abstract: Mineral weathering and industrial activities cause elevated concentration of hexavalent chromium (Cr(VI)) in groundwater, and this poses potential health concern (>10 ppb) to southwestern USA. The conversion of Cr(VI) to Cr(III) – a fairly soluble and non-toxic form at typical pH of groundwater is an effective method to control the mobility and carcinogenic effects of Cr(VI). In-situ chemical reduction using SnCl2 was investigated to initiate this redox process using jar testing with buffered ultrapure water and native Arizona groundwater spiked with varying Cr(VI) concentrations. Cr(VI) transformation by SnCl2 is super rapid (<60 seconds) and depends upon the molar dosage of Sn(II) to Cr(VI). Cr(VI) removal improved significantly at higher pH while was independent on Cr(VI) initial concentration and dissolved oxygen (DO) level. Co-existing oxyanions (As and W) competed with Cr(VI) for SnCl2 oxidation and adsorption sites of formed precipitates, thus resulted in lower Cr(VI) removal in the challenge water. SnCl2 reagent grade and commercial grade behaved similarly when freshly prepared, but the reducing strength of the commercial product decreased by 50% over a week after exposing to atmosphere. Equilibrium modeling with Visual MINTEQ suggested redox potential < 400 mV to reach Cr(VI) treatment goal of 10 ppb. Kinetics of Cr(VI) reduction was simulated via the rate expression: r=-k[H+]-0.25[Sn2+]0.5[Cr2O72-]3 with k = 0.146 uM-2.25s-1, which correlated consistently with experimental data under different pH and SnCl2 doses. These results proved SnCl2 reductive treatment is a simple and highly effective method to treat Cr(VI) in groundwater. / Dissertation/Thesis / Masters Thesis Civil, Environmental and Sustainable Engineering 2019

In this research, five different coagulants were evaluated to determine their effectiveness at removing turbidity, color and dissolved organic carbon (DOC) from a surface water in Sarasota County, Florida. Bench-scale jar tests that simulated conventional coagulation, flocculation, and sedimentation processes were used. Iron-based coagulants (ferric chloride and ferric sulfate) and aluminum-based coagulants (aluminum sulfate, polyaluminum chloride (PACl) and aluminum chlorohydrate (ACH)) were used to treat a highly organic surface water supply (DOC ranging between 10 and 30 mg/L), known as the Cow Pen Slough, located within central Sarasota County, Florida. Isopleths depicting DOC and color removal efficiencies as a function of both pH and coagulant dose were developed and evaluated. Ferric chloride and ACH were observed to obtain the highest DOC (85% and 70%, respectively) and color (98% and 97%, respectively) removals at the lowest dose concentrations (120 mg/L and 100 mg/L, respectively). Ferric sulfate was effective at DOC removal but required a higher concentration of coagulant and was the least effective coagulant at removing color. The traditional iron-based coagulants and alum had low turbidity removals and they were often observed to add turbidity to the water. PACl and ACH had similar percent removals for color and turbidity achieving consistent percent removals of 95% and 45%, respectively, but PACl was less effective than ACH at removing organics. Sludge settling curves, dose-sludge production ratios, and settling velocities were determined at optimum DOC removal conditions for each coagulant. Ferric chloride was found to have the highest sludge settling rate but also produced the largest sludge quantities. Total trihalomethane formation potential (THMFP) was measured iv for the water treated with ferric chloride and ACH. As with DOC removal, ferric chloride yielded a higher percent reduction with respect to THMFP.

