Sulfate is one of the most problematic ions present in reject brine in desalination systems due to its high potential of scale formation and membrane fouling; making it an obstacle in the application of zero liquid discharge. The ultra-high lime with aluminum process (UHLA) has shown to effectively remove sulfate. This research involves the study of sulfate removal from the nano-filtration unit in the zero liquid discharge system for inland desalination via a two-stage process using a calcium source to remove sulfate in the first stage and implementing the UHLA process in the second stage. The kinetics, equilibrium characteristics, and effects of different parameters on sulfate removal were studied. Kinetics of sulfate removal was studied on both stages of the process. The observation of fast kinetics in both stages indicated that removal kinetics is not a limitation for the application of the process. Equilibrium characteristics of the UHLA process were performed which revealed efficient sulfate removal at practical ranges of lime and aluminum doses. The effect of pH on sulfate removal in the process was studied. Results showed that sulfate removal in Stage 1 was independent of the pH of the solution while effective sulfate removal in Stage 2 was found to be above a pH of 11. The effect of initial sulfate concentrations on sulfate removal in Stage 1 was investigated and sulfate removal was mainly controlled by calcium sulfate solubility. The effect of initial chloride concentrations on sulfate removal in Stage 2 was evaluated and the results indicated that chloride has negligible effect on the removal of sulfate. Experiments concerning the effect of the recycle of calcium sulfate solids in Stage 1 showed an increase of the reaction rate. In contrast, the recycle of Stage 2 dry solids into Stage 2 revealed no effect on sulfate removal. An equilibrium model was developed to explain the equilibrium characteristics of Stage 2. It was found that a valid explanation for the chemistry of sulfate removal in Stage 2 was the formation of a solid solution consisting of ettringite and monosulfate. XRD analysis confirmed the formation of these solids.

Um reator anaeróbio tratando esgoto sintético de baixa concentração de matéria orgânica (500 mgDQO/L-1) e enriquecido com diferentes concentrações de sulfato (razões DQO/[SO4-2] de 1,34, 0,67 e 0,34) foi submetido à diferentes estratégias de alimentação (batelada e batelada alimentada de 3 h e de 6 h). O reator operou com capacidade de 4,0 L e tratou por ciclo de 8 h um volume de 2,0 L de esgoto sintético. Desta forma, executaram-se 9 condições diferentes que foram submetidas à análise com o objetivo de investigar a influência do tempo de alimentação e da razão DQO/[SO4-2] no desempenho do sistema. A temperatura do reator foi constante em 30 ± 1°C e a agitação mecânica foi fixada em 400 rpm. Como suporte para a imobilização da biomassa foram utilizados cubos de espuma de poliuretano. Os resultados obtidos demonstraram que a operação em batelada alimentada de 3 h com uma razão DQO/[SO4-2] de 0,34 apresentou as melhores condições para a remoção de matéria orgânica (89%). Quanto à remoção de sulfato observou-se uma estagnação neste mesmo modo de operação ao aumentar a concentração de sulfato no afluente, enquanto que na operação com alimentação em batelada alimentada de 6 h, a carga de sulfato removida (CSR) cresceu linearmente. Assim, a maior carga de sulfato removida foi registrada durante o ensaio em batelada alimentada de 6 h com uma razão DQO/[SO4-2] de 0,34, no qual foram removidos 0,55 g SO4-2(L.d). Com uma razão DQO/[SO4-2] de 1,34 e um tempo de enchimento de 6 h, o reator apresentou o melhor desempenho em termos de eficiência de remoção de sulfato (71%). Em todos os ensaios o reator apresentou estabilidade, com uma produção alta de alcalinidade a bicarbonato e a concentração de ácidos voláteis se manteve em níveis adequados. / An anaerobic sequencing batch reactor treating synthetic low strength wastewater (500 mgCOD/L-1) enriched with different sulfate concentrations (COD/[SO42] ratios of 1,34, 0,67 and 0,34) was operated at different fill times (batch mode and sequencing batch mode of 3 h and 6 h fill time). The reactor operated with a capacity of 4,0 L and