With the exceptions of mixing and heating mechanisms, and the recycling of settled solids, no radical changes or improvements have been made to conventional anaerobic digesters treating municipal sewage. These digesters usually function with a hydraulic retention time of 30 to 60 days and at a total solids concentration of 2.6 %(m/v). Volumetric loading is limited since high loadings effect the displacement of the slow growing methanogens. Thus, the hydraulic retention time is coupled to the solids retention time. A crossflow microfiltration unit has been constructed at Northern Waste Water Treatment Works, Durban, to concentrate sludge from a conventional anaerobic digester and, thus, facilitate operation with a higher solids concentration. In addition, this process should result in the retention of the active biomass which would otherwise be lost as a waste product of the treatment process. The solids retention time is, thus, decoupled from the hydraulic retention time. The net result could be higher volumetric loadings, increased microbial activity and increased volatile solids destruction and, hence, improvement in the efficiency of anaerobic digestion of sewage sludge. To test these, different experiments were conducted to specifically determine the effect of higher solids loads. Preliminary experiments were undertaken to determine the biodegradability of primary sludge from the Northern Waste Water Treatment Works. Results showed that primary sludge of 76% VS could be reduced to approximately 48 to 50% VS during an experimental period of 85 days. Reduction of the first 20% VS was rapid if conditions were optimum but subsequent reduction from 55 to 50% VS was slow. It was calculated that approximately 0.88 l gas was produced for every g volatile solids catabolised. Further experiments were conducted to investigate the effects of different solids concentrations on microbial activity. The results showed that the volume of gas produced increased as the solids concentration increased from 2 to 6%(m/v). Digesters with solids concentrations of 6 to 13%(m/v) produced similar volumes of gas. Digesters with solids concentrations of 6 to 13%(m/v) TS produced approximately 300 ml more gas than the control during the 20 days experimental period. The rate of gas production also increased as the solids concentration increased. However, digesters containing 11%(m/v) and 13%(m/v) TS produced similar rates. These results indicate that the introduction of concentrated sludge into the digester improves digestion efficiency. Finally, a semi-continuous digester was operated at a 30 days retention time and at optimum temperature to investigate the efficacy of digesters with increased solids concentrations. The results showed that the rate of gas production increased as the solids concentration increased from 2%(m/v)(control) to 3.8%(m/v). However, the digester operated with 4.7%(m/v) TS produced gas at a rate lower that the digester with 3.8%(m/v) TS. The volatile solids concentrations of all four digesters were similar, indicating neither favourable nor unfavourable effects from increased solids concentrations. The digesters operated with 3.8%(m/v) and 4.7%(m/v) TS produced higher concentrations of volatile acids than the control. The alkalinity concentrations (>_4000 mg t-1 ) were similar for all four digesters. / Thesis (M.Sc.)-University of Natal, Durban, 1995.

This thesis is comprised of two phases; the first phase concerns the effect of arsenic on the denitrification process in the presence of naturally-produced volatile fatty acids (VFAs); while the second phase evaluates the arsenic removal efficiency of New Zealand Iron Sand (NZIS) by adsorption. To accomplish the first phase of the study, VFAs were first produced naturally in an acid-phase anaerobic digester by using commercially-available soy flour. Secondly, a denitrifying biomass was cultivated in a sequencing batch reactor (SBR) using domestic wastewater as a feed solution. Finally, a series of biological denitrification batch tests were conducted in the presence of different concentrations of arsenic and nitrate. As mentioned, the VFAs were generated from an anaerobic digester using 40 g/L soy solution as a synthetic feed. The digester was operated at a solids retention time (SRT) and hydraulic retention time (HRT) of 10 days. The pH of the digester was measured to be 4.7 to 4.9 while the mean temperature was 31 ± 4 °C; however, both these parameters were not controlled. In the effluent of the digester, a mean VFA concentration of 5,997 ± 538 mg/L as acetic acid was achieved with acid speciation results of acetic (33 %), propionic (29 %), butyric (21 %), iso-valeric (5%) and n-valeric acid (12 %). The specific VFA production rate was estimated to be 0.028 mg VFA as acetic acid/mg VSS per day. The effluent sCOD was measured to be 14,800 mg/L (27.9 % of the total COD), as compared to 9,450 mg/L (16.8 % of total COD) in the influent of the digester. Thus, the COD solubilization increased by 11.1 % during digestion yielding a specific COD solubilization rate of 0.025 mg sCOD/mg VSS per day. The extent of the digestion process converting the substrate from particulate to soluble form was also evaluated via the specific TOC solubilization rate (0.008 mg TOC/mg VSS per day), and VSS reduction percentage (17.7 ± 1.8 %). A denitrifying biomass was developed successfully in an SBR fed with domestic sewage (100 % denitrification was achieved for the influent concentration of sCOD = 285 ± 45 mg/L and NH₄⁺-N = 32.5 ± 3.5 mg/L). A mean mixed liquor suspended solids (MLSS) of 3,007 ± 724 mg/L and a mean SRT of 20.7 ± 4.4 days were measured during the period of the research. The settleability of the SBR sludge was excellent evidenced by a low sludge volume index (SVI) measured to be between 50-120 mL/g (with a mean value of 87 ± 33 mL/g) resulting in a very low effluent solids concentration (in many cases less than 20 mg/L). Several preliminary tests were conducted to estimate the right dosage of VFAs (digester effluent), nitrates and arsenic to be added and to confirm the occurrence of denitrification in an appropriate time frame of 4-6 h. From these tests, an optimum C/N ratio was observed to be somewhere between 2 to 4, somewhat higher than all the theoretical C/N ratios required for a complete denitrification using the four major VFAs identified in the digester effluent. During the denitrification batch tests, it was also observed that some NO₃⁻- N was removed instantaneously by reacting with As (III) (As₂O₃); while an increase in alkalinity of around 5.60 mg as CaCO₃ produced per mg NO₃⁻- N reduction was also observed. This latter number was very close to the theoretical value of alkalinity production (i.e. 5.41 mg as CaCO₃ per mg NO₃⁻- N). The effect of arsenic on the denitrification process was evaluated by observing the specific denitrification rate in series of denitrification batch tests (with different concentrations of arsenic). Results from the denitrification batch tests showed that there was a clear effect for both As (III) and As (V) on denitrification. In particular, the specific denitrification rate fell from 0.37 to 0.01 g NO₃⁻- N /g VSS per day as the concentration of As (III) increased from 0 to 50 mg/L. In contrast, there was comparatively less effect for As (V); i.e. only a 37 % decrease in the specific denitrification rate (from 0.34 g NO₃⁻- N /g VSS per day to 0.23 g NO₃⁻- N /g VSS per day) when the initial arsenic concentration increased from 0 to a very high level of 2,000 mg/L. The effects of both the As (III) and As (V) forms of inorganic arsenic on the denitrification rate were further quantified by constructing exponential equation models. It was suspected that the effect of As (III) on denitrification was more substantial than the effect of As (V) because of the former’s toxicity to microbes. Finally, the fate of arsenic was tracked by examining bacterial uptake. During the normal denitrification batch tests (i.e. designed for evaluation of the effect of arsenic on denitrification), no significant arsenic removal was observed. However, additional batch tests with a comparatively low concentration of biomass revealed that the denitrifying biomass removed 1.35 µg As (III) /g dry biomass and 2.10 µg As (V) /g dry biomass. In the second phase of this research, a series of arsenic adsorption batch tests as well as a column test were performed to examine the arsenic (As (III) and As (V)) removal efficiency of NZIS from an arsenic-contaminated water. The kinetics and isotherms for adsorption were analysed in addition to studying the effect of pH during the batch tests. Breakthrough characteristics for both As (III) and As (V) were studied to appraise the effectiveness of NZIS treating an arsenic contaminated water. Batch tests were performed with different concentrations of arsenic as well as at different pH conditions. A maximum adsorption of As (III) of approximately 90 % occurred at a pH of 7.5, while the As (V) adsorption reached its maximum value of 97.6 % at a very low pH value of 3. Both Langmuir and Freundlich Models were tested and found to fit with R² values of more than 0.92 in all cases. From the Langmuir adsorption model, the maximum adsorption capacity of NZIS for As (III) was estimated to be 1,250 µg/g, significantly higher (about three times) than for As (V) of 500 µg/g. In column tests, arsenic-contaminated water with total As concentration of 400 µg/L (in either form of As) were treated and a pore volume (PV) of 700 and 300 yielded a total arsenic level less than the WHO guideline value of 10 µg/L for As (III) and As (V) respectively; while, the breakthrough occurred after a throughput of approximately 3,000 PV of As (III) and 2,700 PV of As (V) with an average flow rate of approximately 1.0 mL/min.

