External sulphate attack on concrete can lead to cracking, expansion and sometimes loss of cohesiveness of hardened cement paste. Therefore, aside from using sulphate resistant cementitious binders, it is important to design concrete which can resist sulphate penetration. In this research, both ASTM C1202 and NT Build 492 electrical migration tests were modified such that sulphate rather than chloride penetration resistances were measured. Modifications included exposing concrete specimens to Na2SO4 rather than NaCl solutions and measuring the depth of sulphate penetration visually using BaCl2+KMnO4 rather than AgNO3 solution. Nine concrete mixtures of varying w/cm, slag replacement and cement types were tested in both original standard tests and modified tests to evaluate the influence of these material variables on test results and compare chloride to sulphate results. It was found that while migration coefficients and total charge passing were lower for sulphate, the influence of material variables were relatively similar.

Biological sulphate reduction (BSR) has been identified as a promising alternative technology for the treatment of acid mine drainage. BSR is a process that uses sulphate reducing bacteria to reduce sulphate to sulphide using substrates as nutrients under anaerobic conditions. The performance of BSR is dependent on several factors including substrate, pH, temperature and hydraulic retention time (HRT). In a quest to find a cost effective technology, Mintek conducted bench-scale tests on BSR that led to the commissioning of a pilot plant at a coal mine in Mpumalanga province, South Africa. This current study forms part of the ongoing tests that are conducted to improve Mintek’s process. The purpose of this study was to investigate the robustness of Mintek’s process and to develop a tool that can be used to predict the process’ performance with varying pH, temperature and HRT. Design Expert version 11.1.2.0 was used to design the experiments using the Box-Behnken design. In the design, pH ranged from 4 to 6, temperature from 10 °C to 30 °C and HRT from 2 d to 7 d with sulphate reduction efficiency, sulphate reduction rate and sulphide production as response variables. Experiments were carried out in water jacketed packed bed reactors that were operated in a down-flow mode. The reactors were packed with woodchips, wood shaving, hay, lucerne straw and cow manure as support for sulphate reducing bacteria (SRB) biofilm. Cow manure and lucerne pellets were used as the main substrates and they were replenished once a week. These reactors mimicked the pilot plant. The data obtained were statistically analysed using response surface methodology. The results showed that pH did not have a significant impact on the responses (p>0.05). Temperature and HRT, on the other hand, greatly impacted the process (p<0.05) and the interaction between these two factors was found to be strong. Sulphate reduction efficiency and sulphate reduction rate decreased by over 60 % with a decrease in temperature 30 °C to 10 °C. Generally, a decrease in sulphide production was observed with a decrease in temperature. Overall, a decrease in HRT resulted in a decline of sulphate reduction efficiency and sulphide production but favoured sulphate reduction rate. This study demonstrated that Mintek’s process can be operated at pH as low as 4 without any significant impact on the performance. This decreases the lime requirements and sludge production during the pre-neutralisation stage by close to 50 %. There was, however, a strong interaction between temperature and HRT which can be used to improve the performance especially during the winter season. / Dissertation (MEng)--University of Pretoria, 2020. / Chemical Engineering / MEng / Unrestricted

published_or_final_version / Chinese Historical Studies / Master / Master of Arts

Ion exchange for the recovery of metals from solutions is a well established process. It features significantly in terms of being able to recover valuable substances from what would otherwise be waste streams as well as recovering substances that could be harmful to the environment if left in the waste stream. The more popular options for ion exchange processes could be batch, fixed bed, fluidized, moving bed, and chromatographic columns. Although most ion exchange processes tend to be batch processes making use of the fixed bed columns, technological developments enable the use of fluidized beds to be explored. The main purpose of this research was to compare the performance of a fixed bed ion exchange system with a fluidized ion exchange system for the recovery of copper from a cupric sulphate solution. By experimentation the bed depth required for each type of equipment (in order to achieve a specified percentage recovery of copper from a specified feed) was determined. The comparative advantage of one type of equipment over the other ensures the correct type of system to be used for a sulphate solution of a particular concentration. This study provides a basis for comparative studies of contacting equipment for the removal of other substances from dilute solutions. / Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2005.