The Ceratium species occurring in the Vaal River since 2000, was identified as Ceratium hirundinella (O.F. Müller) Dujardin as proposed by Van Ginkel et al (2001). Ceratium hirundinella is known to cause problems in drinking water purification and has been penetrating into the final drinking water of Rand Water since 2006. Ceratium hirundinella is associated with many other water purification problems such as disrupting of the coagulation and flocculation processes, blocking of sand filters and algal penetration into the drinking water. Ceratium hirundinella also produce fishy taste and odorous compounds and causes discolouration of the water. The aims of this study were to determine the main environmental factors which are associated with the bloom formation of C. hirundinella in the source water and to investigate the influence of C. hirundinella on the production of potable water. In order to optimise treatment processes and resolve problems associated with high C. hirundinella concentrations during the production of potable water, jar testing and chlorine exposure experiments were performed. Multivariate statistical analyses were performed to determine the main environmental variables behind C. hirundinella blooms. Ten years data (2000 - 2009) from the sampling point C–VRB5T in the Vaal River, (5 km upstream from the Barrage weir) were used for this investigation, because C. hirundinella occurred there frequently during the ten year period. In this study, it was found that C. hirundinella was favoured by high pH, Chemical Oxygen Demand (COD), orthophoshapte (PO4), and silica concentrations, as well as low turbidity and low dissolved inorganic nitrogen (DIN) concentrations. No correlation was found between C. hirundinella and temperature, suggesting that this alga does not occur during periods of extreme warm or extreme cold conditions, but most probably during autumn and spring. The results of the multivariate statistical analysis performed with historical data from Vaalkop dam, indicate that the dinoflagellate C. hirundinella seems to be favoured by low temperature and turbidity, and high DIN, Fe, Methyl–orange alkalinity, Cd, PO4, Conductivity, pH, hardness and SO4 concentrations. In order to optimise treatment processes such as coagulation, flocculation and sedimentation, jar testing experiments were performed to investigate different coagulant chemicals namely: cationic poly–electrolyte only, cationic poly–electrolyte in combination with slaked lime (CaO) and CaO in combination with activated silica. Water from four different sampling localities were chosen to perform the different jar testing experiments: 1) sampling point M–FOREBAY (in the Forebay, connecting the canal to the Zuikerbosch Purification plant) near Vereeniging due to its proximity to the Zuikerbosch treatment plant, 2) M–CANAL_VD (upstream from the inflow of the recovered water from Panfontein) to determine the influence of (if any) the recovered water from Panfontein on Forebay source water, 3) source water from Vaalkop Dam (M–RAW_VAALKOP) and 4) source water from Rietvlei Dam (water from both Vaalkop and Rietvlei Dams contained high concentrations of C. hirundinella at that time of sampling) to determine which coagulant chemical is the most effective in removing high concentrations of C. hirundinella cells during the production of drinking water. The jar testing experiments with Vaalkop Dam and Rietvlei Dam source water (rich with C. hirundinella) indicated that using cationic poly–electrolyte alone did not remove high concentrations of C. hirundinella efficiently. However, when CaO (in combination with cationic poly–electrolyte or activated silica) were dosed to Vaalkop Dam source water a significant decrease of C. hirundinella concentration was observed. This indicates that the C. hirundinella cells were “shocked or stressed” when exposed to the high pH of the CaO, rendering it immobile and thereby enhancing the coagulation and flocculation process. However, when 10 mg/L CaO in combination with poly–electrolyte was dosed to Rietvlei Dam source water the turbidity and chlorophyll–665 results indicated that this coagulant chemical procedure was ineffective in removing algal material from the source water. The jar testing experiments using the cationic poly–electrolyte alone or cationic poly–electrolyte in combination with CaO on M–FOREBAY and M–CANAL_VD source water, showed a decrease in turbidity, chlorophyll–665 concentration, and total algal biomass, with an increase of coagulant chemical. When CaO in combination with activated silica was dosed, the inherent turbidity of the lime increased the turbidity of the Vaalkop Dam, M–FOREBAY and M–CANAL_VD source water to such an extent that it affected coagulation negatively, resulting in high turbidity values in the supernatant. Regardless of the turbidity values, the chlorophyll–665 concentration and total algal biomass (C. hirundinella specifically in Vaalkop Dam source water) decreased significantly when CaO was dosed in combination with activated silica. Therefore it was concluded that a cationic poly–electrolyte alone is a good coagulant chemical for the removal of turbidity, but when high algal biomass occur in the source water it is essential to add CaO to “stress” or “shock” the algae for the effective removal thereof. However, when CaO in combination with activated silica was dosed to Rietvlei Dam source water a decrease in turbidity and chlorophyll–665 concentration was found with an