A local integrated pulp and paper Kraft mill had come under pressure from the local communities and mill personnel to reduce the odours that were perceived to be generated at the Farm Dams and irrigation farm situated adjacent to the mill. The typical odours associated with Kraft mills are due to the generation of four reduced sulphur compounds such as hydrogen sulphide (H2S), methyl-mercaptan (CH3SH), dimethyl-sulphide (CH3)2S and dimethyl-disulphide (CH3)2S2. These compounds are collectively referred to as Total Reduced Sulphur (TRS) components which are generated as a direct result of the Kraft pulping and chemical recovery process. These components can either be in the gaseous or aqueous phase depending on the characteristics of the effluent. Gaseous and aqueous TRS profiling of the mill indicated that hydrogen sulphide (H2S) was the main odour component generated and emitted from the Clarifiers and the Treated Effluent Transfer Sump (TETS) at the effluent treatment plant. The hydrogen sulphide (H2S) emission levels were affected by process upsets, sludge removal frequencies, chemical composition of the effluent, Sulphate Reducing Bacteria (SRB) activity, pH and temperature fluctuations. Treatment options such as pH control using slaked lime, dosing of biocides, addition of biomodifiers and/or a sulphate reduction inhibitor were investigated. The use of slaked lime, Ca(OH) 2, for pH control was not practical due to continuous pH fluctuations, increasing the pH would increase the scaling tendencies of the effluent and would also affect the soil cation-anion exchange properties of the irrigated farm land. The use of non-oxidising biocides was effective in reducing SRB activity between 99.2% and 99.8% at dosages between 4 mg/l and 25 mg/l. However, the use of biocides was not considered as a long term treatment option due to the various disadvantages such as the stability of the biocides at fluctuating pH and temperatures, half-life, environmental accumulation, toxicity and costs. The aqueous H2S level was reduced by 79% using different combinations of biomodifiers (nitrates, nitrites, molybdenum). Increasing the dosages of the biomodifiers (> 500mg/l) would be required to increase the reduction of H2S levels by more than 79%. The increased dosages would significantly increase the cost of the treatment programme. The accumulation of nitrates, nitrites and molybdenum could affect the soil texture, cation-anion exchange capacity, permeability, Sodium Absorption Ratio (SAR) and nutrient availability. A more environmentally friendly and cost effective treatment was found using sodium nitrate (biomodifier) together with AQ (sulphate reduction inhibitor). The continuous dosing of 50 mg/l sodium nitrate together with 4 mg/l AQ would be effective in reducing the average aqueous H2S levels (40 mg/l) by at least 92%. This treatment would also be compatible with aeration or oxidation procedures to further increase the removal of H2S to achieve an aqueous H2S level of <1 mg/l. Aeration or oxidation would also increase the dissolved oxygen and COD levels, increase the inhibition of SRB activity and oxidise any reduced sulphur. The dosing of sodium nitrate and AQ to control the generation of H2S is not patented in South Africa. It can, therefore, be used to treat the Kraft mill effluent without violating any intellectual property rights in South Africa. / Dissertation (MSc(Applied Science))--University of Pretoria, 2008. / Chemical Engineering / unrestricted

The enormous rate of increase in waste generation across the world is a serious threat to the future generation, if not handled properly, due to the creation of health hazards and global warming. This was awakened many engineers and researchers to find an appropriate solution for efficient management of waste. The land filling of the waste is the most widely adopted method for its disposal, whose efficiency mainly depends on the engineered barrier system in place. Though possessing many limitations, clay liner solely or along with Geo-membrane is often used to avoid ground and surface water contamination. The thickness of the liner of a given breakthrough time depends on the transport rates of the selected contaminants. To estimate the transport rate of any given contaminant, it is necessary to understand the different migration processes of contaminants through the liner material. It was observed from the literature that, the transport rate of contaminants mainly depends on Dispersion coefficient (D) and Distribution coefficient (K) which are the main contaminant transport parameters. The amount of contaminant transport through the liner system for a desired time period is thus estimated from these contaminant transport parameters using