The use of black liquor gasification as an alternative to conventional chemical and energy recovery systems for spent liquors is an area of particular interest to the pulp and paper industry. The motivation to explore this technology is to improve the thermal efficiency of the recovery process by utilizing the energy content of the spent black liquor more effectively and provide chemical recovery for sodium and sulphur containing liquors for a local pulp and paper mill. A study of the available gasification technologies showed that the steam reforming process marketed by ThermoChem Recovery International is particularly suited to the mill in that it can handle a change to a sulphite pulping chemistry and also handle silica removal which is an inherent problem with the bagasse raw material that the mill uses. However the technology required further development and confirmation of process suitability before implementation at the mill. This aim of this project was to build and operate a gasifier based on the TRI concept to determine if this process is suitable for recovery of SASAQ black liquor from bagasse pulping. This included gaining an understanding of the process variables like the black liquor solids composition and the non-process element levels and required carrying out a mass balance on inorganic components across the reactor as well. The focus of this investigation was primarily on the front end of the project and entailed basic and detailed design of a pilot gasification unit. The pilot unit was subsequently constructed, commissioned and operated to prove the unit met the design intent. Preliminary results showing the conceptual proof of the technology are presented as well as performance tests showing the unit capability of gasifying a 3.1 1Ihr 60% solid content black liquor feed. Problematic areas that could influence the design of a scale-up unit were identified and highlighted for further development, with proposed solutions. / Thesis (M.Sc.)-University of KwaZulu-Natal, Durban, 2005.

A series of studies was undertaken at Plastic Lake-1 (PC1) to determine the sources and controls on S cycling in small headwater catchments on the Precambrian Shield in south-central Ontario. Two observations were made about the S cycle in this region: (1) all streams exhibit highly coherent temporal patterns in SO4 concentrations and export, and (2) most catchments exported more SO4 in stream water than is received in bulk deposition during the past 2 decades. Synchronous temporal patterns in annual SO4 concentrations in both upland and wetland-draining streams were related to changes in climate, specifically those factors that determine catchment dryness. The number of days with no stream flow or stream flow below a critical threshold was a good predictor of the average stream SO4 concentration in a particular year. Sulphate chemistry in the PC1 outflow is highly dependent on processes occurring in a conifer <i>Sphagnum</i> swamp located immediately upstream of the chemical sampling station. Hydrologic inputs to the swamp during the summer determine whether S is retained or released from peat on an annual basis. Drying and re-wetting of <i>Sphagnum</i>-derived peat caused a substantial increase in soluble SO4 in laboratory experiments, which was slightly enhanced at higher temperature, but alternating moisture conditions had no immediate effect on <i>Sphagnum</i>. Despite large inter-annual changes in SO4 release, over the long-term (<i>i. e. </i> 20-years) SO4 inputs and exports from the swamp are in approximate balance. In contrast, the upland portion of PC1 (<i>i. e. </i> PC1-08) consistently exports more SO4 than is input in bulk deposition in every year of record. Even when inputs are increased to account for potential underestimates in dry deposition or weathering, the majority of catchments in this region exhibit net export in many years. Two internal sources are suggested to account for negative budgets: desorption and mineralization. Adsorption/desorption reactions respond directly to changes in SO4 input concentration, and lysimeter data indicate the importance of these processes for buffering short-term changes in SO4 concentration in LFH percolate. Desorption may be the primary direct response of upland soil to decreasing SO4 inputs in deposition and may substantially extend the period of net SO4 export in catchments that have large adsorbed SO4 pools such as PC1. However, the adsorbed pool may be sustained by continuous net release from mineralization, and should also be considered in budget calculations. Mineralization was shown to be responsive to drying and re-wetting events and temperature, although results varied among different materials. Sulphate release from mineral soil did not appear to be influenced by changing moisture, temperature or deposition chemistry in laboratory experiments, although adsorption/desorption reactions may have largely masked small changes in SO4 release <i>via</i> mineralization. The magnitude of organic S storage in mineral soil indicates that this pool could be an important source of export over the long-term. While it is unknown why (or if) mineralization is a net source of SO4 to drainage streams, changes in climate and/or deposition could potentially influence SO4 release from organic compounds. Soil moisture and temperature are important controls on microbial processes in soil, and changes in climate that bring about changes in soil moisture or temperature conditions could affect decomposition and mineralization processes. Similarly, historically high inputs of S and N in deposition may have brought about slow shifts in litter quality (<i>i. e. </i> decreased C:N, C:S) which could also potentially influence decomposition and mineralization rates. In order to predict the future response of surface water chemistry to changes in SO4 (and N) deposition, it is important to consider not only the magnitude of S pools in soil, but also the potential for SO4 cycling between pools. Likewise, models that predict changes in stream SO4 by adsorption isotherm data alone will underestimate the importance of desorption unless the potential for continual replenishment of the adsorbed pool through the relatively slower process of mineralization is also considered. In general, predictions of recovery from S deposition can only be made from a complete understanding of S pools, transformations, and the effects of climate, which are superimposed upon the long-term trend in deposition.