increasing coagulant chemical concentration. These results confirm the fact that coagulant chemicals may perform differently during different periods of the year when water chemistry changes and that certain coagulant chemicals may never be suitable to use for certain source waters. For the effective removal of algae during water purification, it is recommended that cationic poly–electrolyte in combination with CaO are used as coagulant chemical at the Zuikerbosch Water Purification Plant. Turbidity is not a good indication of algal removal efficiency during jar testing experiments. If problems with high algal concentrations in the source water are experienced it is advisable to also determine the chlorophyll–665 concentrations of the supernatant water during the regular jar testing experiments, since it will give a better indication of algal removal. Chlorine exposure experiments were performed on water from Vaalkop Dam (M–RAW_VAALKOP) and Rietvlei Dam source water, to determine the possibility of implementing pre– or intermediate chlorination with the aim to render the cells immobile for more effective coagulation. The chlorine exposure experiments with Vaalkop Dam and Rietvlei Dam source water showed similar results. The chlorine concentration to be dosed as part of pre– or intermediate chlorination will differ for each type of source water as the chemical and biological composition of each water body are unique. When the effect of chlorine on the freshwater dinoflagellate C. hirundinella was investigated, it was found that the effective chlorine concentration where 50 % of Ceratium cells were rendered immobile (EC50) was approximately 1.16 mg/L for Vaalkop Dam source water. For the source water sampled from Rietvlei Dam, it was found that the EC50 was at approximately 0.87 mg/L. Results of analyses to determine the organic compounds in the water after chlorination revealed that an increase in chlorine concentration resulted in increase in total organic carbon concentration (TOC), as well as a slight increase in MIB and trihalomethanes (CHCl3). Pre– or intermediate chlorination seem to be an effective treatment option for the dinoflagellate C. hirundinella to be rendered immobile and thereby assisting in its coagulation process. The use of pre– or intermediate chlorination to effectively treat source waters containing high concentrations of C. hirundinella is a viable option to consider. However, the organic compounds in the water should be monitored and the EC50 value for each source water composition should be determined carefully as to restrict cell lysis and subsequent release of organic compounds into the water. / Thesis (M.Sc. (Environmental Science))--North-West University, Potchefstroom Campus, 2012.

The Ceratium species occurring in the Vaal River since 2000, was identified as Ceratium hirundinella (O.F. Müller) Dujardin as proposed by Van Ginkel et al (2001). Ceratium hirundinella is known to cause problems in drinking water purification and has been penetrating into the final drinking water of Rand Water since 2006. Ceratium hirundinella is associated with many other water purification problems such as disrupting of the coagulation and flocculation processes, blocking of sand filters and algal penetration into the drinking water. Ceratium hirundinella also produce fishy taste and odorous compounds and causes discolouration of the water. The aims of this study were to determine the main environmental factors which are associated with the bloom formation of C. hirundinella in the source water and to investigate the influence of C. hirundinella on the production of potable water. In order to optimise treatment processes and resolve problems associated with high C. hirundinella concentrations during the production of potable water, jar testing and chlorine exposure experiments were performed. Multivariate statistical analyses were performed to determine the main environmental variables behind C. hirundinella blooms. Ten years data (2000 - 2009) from the sampling point C–VRB5T in the Vaal River, (5 km upstream from the Barrage weir) were used for this investigation, because C. hirundinella occurred there frequently during the ten year period. In this study, it was found that C. hirundinella was favoured by high pH, Chemical Oxygen Demand (COD), orthophoshapte (PO4), and silica concentrations, as well as low turbidity and low dissolved inorganic nitrogen (DIN) concentrations. No correlation was found between C. hirundinella and temperature, suggesting that this alga does not occur during periods of extreme warm or extreme cold conditions, but most probably during autumn and spring. The results of the multivariate statistical analysis performed with historical data from Vaalkop dam, indicate that the dinoflagellate C. hirundinella seems to be favoured by low temperature and turbidity, and high DIN, Fe, Methyl–orange alkalinity, Cd, PO4, Conductivity, pH, hardness and SO4 concentrations. In order to optimise treatment processes such as coagulation, flocculation and sedimentation, jar testing experiments were performed to investigate different coagulant chemicals namely: cationic poly–electrolyte only, cationic poly–electrolyte in combination with slaked lime (CaO) and CaO in combination with activated silica. Water from four different sampling localities were chosen to perform the different jar testing experiments: 1) sampling point M–FOREBAY (in the Forebay, connecting the canal to the Zuikerbosch Purification