Fischer-Tropsch Reaction Water (FTRW) is a high organic strength wastewater produced as a by-product in Sasol’s Fischer-Tropsch Reactors. Typically it has an organic load of 18000 mgCOD/L and is highly acidic with a pH of approximately 3.8. It is deficient in nutrients (N and P and other micronutrients). This dissertation deals with the biological and physico-chemical model development of a dynamic anaerobic digestion model, and explores two different approaches to representing the physico-chemical processes that complement and interact with the bioprocesses. The performances of the resultant two dynamic models (ADFTRW1 & AD-FTRW2) were compared in order to assess to what extent the more detailed and rigorous ionic speciation modeling in AD-FTRW2 addressed the shortcomings attributed to the simplified physicochemical modeling in AD-FTRW1. The ionic speciation model used in AD-FTRW2 uses a classic equilibrium formulation along the same lines as in the UCTADM2 model for anaerobic digestion of municipal wastewater sludges (Brouckaert et al., 2010), while AD-FTRW1 uses a simplification of the approach developed by Musvoto et al. (2000) in order to represent short chain fatty acid (SCFA) dissociation and the weak acid base chemistry of the inorganic carbon system. A 44 day extract from a 700 day laboratory-scale dataset (Van Zyl et al. 2008) was used as the basis for comparing the models. During this period the membrane bio-reactor was subjected to varying flow and load conditions. To validate the models, the experimentally measured and model predicted process variables of reactor alkalinity, reactor pH, biogas production and effluent SCFA concentration were compared. It was found that AD-FTRW2 provided superior agreement with pH data, but predictions of alkalinity, gas production rate and effluent short-chain fatty acids were not significantly improved in AD-FTRW2 relative to AD-FTRW1. This outcome was hypothesized since pH is strongly dependent on physico-chemical processes such as ionic interactions in solution and gas exchange which were the components to the models (AD-FTRW1 versus AD-FTRW2) which differed most significantly. Alkalinity, which is also highly influenced by physico-chemical model representations showed substantial improvement however statistical analysis could not show this improvement to be significant. The other two variables that were compared, biogas production and effluent SCFA concentration, displayed very similar agreement with experimental data. These variables depend more on mass balance effects and biological kinetics and were therefore not significantly altered by the more rigorous handling of aqueous chemistry in AD-FTRW2. It was concluded that AD-FTRW2 constitutes an improvement in model predictive power over AD-FTRW1 at a small cost in computing time. / Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2013.