treated per 8-h cycle 2,0 L of synthetic wastewater. Thus, 9 different configurations resulted from this configuration and were submitted under analyses with the objective to investigate the influence of each of those parameters on the performance of the system. The reactor was operated at a constant temperature of 30 ± 1°C and an mechanical agitation rate of 400 rpm. Cubic particles of polyurethane were used as support material for anaerobic biomass immobilization. The results showed that operating the reactor with a fill time of 3 h and a COD/[4-2] ratio of 0,34 was the most eficient strategy for COD removal (89%). During the same operation mode (3 h fill time) sulfate removal seemed to suffer stagnation due to the increasing sulfite concentation in the reactor, whereas with a fill time of 6 h the sulfate load removal increased linerally with increasing sulfate load. So the biggest removal, in terms of volumetric sulfate load, was obtained operating the reactor in sequencing batch mode with a fill time of 6 h and a COD/[4-2] ratio of 0,34. During this test the reactor removed 0,55 gSO4-2/(L.d) of 2,29 gSO4-2/(L.d) applied on the system. Operating at a COD/[SO4-2] ratio of 1,34 and a fill time of 6 h the reactor obtained the best results in terms of sulfate removal efficiency, with 71% of the sulfate removed from the system. In the entire period of analisis the reactor showed stability with a suficient production of alkalinity to maintain the concentration of volatil acids in adequate levels.

Um reator anaeróbio tratando esgoto sintético de baixa concentração de matéria orgânica (500 mgDQO/L-1) e enriquecido com diferentes concentrações de sulfato (razões DQO/[SO4-2] de 1,34, 0,67 e 0,34) foi submetido à diferentes estratégias de alimentação (batelada e batelada alimentada de 3 h e de 6 h). O reator operou com capacidade de 4,0 L e tratou por ciclo de 8 h um volume de 2,0 L de esgoto sintético. Desta forma, executaram-se 9 condições diferentes que foram submetidas à análise com o objetivo de investigar a influência do tempo de alimentação e da razão DQO/[SO4-2] no desempenho do sistema. A temperatura do reator foi constante em 30 ± 1°C e a agitação mecânica foi fixada em 400 rpm. Como suporte para a imobilização da biomassa foram utilizados cubos de espuma de poliuretano. Os resultados obtidos demonstraram que a operação em batelada alimentada de 3 h com uma razão DQO/[SO4-2] de 0,34 apresentou as melhores condições para a remoção de matéria orgânica (89%). Quanto à remoção de sulfato observou-se uma estagnação neste mesmo modo de operação ao aumentar a concentração de sulfato no afluente, enquanto que na operação com alimentação em batelada alimentada de 6 h, a carga de sulfato removida (CSR) cresceu linearmente. Assim, a maior carga de sulfato removida foi registrada durante o ensaio em batelada alimentada de 6 h com uma razão DQO/[SO4-2] de 0,34, no qual foram removidos 0,55 g SO4-2(L.d). Com uma razão DQO/[SO4-2] de 1,34 e um tempo de enchimento de 6 h, o reator apresentou o melhor desempenho em termos de eficiência de remoção de sulfato (71%). Em todos os ensaios o reator apresentou estabilidade, com uma produção alta de alcalinidade a bicarbonato e a concentração de ácidos voláteis se manteve em níveis adequados. / An anaerobic sequencing batch reactor treating synthetic low strength wastewater (500 mgCOD/L-1) enriched with different sulfate concentrations (COD/[SO42] ratios of 1,34, 0,67 and 0,34) was operated at different fill times (batch mode and sequencing batch mode of 3 h and 6 h fill time). The reactor operated with a capacity of 4,0 L and treated per 8-h cycle 2,0 L of synthetic wastewater. Thus, 9 different configurations resulted from this configuration and were submitted under analyses with the objective to investigate the influence of each of those parameters on the performance of the system. The reactor was operated at a constant temperature of 30 ± 1°C and an mechanical agitation rate of 400 rpm. Cubic particles of polyurethane were used as support material for anaerobic biomass immobilization. The results showed that operating the reactor with a fill time of 3 h and a COD/[4-2] ratio of 0,34 was the most eficient strategy for COD removal (89%). During the same operation mode (3 h