plant) near Vereeniging due to its proximity to the Zuikerbosch treatment plant, 2) M–CANAL_VD (upstream from the inflow of the recovered water from Panfontein) to determine the influence of (if any) the recovered water from Panfontein on Forebay source water, 3) source water from Vaalkop Dam (M–RAW_VAALKOP) and 4) source water from Rietvlei Dam (water from both Vaalkop and Rietvlei Dams contained high concentrations of C. hirundinella at that time of sampling) to determine which coagulant chemical is the most effective in removing high concentrations of C. hirundinella cells during the production of drinking water. The jar testing experiments with Vaalkop Dam and Rietvlei Dam source water (rich with C. hirundinella) indicated that using cationic poly–electrolyte alone did not remove high concentrations of C. hirundinella efficiently. However, when CaO (in combination with cationic poly–electrolyte or activated silica) were dosed to Vaalkop Dam source water a significant decrease of C. hirundinella concentration was observed. This indicates that the C. hirundinella cells were “shocked or stressed” when exposed to the high pH of the CaO, rendering it immobile and thereby enhancing the coagulation and flocculation process. However, when 10 mg/L CaO in combination with poly–electrolyte was dosed to Rietvlei Dam source water the turbidity and chlorophyll–665 results indicated that this coagulant chemical procedure was ineffective in removing algal material from the source water. The jar testing experiments using the cationic poly–electrolyte alone or cationic poly–electrolyte in combination with CaO on M–FOREBAY and M–CANAL_VD source water, showed a decrease in turbidity, chlorophyll–665 concentration, and total algal biomass, with an increase of coagulant chemical. When CaO in combination with activated silica was dosed, the inherent turbidity of the lime increased the turbidity of the Vaalkop Dam, M–FOREBAY and M–CANAL_VD source water to such an extent that it affected coagulation negatively, resulting in high turbidity values in the supernatant. Regardless of the turbidity values, the chlorophyll–665 concentration and total algal biomass (C. hirundinella specifically in Vaalkop Dam source water) decreased significantly when CaO was dosed in combination with activated silica. Therefore it was concluded that a cationic poly–electrolyte alone is a good coagulant chemical for the removal of turbidity, but when high algal biomass occur in the source water it is essential to add CaO to “stress” or “shock” the algae for the effective removal thereof. However, when CaO in combination with activated silica was dosed to Rietvlei Dam source water a decrease in turbidity and chlorophyll–665 concentration was found with an increasing coagulant chemical concentration. These results confirm the fact that coagulant chemicals may perform differently during different periods of the year when water chemistry changes and that certain coagulant chemicals may never be suitable to use for certain source waters. For the effective removal of algae during water purification, it is recommended that cationic poly–electrolyte in combination with CaO are used as coagulant chemical at the Zuikerbosch Water Purification Plant. Turbidity is not a good indication of algal removal efficiency during jar testing experiments. If problems with high algal concentrations in the source water are experienced it is advisable to also determine the chlorophyll–665 concentrations of the supernatant water during the regular jar testing experiments, since it will give a better indication of algal removal. Chlorine exposure experiments were performed on water from Vaalkop Dam (M–RAW_VAALKOP) and Rietvlei Dam source water, to determine the possibility of implementing pre– or intermediate chlorination with the aim to render the cells immobile for more effective coagulation. The chlorine exposure experiments with Vaalkop Dam and Rietvlei Dam source water showed similar results. The chlorine concentration to be dosed as part of pre– or intermediate chlorination will differ for each type of source water as the chemical and biological composition of each water body are unique. When the effect of chlorine on the freshwater dinoflagellate C. hirundinella was investigated, it was found that the effective chlorine concentration where 50 % of Ceratium cells were rendered immobile (EC50) was approximately 1.16 mg/L for Vaalkop Dam source water. For the source water sampled from Rietvlei Dam, it was found that the EC50 was at approximately 0.87 mg/L. Results of analyses to determine the organic compounds in the water after chlorination revealed that an increase in chlorine concentration resulted in increase in total organic carbon concentration (TOC), as well as a slight increase in MIB and trihalomethanes (CHCl3). Pre– or intermediate chlorination seem to be an effective treatment option for the dinoflagellate C. hirundinella to be rendered immobile and thereby assisting in its coagulation process. The use of pre– or intermediate chlorination to effectively treat source waters containing high concentrations of C. hirundinella is a viable option to consider. However, the organic compounds in the water should be monitored and the EC50 value for each source water composition should be determined carefully as to restrict cell lysis and subsequent release of organic compounds into the water. / Thesis (M.Sc. (Environmental Science))--North-West University, Potchefstroom Campus, 2012.