Hydrogen gas production occurs in permeable reactive iron barriers (PRBs) due to the anaerobic corrosion of granular iron. Once produced, this hydrogen gas can have detrimental physical effects on PRB performance. Corrosion-produced hydrogen may accumulate in pore spaces within the PRB, thereby reducing the porosity and permeability. It may also escape the PRB system, representing a lost electron resource that may otherwise be used in reductive remediation reactions. In addition to these physical effects of hydrogen on PRB performance, chemical interactions between hydrogen and iron also occur. Hydrogen may become absorbed by the iron and stored as an electron resource within lattice imperfections. It may also interact with iron surfaces to influence the corrosion rate of the iron. These chemical interactions between hydrogen and iron may impact the reactivity of the iron granules and therefore affect PRB performance. Currently, the chemical effects of hydrogen on PRB performance remain largely unexplored. In this study, the effect of hydrogen on iron reactivity was investigated by considering hydrogen absorption into iron and hydrogen induced changes to iron corrosion rates. Hydrogen absorption by iron creates a stored electron resource within the iron granules. Release of this stored hydrogen from trapping sites represents an additional electron resource that may be used in contaminant degradation reactions. Therefore, improved hydrogen absorption may contribute to increased iron reactivity. Hydrogen absorption by granular irons has been largely unexplored in PRB performance investigations and the effect of hydrogen absorption on contaminant remediation remains unknown. In this study, an investigation of the factors governing hydrogen absorption by three granular irons, H2Omet56, H2Omet58 and H2Omet86 was conducted. The results demonstrated that rapidly corroding H2Omet86 absorbed hydrogen at a higher rate than the other more slowly corroding irons. The presence of an oxide film on H2Omet56 appeared to improve the proportion of hydrogen absorption compared to the bare irons. Ultrasonic treatment was explored as potential method of release of trapped hydrogen for improved iron reactivity. Ultrasonic treatment appeared to be unsuccessful at releasing stored hydrogen from trapping sites, but further investigations into different ultrasound conditions as well as other methods of hydrogen release could prove useful. Hydrogen gas may also influence iron reactivity by interacting with iron surfaces to alter the corrosion rate of the iron. This may occur by processes such as hydrogen enhanced anodic dissolution, hydrogen induced cracking, enhanced pitting susceptibility and reduction of iron oxides by hydrogen gas. In this study, the effect of hydrogen on iron corrosion rates was assessed by treating two iron materials (H2Omet56 and Connelly) under high pressures of hydrogen for 14 d, then comparing the post-treatment corrosion rates of hydrogen treated irons to the post-treatment corrosion rates of corresponding irons treated under low hydrogen pressures for the same period. The results demonstrated that the post-treatment corrosion rate of high hydrogen treated H2Omet56 iron was lower than the post-treatment corrosion rate of low hydrogen treated H2Omet56 iron. Hydrogen treatment did not appear to affect the post-treatment corrosion rates of Connelly iron. The effect of hydrogen on the corrosion rate of H2Omet56 iron may be a result of hydrogen enhanced anodic dissolution. The presence of a continuous oxide film on Connelly iron appeared to inhibit the effect of hydrogen enhanced anodic dissolution on Connelly iron corrosion rates. The effects of iron oxide reduction by hydrogen and hydrogen induced pitting corrosion were also considered.

Title: Food waste from grocery stores in Umeå- the potential for taking care of and reducing the amount of food waste. Author: Helene Myhrberg Abstract Food waste from grocery stores is an increasing problem in Sweden, and amounts to roughly 67 000 ton per year. This has consequences both for sustainability in general, but also for achieving the targets stipulated by the EU. Given this, it should be relevant for the society that grocery stores both decrease the amount of food waste but also develop better ways of dealing with food waste. Although there exist methods for this, the practicability of such measures are unknown. In this thesis I assess these issues by conducting interviews with owners and employees at five grocery stores in Umeå, asking them how they think about these questions. In particular, I focus on how to take care of and prepare food waste for anaerobic digestion and how to decrease volumes of food waste. In essence, I find that both the knowledge of, and interest in, these issues vary substantially between grocery stores. Further, for these measures to be feasible, it requires the process to be both economically efficient while not requiring too much time of work. With this in mind, it seems necessary to have a facility that can take care of both packed and unpackaged food waste, making it as cheap and simple as possible for the grocery stores. For reducing volumes of waste, most grocery stores agrees on better planning as the way to go. Key words: food waste, grocery stores, anaerobic digestion, decreasing of food waste.