the Advection-Dispersion Equation (ADE). The unregulated open dumps are another cause of serious environmental problem, where the contaminants are free to migrate in any direction through the underground soil. The percolation rate and the accumulation of leachate increase during the rainy season, which picks up more contaminants from the waste and thus the threat of the leachate increases. The leachate normally migrates in vertical and lateral directions, causing contamination of ground and surface water resources, and hence, there is a need to estimate the transport rates of contaminants in the porous media. These transport rates are not only useful for designing barrier systems, but also useful to find a suitable remediation technique for the removal of contaminants from a contaminated site. Thus, determination of transport rate is very important in effective waste management systems. Most of the researchers have obtained the contaminant transport parameters through the column tests to simulate one dimensional flow. Often, it is a lengthy process and there is a need to find an easy and effective method of determining these parameters which can reduce the time and effort. Generally, the metallic contaminants such as Cadmium (Cd), Copper (Cu), Lead (Pb), Mercury (Hg), Nickel (Ni) and Zinc (Zn) which are most hazardous are considered for the contaminant migration studies. In the present study, the transport rates of two heavy metals Copper and Zinc through locally available Black Cotton soil and Red soil were studied. Column experiments were conducted to simulate the field conditions under two types of test conditions i.e., Constant and Decreasing source concentrations. For Black Cotton soil as the hydraulic conductivity was very less and was taking a long time for achieving complete breakthrough, the soil sectioning method was used to get the depth versus concentration. The soil sectioning method involves the determination of pore water concentration of any given contaminant in different sections of the soil column. The depth versus concentration profile can serve as the same purpose as that of complete column test after breakthrough. The column experiments can be done only up to a relative concentration (C/C0) of about 0.2 instead of 0.8 or more. The soil samples were compacted to different densities to know the effect of density on transport parameters. The Black Cotton Soil samples were compacted to 0.76-0.97 times of maximum dry density and Red Soil samples were compacted to 0.81-0.98 times of maximum dry density. The samples were compacted to lesser densities to reduce the experimentation time. The transport parameters for field densities can be determined by setting „Forecast Trend Lines‟ to the density versus dispersion coefficient and density versus distribution coefficient plots. The contaminant transport was modeled by various methods i.e., Analytical, Semi-analytical, Explicit Finite Difference and Implicit Finite Difference methods. These models can be extended to predict the contaminant migration through soil liners constructed with similar soils. During the lifetime of a landfill, it may be subjected to both constant and decreasing source concentration conditions and thus the contaminant transport parameters determined by both constant and decreasing tests will be useful to estimate the optimum thickness of soil liner. The disposal of waste solutions and sludges by industries has led to problems with the contamination of both soil and groundwater. Much research work has not been carried out in the past for the remediation of contaminated soils in India. Thus an attempt has been made to study in detail the different remediation techniques on various contaminated soils. Three heavy metal contaminated soils were studied with two remediation techniques i.e., Soil washing and immobilization. As a case study, Zinc contaminated soil was collected from Hindustan Zinc Limited located near Udaipur in Rajasthan State, India and column leach tests were conducted on this soil with different leaching solutions to study the efficiency of the soil washing technique. The leaching solutions used for removing zinc from this soil were 0.1N HCl, 0.1N EDTA, 0.1N HCl+0.1N EDTA and 0.1N FeCl3. It was found that 0.1N FeCl3 was more efficient to remove zinc from this soil. The removal efficiency was also high with 0.1N HCl+0.1N EDTA solution. The transport rates were determined by matching the theoretical elution curves with experimental elution curves. The contaminant transport for column leach tests was modeled using analytical solution based on the Leaching Mass Ratio approach. These transport rates are useful to estimate the rate of treatment as well as the amount of flushing solution