Dissimilatory sulphate reduction, brought about by the action of sulphate reducing bacteria (SRB) was used in the treatment of acid mine drainage (AMD) in a fluidised bed bioreactor. Biologically produced hydrogen sulphide and bicarbonate ions, by SRB, facilitated the precipitation of heavy metals and the generation of alkalinity in the synthetic acid mine water, respectively. The SRB that had been selected were able to utilize acetate as the sole carbon source and were capable of growing in the bioreactors at low pHs, facilitating an increase in the influent pH from 2.75-7.0 to 5.4-7.8, after a 24-hour hydraulic retention time (HRT). The precipitation efficiencies for Fe, Mn, Zn, Cu, Cr and Al after a HRT of 24 h as metal sulphides ranged between 84- 99% for influent pH values of between 4 and 7, and above 54% for influent pH values between 2.75 and 4. Microbial metabolic activity decreased with decreasing influent pH. This was inferred from the decreasing differences in chemical oxygen demand (COD) depletion rate over a 24 h HRT, as influent acidity levels approached pH 2.75. Molecular studies, using PCR-DGGE analysis on the microbial consortium in the bioreactor, revealed the presence of at least 8 different bacterial species in the consortium. Attempts at sequencing these bands yielded inconclusive results, with the bands showing sequence homology to a large number of previously uncultured and undescribed bacteria. Scanning electron microscopy confirmed the presence of bacteria of different morphology, as well as the presence of biofilms, which account for the heavy metal and low pH tolerances that the bacteria sustained.