fill time) sulfate removal seemed to suffer stagnation due to the increasing sulfite concentation in the reactor, whereas with a fill time of 6 h the sulfate load removal increased linerally with increasing sulfate load. So the biggest removal, in terms of volumetric sulfate load, was obtained operating the reactor in sequencing batch mode with a fill time of 6 h and a COD/[4-2] ratio of 0,34. During this test the reactor removed 0,55 gSO4-2/(L.d) of 2,29 gSO4-2/(L.d) applied on the system. Operating at a COD/[SO4-2] ratio of 1,34 and a fill time of 6 h the reactor obtained the best results in terms of sulfate removal efficiency, with 71% of the sulfate removed from the system. In the entire period of analisis the reactor showed stability with a suficient production of alkalinity to maintain the concentration of volatil acids in adequate levels.

In recent years, the excessive specific conductance (SC) of Appalachian coal mining runoff waters has become a parameter of concern with the EPA due to its negative effect on aquatic life and water quality. In order to comply with the EPA guidance suggesting an effluent SC of 500 µS/cm, the Appalachian Research Initiative for Environmental Science (ARIES) Center at Virginia Tech requested that testing be done to determine the most effective technologies for reduction of SC. Runoff water was collected from two sites in southwestern Virginia and characterized to determine the source of SC in the water. The main contributing ions were determined to be Na⁺, Mg²⁻, Ca²⁺, and SO₄²⁻. Testing was performed to assess the possibility of using the speciation software, MINEQL+, with a set of empirical equations which predict SC using ionic composition for natural waters with a low to medium SC. The physicochemical treatment methods tested were ion exchange, excess lime-soda softening, and the Cost Effective Sulfate Removal (CESR) process. Both cation (H⁺ exchanger) and anion (Cl⁻ exchanger) exchange media were tested separately in batch reactors, which resulted in a higher effluent SC than initial SC. The softening method investigated, excess lime-soda softening, also resulted in increased SC levels because non-carbonate hardness levels were high and carbonate concentrations were low. The CESR process successfully lowered SC from 1,500-2,500 µS/cm to below the proposed EPA limit of 500 µS/cm. The success of this process was due to its ability to remove more than 85% of the calcium, magnesium, and sulfate from the water, which together accounted for more than 90% of ions in the source water. / Master of Science / In recent years, mining activities have generated large amounts of unweathered rock from blasting. This rock, which is often stored in valleys near the blasting sites, releases salts into water that passes over the rocks when it rains. The salty water flows into nearby streams populated with freshwater fish and other organisms that suffer when their environmental conditions are changed. The Appalachian Research Initiative for Environmental Science (ARIES) Center at Virginia Tech requested that testing be done to determine which engineering techniques would be most effective for reduction of these salts. The amount of salt in the water is measured by specific conductance (SC), which measures how well the water conducts electricity. Testing was also done to determine which types of salts were in the water; the results showed that the largest contributors were sodium, magnesium, calcium, and sulfate ions. Three engineering techniques were investigated for removal of the contributing ions: ion exchange, softening, and the Cost Effective Sulfate Removal (CESR) process. Two types of ions exchange, one that targeted the positive ions (cation exchange) and one that targeted the negative ions (anion exchange), were tested. Both forms of ions exchange raised the SC to a higher concentration than the original water. Softening had a similar effect because one of the chemicals added during the process released additional sodium ions into the water. Finally, the CESR process was able to successfully reduce the SC below the limit proposed by the EPA as safe for stream life. This was due to the large reduction of three of the four major ions that was achieved during the CESR process.