, orthophosphates, BOD, alkalinity, hardness, and optical brighteners (OB) were monitored at fourteen stations monthly for one year. Site 3 (agricultural region) exhibited the highest average nitrate-N loadings (627.34 mg/sec) and orthophosphate (as PO43-) loadings (84.83 mg/sec). Alkalinity loadings ranged from 10.00 mg as CaCO3/sec to 163,500.00 mgCaCO3/sec. Hardness loadings ranged from 2.00 mg as CaCO3/sec to 96,200.00 mgCaCO3/sec. The agricultural sites exhibited higher loadings for all water quality parameters measured (except OB) than the urban and forest areas. Nutrient loadings appeared to be related to agricultural land use patterns.

This dissertation includes theoretical and applied components that address the effect of coatings on rates of mineral reactions that occur in acid mine drainage (AMD) environments. The two major projects investigated how diffusion-limited transport of reactants through pore spaces in coatings on mineral grains affects the reaction rate of the underlying mineral. The first project considered the growth of gypsum coatings on the surface of dissolving limestone in anoxic limestone drains (ALD), which reduces the neutralization rate of the dissolving limestone and the subsequent effectiveness of this treatment. The second project investigated the conditions where iron oxyhydroxide coatings form on oxidizing pyrite and the potential strategies to prevent "runaway" AMD by reducing the rate of acid production to the point that the acid can be neutralized by the surrounding rocks. In both studies, experiments were conducted to measure reaction rates for the underlying minerals, as coatings grew thicker. These experimental data were fit to a diffusion model to estimate diffusion coefficients of reactants through pore spaces in coatings. These models are extrapolated to longer times to predict the behavior of the coated grains under field conditions. The experimental results indicate that management practices can be improved for ALDs and mine waste piles. For example, supersaturation with respect to gypsum, leading to coating formation, can be avoided by diluting the ALD feed solution or by replacing limestone with dolomite. AMD can be prevented if the rate of alkalinity addition to mine waste piles is faster than acid is produced by pyrite oxidation. The diffusion model developed in this study predicts when iron oxyhydroxide coatings will become thick enough that alkalinity from the surroundings is sufficient to neutralize acid produced by coated pyrite oxidation and additional alkalinity is no longer required. / Ph. D.

Municipal wastewater treatment plants (WWTP) are important infrastructural components in a society and also important for sustainability. In a WWTP the most common treatment configuration is mechanical, biological, and chemical treatment of the wastewater. The treatments reduce nutrients and organic matter before the water is transferred to the recipient. During wastewater treatment, sludge is produced and then stabilized in an anaerobic digestion (AD) process.  The Käppala Association operates the third largest WWTP in Sweden. In the future the Käppala plant is expecting an increased number of connected households and also stricter sludge hygienization regulations. This implies that current strategies for the WWTP have to be developed. One idea has been to use a thermophilic AD process instead of mesophilic AD.Thermophilic AD has previously been shown to have higher capacities, lower hydraulic retention times (HRT) and increased pathogenic destruction compared to their mesophilic counterpart. A common negative aspect for a thermophilic process has been process instability.  In this study a 5 m3 pilot plant rented from Research Institutes of Sweden (RISE) was used to evaluate maximal organic loading rate (OLR) for a stable thermophilic AD process using mixed sludge as substrate. Four HRT were chosen, and each HRT was maintained for 3 retention times. Laboratory analyzes of the raw and digested sludge and on-line monitoring were performed regularly to collect information about process stability and efficiency. The pilot plant was controlled through a surveillance system where operating parameters were introduced. The main objectives of this study were to investigate how an increase of OLR affected pH, alkalinity, and volatile fatty acid (VFA) content and