Submitted by Luiz Felipe de Melo Santos (felipemelo.biologia@gmail.com) on 2019-01-26T15:00:46Z No. of bitstreams: 1 001-2019-Luiz Felipe de Melo Santos.pdf: 2201809 bytes, checksum: 0858caf6045635fdc1eb50f8be76eb88 (MD5) / Approved for entry into archive by Fabio Sampaio Rosas null (fabio@dracena.unesp.br) on 2019-01-28T12:24:37Z (GMT) No. of bitstreams: 1 Santos_lfm_me_dra.pdf: 2201809 bytes, checksum: 0858caf6045635fdc1eb50f8be76eb88 (MD5) / Made available in DSpace on 2019-01-28T12:24:37Z (GMT). No. of bitstreams: 1 Santos_lfm_me_dra.pdf: 2201809 bytes, checksum: 0858caf6045635fdc1eb50f8be76eb88 (MD5) Previous issue date: 2018-11-27 / O enxofre é, provavelmente, o macronutriente menos empregado nas adubações, o que resulta na redução de rendimento e qualidade de forragem. Entre os nutrientes, apresenta um importante papel por participar em várias funções biológicas, faz parte da composição dos aminoácidos cisteína, metionina e cistina, acetil-CoA, bem como de enzimas que participam da fotossíntese e o metabolismo do nitrogênio. O objetivo foi avaliar a produção e estado nutricional dos capins Piatã e Mombaça em resposta a aplicação de doses e fontes de sulfato e enxofre elementar em Argissolo Vermelho Amarelo. Em virtude disso, realizou-se dois experimentos em casa de vegetação na Faculdade de Ciências Agrárias e Tecnológicas, UNESP, Campus de Dracena – SP, o primeiro foi no período de janeiro a março de 2017 e o segundo de outubro a janeiro de 2018, com o capim Piatã e de Mombaça, respectivamente. O delineamento experimental foi em blocos casualizados com quatro repetições, arranjados em esquema fatorial, 4x5, com quatro fontes de enxofre (Gipsita, Fosfogesso, S elementar em pó e S elementar pastilhado) e cinco doses de enxofre (0, 50, 100, 150 e 200 mg kg-1).Foram determinados os parâmetros biométricos como número de perfilhamento, massa seca da parte aérea (MSPA) e massa seca de raízes (MSR). O estado nutricional das plantas foi avaliado por meio da leitura SPAD e análise de macronutrientes N, P, K, Ca, Mg, S na parte aérea das plantas. Avaliou-se também o enxofre residual do solo e o pH do solo. Os resultados demonstraram que adubação com S aumentou a produção de MSPA, MSR, número de perfilhos, quantidade de folhas por colmo, índice SPAD e promoveu uma melhor qualidade de estado nutricional da forragem em ambos os experimentos. A granulométrica das fontes apresentou uma forte influencia na disponibilização de S, o que é possível de ser constado pelos menores incrementos na produção e absorção de S verificados com o uso da fonte SEPA em relação às demais fontes, tanto na espécie Urochloa brizantha quanto da espécie Megathyrsus maximum. De forma geral a aplicação ideal de S foi essencial para otimizar o rendimento dos capins Piata e Mombaça em todas as fontes testadas de S, enquanto a baixa oferta de S resulta em desequilíbrio nutricional e menor rendimento. / Sulfur is probably the least used macronutrient in fertilization, which results in reduced yield and forage quality. Among nutrients, it plays an important role because it participates in several biological functions, is part of the composition of the amino acids cystine, methionine and cysteine, acetyl-CoA, as well as enzymes involved in photosynthesis and nitrogen metabolism. The objective was to evaluate the production and nutritional status of the Piatã and Mombasa grass in response to the application of doses and sources of sulfate and elemental sulfur in Yellow Red Ultisol. In view of that, two greenhouse experiments were carried out at the Faculty of Agrarian and Technological Sciences, UNESP, Dracena Campus - SP, the first one was in the period from January to March 2017 and the second from October to February 2018, with Piatã grass and Mombasa grass, respectively. The experimental design was in randomized blocks with four replications, arranged in a factorial scheme, 4x5, with four sulfur sources (Fosfogesso, Grajau, S-Elementar and Sulfurgran) and five doses of sulfur (0, 50, 100, 150 e 200 mg kg-1). Biometric parameters such as tillering number, shoot dry mass and roots dry mass were determined. The nutritional status of the plants was evaluated by SPAD reading and analysis of N, P, K, Ca, Mg and S macronutrients in shoot dry mass. Residual sulfur and soil pH were also evaluated. The results showed that S fertilization increased the yield of MSPA, MSR, number of tillers, number of leaves per stem, SPAD index and promoted a better quality of forage nutritional status in both experiments. The granulometric of the sources had a strong influence on the availability of S, which is possible to be consisted of the smaller increases in the production and absorption of S verified with the use of the SEPA source in relation to the other sources, both in the species Urochloa brizantha and of the species Megathyrsus maximum. In general, the ideal application of S was essential to optimize the yield of the Piata and Mombasa grasses in all tested sources of S, while the low supply of S results in nutritional imbalance and lower yield.