required to remove Zinc knowing the area of contamination and in-situ soil conditions. One of the potential sources of soil and ground water contamination with toxic metal ions is Effluent Treatment Plant sludge (ETP Sludge). The efficiency of soil washing technique was also studied on ETP Sludge using five leaching solutions i.e., distilled water, 0.1N HCl, 0.1N EDTA, 0.1N HCl+0.1N EDTA and 0.1N FeCl3. ETP sludge was collected at a filter press, KIADB industrial area, Doddaballapur, Bangalore. The removal efficiencies of these leaching solutions for removal of different metal ions (Copper, Zinc, Iron, Nickel, Cadmium, Lead and Chromium) were studied. The highest removal efficiencies were observed with 0.1N FeCl3 and 0.1N HCl+0.1N EDTA. The transport rates of different metals were determined which will be useful to estimate the quantity of leaching solution required in the field to remediate this sludge using soil washing technique. Even though soil washing technique is more effective than immobilization, for less permeable soil with more clay content, it is not a cost effective method. In such cases immobilization technique can be used to remediate the contaminated soil. The immobilized metals will not migrate through soil to groundwater and will not give adverse environmental hazards in their treated state. In the present study, immobilization technique was studied on two materials, (i) contaminated soil from open dump and (ii) ETP Sludge. The contaminated soil was collected from an open dump located at the Bingipura dumping yard, Bangalore and was tested for the presence of heavy metal ions. The efficiency of treatment to immobilize the metals was studied with different additives. The chemical agents with which can decrease the solubility product will be effective to immobilize the metal ions. The stabilizing agents used for treating these materials were lime water, NaOH and cement. These stabilizing agents were selected after preliminary batch tests. Since most of the heavy metals in soils become less mobile with increase in pH, the lime water / NaOH was added to the soil/sludge to adjust the pH of the mixture to 7.0, 8.5 and 10.0. The cement: soil ratios used were, 1:100 (pH=6. 8), 1:50 (pH=8. 1) and 1:25 (pH=9. 8) by weight. Leaching tests were conducted on the amended soils to know the long term efficiencies of the chemical agents for immobilizing the metal ions. The work carried out in this thesis is presented in different chapters as given below: For the design of the liner system, it is necessary to know the different contaminant transport processes, the determination of their rates and modeling. For remediation of contaminated soil, it is required to find the suitable remediation technique based on the amount and type of pollutants, the type of soil and other geological conditions. The detailed information about sources of heavy metals, effects of heavy metal contamination on health and the environment, contaminant transport processes, methods of determining transport rates, and different modeling techniques for contaminant transport are explained in Chapter 1. The Background information along with the scope and objectives of this study are presented in this chapter. The extensive review of literature related to column experiments, various solutions to Advection-Dispersion Equation, and different remediation techniques to treat the contaminated soil, is also presented in this chapter. Chapter 2 gives detailed information about various materials and methods used in this study. The characteristics of soils used in the present study and preparation of different chemical solutions were explained. The experimental procedures of batch tests, column tests and soil sectioning to determine the contaminant transport parameters were given in detail. The experimental procedures that are required for assessing the efficiency of soil washing technique i.e., Batch leach tests and column leach tests were also explained. The laboratory assessment of immobilization efficiency through leaching test was explained briefly. The analytical and numerical solutions used for this study were discussed in detail. This chapter also includes a method of prediction of breakthrough curves from the incomplete column test data. The contaminant transport parameters of metal ion Copper in two locally available soils i.e., Black cotton soil and Red soil were determined by various techniques i.e., Analytical (using MATLAB v7 software), semi-analytical (using POLLUTE v7 software), Explicit Finite Difference Method with two software tools (MATLAB v7 and M.S.EXCEL 2010), Implicit Finite Difference method with three schemes (BTCS, UPWIND & CRANK NICOLSON) using two software tools (MATLAB v7 and M.S.EXCEL 