also how the alkalinity and VFA affected the process stability. Gas composition, gas production, degree of digestion (DD) and foaming were also investigated throughout this study. Results showed that VFA initially increased, and alkalinity decreased when every OLR increase occurred. The VFA and alkalinity returned to lower values after the process was given time to recover during constant OLR. The OLR increase caused slight variations in process pH but not enough for process failure. Increased OLR did not seem to have a large impact on the DD since it seemed to remain between 40-50% throughout the entire study. Composition monitoring showed an increased hydrogen sulfide content in the gas as a consequence of increased OLR. An OLR increase also lead to a volumetric gas production (VGP) and volumetric methane production (VMP) increase while efficiency of the AD process was seen to decrease when evaluating specific gas production (SGP) and specific methane production (SMP). The conclusion of the study was that a stable thermophilic AD process using mixed sludge as substrate could be operated with an OLR of 6.55 ± 0.06 kg VS m-3d-1and a HRT of 7 days. Maximal OLR for a stable thermophilic AD process was never achieved due to the process remaining relatively stable the entire experimental period. The process recovered from signs of instability during all HRT-transition times indicating it can maintain all investigated OLR. / Kommunala avloppsreningsverk är en viktig infrastruktur i ett samhälle och även viktigt för hållbarheten. I ett avloppsreningsverk renas spillvatten genom mekaniska, biologiska och kemiska behandlingar processteg. Behandlingarna minskar näringsämnen och organiskt material innan vattnet rinner ut i recipienten. Vid rening av avloppsvatten erhålls slam. Slammet kan användas som substrat för en anaerobisk nedbrytningsprocess. Käppalaförbundet driver det tredje största reningsverket i Sverige. I framtiden förväntas antal anslutna hushåll till reningsverket att öka samt strängare slamhanteringskrav appliceras. Detta innebär att nuvarande slamstrategi måste utvecklas. En idé är att tillämpa en termofilrötnings process. En termofil rötningsprocess har visat sig ha högre kapacitet, lägre uppehållstider och ökad patogen reduktion i jämförelse med en mesofil rötning. En nackdel med termofil rötning är den försämrade processtabiliteten.  I denna studie har en 5 m3 pilotanläggning inhyrd från RISE använts för att utvärdera den maximala organiska belastningen för en stabil termofil rötningsprocess med blandslam som substrat. Fyra uppehållstider valdes och varje uppehållstid hölls tre gånger. Regelbundna analyser av rå och rötslam utfördes för att erhålla information om process stabilitet och effektivitet. Pilotanläggningen styrdes genom ett människa-maskingränssnitt där driftparametrar matades in. Huvudmålen för studien var att se hur en ökning av organisk belastning påverkade pH, alkaliniteten och halt av flyktiga fettsyror samt att undersöka alkalinitetens och halten av flyktiga fettsyrors påverkan på processtabiliteten. Påverkan av en ökad organisk belastning på gas sammansättning, gasproduktion, rötningsgrad har även undersökts. Resultaten visade att flyktiga fettsyror initialt ökade och alkaliniteten minskade vid en belastnings ökning. Flyktiga syror och alkalinitet återgick till mer stabila värden efter processen fick återhämta sig vid en konstant belastning. Belastningsökningen orsakade små variationer i pH värdet men inte tillräckligt för att orsaka processkollaps. En ökad belastning verkade inte ha någon större påverkan på rötningsgraden då den låg runt 40–50% hela rötningsperioden. Skumutvecklingen visade sig inte heller vara ett problem. Resultaten visade även att väte sulfid ökade i gasen när en belastningsökning gjordes. Den volymetriska gas och metan produktionen ökade vid en ökad OLR medan specifika gas och metan produktionen minskade. Slutsatsen var att en stabil termofil rötningsprocess av blandslam kan drivas med en organisk belastning på 6.55 ± 0.06 kg VS m-3d-1 och en uppehållstid på 7 dagar. Maximal belastning för stabil termofil rötningsprocess uppnåddes dock ej då processen förblev relativt stabil under alla undersökta uppehållstider. Processen återhämtade sig även efter tecken på instabilitet vilket indikerar att AD processen kan behålla stabilitet vid de undersökta belastningar.