Lime stabilisation is a ground improvement technique used to improve the engineering properties of cohesive fill materials. During earthworks operations, specialist plant is used to rotovate the clay fill material and intermix lime binder around clay clods. After completion of the lime treatment, the layer is compacted in the usual way. Immediately after mixing, the lime instigate a series of physico-chemical reactions within the clay soil. Where the chemical reactions are favourable and with time after compaction (curing) the material becomes progressively stronger and durable to environmental influences, e.g. inundation by surface or ground water. However, where sulphate is present within the soil, the reactions may change and the ingress of water into the layer can result in the expansive growth of deleterious minerals e.g. ettringite. While sulphate swell issues are relatively rare, when they do occur the degree of expansion can be very high. A high profile sulphate swell failure developed during the construction of the M40, Oxford, UK in 1989. Over the winter period after the lime stabilisation works, a 250mm deep lime treated layer heaved by up to 150mm - destroying the overlying road construction. Since the M40 failure, a substantial amount of effort has been undertaken to better understand the sulphate swell reactions and in this regard the state of scientific knowledge is relatively strong. A fundamental issue for field applications of lime stabilisation is that the vast majority of research has been undertaken on laboratory specimens prepared using methods which do not reflect site practice. Laboratory studies often use oven dried and finely crushed clay, whereas site operations will treat much larger clay clods to result in a more heterogeneous distribution of lime through the compacted soil body. With large clay clods, the chemical reactants must migrate through clods and this may cause the sequence of chemical reactions to change. A further challenge is that laboratory studies are typically undertaken with cure temperatures of 20°C, whereas a typical near surface temperature in the UK is <10°C. This is of particular relevance to sulphate swell failures which are reported to coincide with a reduction in ambient temperature over winter periods. Thus, the direct relevance of laboratory studies to site application was unclear. A series of laboratory experiments using a preparation method which reflects field applications of lime stabilisation was used to investigate the influence of large clay clods on the durability of lime stabilised clay soil. This method was applied to both low and high sulphate clay soils. A fundamental discovery from work on low sulphate clay is that the addition of lime binder to the surface of the clay clods causes a physico-chemical boundary to form. This boundary develops due to the rapid increase to the plastic limit of the clay preventing adjacent clods from joining together during compaction. This causes the engineering properties of each individual clod to develop independent to its neighbours and for each clay clod to be separated by an inter-clod pore space. The strength of each individual clay clod will increase with curing as the added lime dissociates into Ca2+ and OH- and migrates to form C-S-H deep within the clods. Where the material is compacted wet of the optimum water content, this condition improves ion migration and enables development of diffuse cementation deep within clods. The inter-clod porosity remains as a weakness throughout curing especially during specimen soaking, where the pore channels comprise a pathway, accelerating the ingress of soaking water. With low sulphate soil, the soaking water softens the treated material, however, with high TPS soil substantial sulphate swelling may develop. Thus, efforts to minimise this porosity during preparation is important and the use of quicklime with longer mellowing periods can cause the clay clods to develop high strength before compaction. The high strength clods resist compaction and the degree of inter-clod porosity in the compacted mass increases, worsening specimen durability to water ingress. The investigations into high sulphate clays included the development of a Novel Swell Test (NST) to assess volume change. A unique aspect of the NST was that the sulphate swell response of the lime treated material was investigated at site realistic temperatures of 8°C. It was identified that, when compared with standard laboratory test temperatures of 20°C the rate of sulphate swell is substantially higher at the low temperature. The mineralogical testing has permitted the hypothesis that, at 8°C the growth of crystalline ettringite becomes slower and the ettringite precursor, which has a high affinity to imbibe water, remains in this state for much longer. Thus, laboratory swell tests at 20°C may substantially underestimate the degree of swell that may develop in the field. As a pressing need, it is recommended that the industry adapt sulphate swell test methods to appraise the degree of swell at field realistic temperatures i.e. < 10°C. The work also identifies that the primary defence against sulphate swell is to condition the fill so that the risk of post compaction water ingress, via inter-clod porosity, is minimised. The use of GGBS and water addition during extended mellowing periods also reduces the degree of sulphate swell in natural clay soils. This work concludes that working methods for lime stabilisation of medium high plasticity soils of a potentially high sulphate content, should be adapted to encourage diffuse cementation and minimise the degree of (post compaction) inter-clod porosity. Practically this involves the use of hydrated lime and the addition of mixing water throughout extended mellowing periods. Fundamentally, the study recommends that where construction programmes allow, the long term durability of a fill material should be the priority over immediate strength.

Orientador: Reges Heinrichs / Resumo: O enxofre é, provavelmente, o macronutriente menos empregado nas adubações, o que resulta na redução de rendimento e qualidade de forragem. Entre os nutrientes, apresenta um importante papel por participar em várias funções biológicas, faz parte da composição dos aminoácidos cisteína, metionina e cistina, acetil-CoA, bem como de enzimas que participam da fotossíntese e o metabolismo do nitrogênio. O objetivo foi avaliar a produção e estado nutricional dos capins Piatã e Mombaça em resposta a aplicação de doses e fontes de sulfato e enxofre elementar em Argissolo Vermelho Amarelo. Em virtude disso, realizou-se dois experimentos em casa de vegetação na Faculdade de Ciências Agrárias e Tecnológicas, UNESP, Campus de Dracena – SP, o primeiro foi no período de janeiro a março de 2017 e o segundo de outubro a janeiro de 2018, com o capim Piatã e de Mombaça, respectivamente. O delineamento experimental foi em blocos casualizados com quatro repetições, arranjados em esquema fatorial, 4x5, com quatro fontes de enxofre (Gipsita, Fosfogesso, S elementar em pó e S elementar pastilhado) e cinco doses de enxofre (0, 50, 100, 150 e 200 mg kg-1).Foram determinados os parâmetros biométricos como número de perfilhamento, massa seca da parte aérea (MSPA) e massa seca de raízes (MSR). O estado nutricional das plantas foi avaliado por meio da leitura SPAD e análise de macronutrientes N, P, K, Ca, Mg, S na parte aérea das plantas. Avaliou-se também o enxofre residual do solo e o pH do solo. Os res... (Resumo completo, clicar acesso eletrônico abaixo) / Mestre