2010). Modifications were done in the spreadsheet solution of non-reactive solute available from the literature to incorporate the retardation factor as the solutes used in this study are reactive in nature. These results are presented in Chapter 3. The contaminant transport parameters determined for different test conditions (constant and variable source concentrations) and for different densities of soil are reported in this chapter. Determination of transport rates corresponding to maximum dry density using trend lines and preparation of design charts to estimate the thickness of the liner are also discussed in this chapter. The contaminant transport parameters were also determined for metal ion Zinc in the same soils with the same techniques as that of Copper and the migration rates were compared for both the ions. These models and comparative results are presented Chapter 4. It was observed that with increase in density, the dispersion coefficient decreases and Distribution coefficient increases. It was also found that the dispersion coefficient of Black Cotton Soil was lower than that of Red Soil whereas the distribution coefficient of Black Cotton soil is much higher than that of Red Soil. Further, it was observed that the dispersion coefficient of Copper was less than that of Zinc whereas the distribution coefficient of Copper was higher than Zinc. The design of liner thickness, based on transport rates of Zinc is briefly discussed in this chapter. A case study has been explained for the remediation of Zinc contaminated sandy soil using soil washing technique. The undisturbed soil samples collected from four locations of waste disposal site of Hindustan Zinc Limited located near Udaipur in Rajasthan State of Western India were assessed to find the suitable leaching solution and number of pore volumes for the effective removal of Zinc from this soil. The chelates/ solvents used for this soil were 0.1N HCl, 0.1N EDTA, 0.1N HCl+0.1N EDTA and 0.1N FeCl3. The contaminant transport parameters were also determined from the column leach tests based on the Leaching Mass Ratio approach and the results are presented in Chapter 5. From the experimental study it was observed that 0.1N FeCl3 and 0.1N HCl+0.1N EDTA are the most suitable leaching solutions to treat this soil. The Chapter 6 contains the sludge analysis of an industrial ETP sludge, column leach test results of this sludge with different leaching solutions, removal efficiencies of different solutions used and the transport rates of different contaminants. The leaching solutions used for this sludge were distilled water, 0.1N HCl, 0.1N EDTA, 0.1N HCl+0.1N EDTA and 0.1N FeCl3. It was observed that 0.1N FeCl3 and 0.1N HCl+0.1N EDTA are the most suitable leaching solutions to treat this sludge. Other solutions have also removed the contaminants by more than 50%, but the number of pore volumes required to leach out the contaminants was high. The order of removal efficiencies of different solutions is presented below: 0.1N FeCl3 > 0.1N HCl + 0.1N EDTA > 0.1N EDTA > 0.1N HCl > distilled water. The transport rates of different contaminants (Cu, Zn, Cd, Fe, Ni, Pb and Cr) were determined using analytical solution and are presented in this chapter. These transport rates are useful to estimate the quantity of leaching solution required in the field to remediate the sludge using soil washing technique. A contaminated soil collected from an open dump site within Bangalore city and ETP Sludge were analyzed to know the efficiency of immobilization/ solidification technique of remediation using three chemical agents lime, NaOH and cement. The soil samples were mixed with different proportions of these chemicals to adjust the pH of the mixtures to 7.0, 8.5 and 10.0. Leaching tests were conducted on the modified soils to know the long term efficiency of these chemical agents to immobilize the contaminants and these results are discussed in Chapter7. The results showed that highest immobilization efficiencies can be achieved with lime for this contaminated soil and cement is the most suitable chemical agent to treat this sludge. The immobilization efficiencies of different stabilizing agents for various metals were studied and the results analyzed. The Chapter 8 includes the major observations and conclusions of the present research work which will be useful for Geotechnical and Geo-environmental engineers to estimate the transport rates of contaminants, to design the soil liners, to assess the efficiency of soil washing technique to remediate the contaminated soil, to estimate the quantity of leaching solution required in the field for soil washing and to find the suitable chemical agent for remediating the contaminated soil by immobilization technique.