<p>Hydrated portland cement provides the solid adhesive matrix necessary to bind aggregate (sand and gravel) into concrete. The hydration reaction requires water, however the products of the reaction limit further diffusion of water to unreacted cement. Superabsorbent polymer (SAP) hydrogel particles absorb mixing water, then subsequently desorb when the relative humidity drops, serving as internal water reservoirs within the cement matrix to shorten diffusion distances and promote the hydration reaction in a process called internal curing. Internally cured cementitious mixtures exhibit an increased degree of hydration and reduced shrinkage and cracking, which can increase concrete service life. Increased service life can, in turn, reduce overall demand for portland cement production, thereby lowering CO2 emissions.</p> <p>This dissertation addresses practical implementation questions key to the translation of SAP hydrogel internal curing technology to from the benchtop to the field in transportation applications, including: (1) What effects do mix design adjustments made to increase mixture flow when using SAP have on cementitious mixture properties? and (2) What effect do cementitious binder characteristics have on SAP performance?</p> <p>The addition of SAP to a cementitious mixture changes the mixture’s flow behavior. Flow behavior is an important aspect of concrete workability and sufficient flow is necessary to place well consolidated and molded samples. Often, additional water is added to mixtures using SAP to account for the absorbed water, however cementitious mixture workability is often tuned using high range water reducing admixtures (e.g., polycarboxylate ester-based dispersants). Fresh and hardened properties of mortars were characterized with respect to flow modification method (using the mortar flow table test; compressive strength at 3, 7, and 28 days; flexural strength at 7 and 28 days; and microstructural characterization of 28-day mortars). At typical doses, it was found that the addition of extra water lowers the resulting compressive and flexural strength, while high range water reducing admixtures administered at doses to achieve sufficient mortar flow did not compromise compressive or flexural strength.</p> <p>The SAPs used in cement are generally poly(acrylamide-acrylic acid) hydrogels and are not chemically inert in high ionic-load environments, such as cement mixtures. The behavior of an industrial SAP formulation with characterized across five different cement binder compositions with respect the cement hydration reaction (using isothermal calorimetry, thermogravimetric analysis of hydration product fraction, and scanning electron microscopy (SEM)/energy dispersive x-ray spectroscopy (EDS) microstructural analysis), the absorption behavior of the SAP, and the fresh and hardened properties of SAP-cement composites (mortar flow and compressive and flexural strength). The change in properties induced by the addition of SAP was similar across ASTM Type I cements from three manufacturing sources, suggesting that SAP internal curing can be implemented predictably over time and geography. Excitingly, in analysis of cement systems meeting different ASTM standards (Type III and Type I with 30% replacement by mass with ground blast furnace slag), synergistic and mitigating reaction behaviors were observed, respectively, in Type III and slag cement, suggesting that further study of SAP with these cement systems could be of particular interest.</p>

[Truncated abstract] Acidic mine lakes are formed as a result of the oxidation and dissolution of metal sulfide minerals and are primarily characterized by low pH values of 2 – 4. Many strategies for the bioremediation of acidic mine lakes depend on the alkalinity generation capabilities of microbial ferric and/or sulfate reducing bacteria. However nearly all mine lakes are oligotrophic, with very low concentrations of available organic carbon and nutrients; all required for healthy microbial growth. There is also an unusual class of mine lakes characterized by low concentrations of organic carbon and also very low concentrations of dissolved iron and sulfate. Our ability to promote microbial activity in these systems is especially challenging. This study focuses on one of these systems, Lake Kepwari, a coal mine lake in Western Australia. Numerical modeling of remediation strategies is an efficient way of testing scenarios prior to expensive in-field trials. However such modeling relies on good descriptions of microbial processes, including kinetic parameterizations of ferric and sulfate reduction. There has been little research to date on the study of kinetic parameterizations of the chemical and biological alkalinity generation in acidic mine lakes. The objectives of this thesis were to investigate the viability of microbial ferric and sulfate reduction in an ultraoligotrophic, acidic mine lake, to assess the impact of these microbial processes on water quality and to parameterize the Dual Monod kinetics of neutralization under dual limitation conditions. Molecular analyses including most probable number, DNA extraction, polymerase chain reaction, polymerase chain reaction – denaturing gradient gel electrophoresis were used to examine the microbial communities in the lake sediments. ... The Monod maximum specific microbial growth rates with respect to dissolved organic carbon and ferric, and as determined in batch experiments, were 0.07 ± 0.01 and 0.048 ± 0.02 day-1, respectively, and their corresponding Monod half saturation constants and were 14.37 and 5.6 mmol L-1. The Monod maximum consumption rates under ferric and OC limitation were also estimated. The Monod maximum specific microbial growth rates with respect to dissolved organic carbon and sulfate, , and were 0.05 ± 0.01, 0.08 ± 0.01 and 0.07 ± 0.02 day-1, respectively, and their corresponding Monod half saturation constants, and were 75.5, 131.8 and 10.2 mmol L-1. The Monod maximum consumption rates under sulfate and OC limitation were also estimated. The results of this study suggest that strategies for the remediation of ultraoligotrophic, acidic mine lakes may rely on microbial ferric and sulfate reduction, however additions of both organic carbon and sulfate/ferric are essential. These results can be immediately applied to mesocosm studies in outdoor enclosures and to the management of acidic mine lakes. Furthermore, this thesis has provided a new, valuable understanding on the Dual Monod kinetic parameterizations of neutralization for an ultraoligotrophic, acidic mine lake environment. These parameterizations are essential for the lake ecological models that will be used to investigate remediation scenarios for acidic mine lakes.

Soils in irrigated fields are impacted by irrigation water quality. Salts in the irrigation water may accumulate in the soil depending on amount of leaching, the quality of water and type of ions present. Salinity is an environmental hazard that is known to limit agriculture worldwide. The quality of irrigation water is thus of concern to agriculturists. More so is the impact it has on productivity. The objective of this study was to quantify the impact due to use of ground water of such quality, with respect to salinity, as found in Berambadi watershed of Southern India, under farmers‟ field conditions. Turmeric (Curcuma Longa L.) was used for the study, based on salt sensitivity, under furrow irrigation. Study sites were selected basing on quality of water, with respect to salinity, crop and irrigation method. Samples of both soil and water were collected from each site and analyzed in the laboratory. The samples were analysed for salinity, alkalinity, pH and Cations of Magnesium, Sodium, Calcium and potassium as well as Chlorides and Sulfates. In addition soil was analysed for texture and Organic matter content. Non destructive plant monitoring for Leaf area (Index), number of leaves and plant height was done up to 210 days from planting. Profile, up to 80 cm depth, soil moisture was monitored at six plots using TDR and surface, up to 6cm depth, soil moisture for all the plots using Theta probe. Potential yield was obtained using STICS 6.9 crop model while field yield was estimated from rhizomes average weight of three plants. For both potential and observed yield estimation, a plant density of 9 plants per M2 was used. The quality parameters in water were correlated to soil parameters and to crop growth and ultimate yield. Impact due to salinity was then identified and quantified using relative yield. Identified quality problems in terms of turmeric response were, salinity, alkalinity and pH there was significant positive correlation between irrigation water salinity and soil salinity. Some wide scatter was observed and could be indicative of irrigation management practices, soil texture difference and other local variations. Observed turmeric yield was significantly negatively correlated to soil salinity. There was a monotonically increasing gap between simulated and observed yield as salinity increased. The maximum observed yield was 71% of the potential. The highest impact due to salinity was observed at 2.1 dS/m amounting to 44 % yield reduction. Excessive chlorosis due to iron deficiency occurred at 24.5% as CaCO3 and pH 7.5. Irrigation water pH was normal as per the guidelines. Soil pH was not so varied; it ranged between 7.1-7.9 except for one site where it was 6. Within the 7.1-7.9 range there was no effect on crop and yield observed. Interaction of stress factors observed was between salinity and alkalinity. The other was rhizome rot disease. Loss of yield to salinity was significant but farmers have no specific plans to leach out salts nor do they have an idea that ground water quality can actually negatively impact productivity. Salinity in irrigation water was in the moderately saline range. While that in the soil was low to slightly saline but could increase given the management practices.