The biogas plant Kungsängens gård, owned by Uppsala Vatten och Avfall AB, produces biogas and biomanure from organic household waste, food processing waste and slaughterhouse waste. In year 2012, 4.4 million Nm3 of biogas were produced from 25 200 tons of waste. Before digestion all substrate is sanitized by pasteurization at 70°C in order to kill pathogens. Another method, integrated thermophilic sanitation (ITS), is of interest in order to decrease the energy demand. The method implies that the substrate is sanitized during ten hours in the digestion chamber, where the temperature is 52°C. The purpose of this thesis was to compare pasteurization with integrated thermophilic sanitation from an energy point of view. The pasteurization´s impact on biogas production and energy yield was examined through experiments with two laboratory digesters, of which one was fed with pasteurized substrate and the other with non-pasteurized substrate. For the present pasteurization system, electricity and heat demand was surveyed. For the integrated thermophilic sanitation, a process design was developed and dimensioned and the electricity and heat demand was calculated. Thereafter, the energy yield and energy demand for the two sanitation systems were compared. The result showed that pasteurization had no effect on biogas production. The energy yield was on average 4.79 kWh/kg VS from non-pasteurized substrate and 4.74 kWh/kg VS from pasteurized substrate. There was no statistically significant difference between the reactors. The energy audit showed that pasteurization required 0.48 kWh/kg VS, which is 85 % of the total energy consumption at the facility. The digester warming demanded 0.077 kWh/kg VS for RK1 and 0.031 kWh/kg VS for RK2. The electricity consumption was 0.041 kWh/kg VS. The process of ITS was designed with a heat exchange from bio manure to substrate, followed by heating to 52°C by steam addition. The heat requirement was 0.24 kWh/kg VS and the electricity demand was 0.034 kWh/kg VS. The warming of the digesters was the same as in the present pasteurization system. The comparison between the existing pasteurization and the ITS showed that switching systems would save 0.243 kWh/kg VS or 46 % of the present energy consumption. This corresponds to annual savings of 1.22 GWh. A sensitivity analysis showed that the results were sensitive to assumptions regarding the heat exchanger in the case of ITS. 10 % energy losses resulted in smaller savings, 34 % or 0.91 GWh per year. There are increased risks of process disruptions if ITS is combined with an increased organic loading rate. 4.2 % reduction of the total biogas production erases the energy savings which means that it is important that process stability is ensured.

The production of biogas through the anaerobic digestion of cattle manure and its subsequent use in the generation of electricity on large Ontario farms is currently economically attractive. While larger farms have advantages of scale, there are substantially more small farms for which individually designed and engineered biogas systems are prohibitively expensive. Although biogas has numerous benefits, it contains hydrogen sulfide, an odourous, poisonous and corrosive gas, which emits sulfur oxides upon combustion. Larger systems can afford to use specialized biogas engines which tolerate some levels of hydrogen sulfide. For smaller scale systems to be financially attractive the hydrogen sulfide needs to be removed inexpensively, allowing for more flexibility in engine choice for electricity generation. In this work, the solid by-products from the anaerobic digestion process were used to create activated carbon, which has a high capacity for hydrogen sulfide. Not only does the carbon adsorb hydrogen sulfide, it allows for the surface oxidation of hydrogen sulfide to elemental sulfur and sulfate. Since the sulfur is in a beneficial form for fertilizer use, and there are no chemicals added to create the carbon, the spent sulfur-containing carbon can be land applied, eliminating any spent carbon disposal costs.

KB-1 is an anaerobic Dehalococcoides-containing microbial culture used industrially to bioremediate sites impacted with chlorinated solvents. The culture is typically grown at pH 7. However, lower pH is often encountered and therefore the effect of pH was investigated. Both sudden and stepwise decreases in pH from 7 to 6 and 5.5 were investigated over a period of 450 days. An electron balance was also calculated to look at the flow of electrons for dechlorination. More than 95% of the reducing equivalents went towards methanogenesis and acetogenesis. Select microorganisms were compared by quantitative Polymerase Chain Reaction. It was found that lower rates of dechlorination correspond to low Dehalococcoides numbers and that different methanogens were enriched on different electron donors.

The production of biogas through the anaerobic digestion of cattle manure and its subsequent use in the generation of electricity on large Ontario farms is currently economically attractive. While larger farms have advantages of scale, there are substantially more small farms for which individually designed and engineered biogas systems are prohibitively expensive. Although biogas has numerous benefits, it contains hydrogen sulfide, an odourous, poisonous and corrosive gas, which emits sulfur oxides upon combustion. Larger systems can afford to use specialized biogas engines which tolerate some levels of hydrogen sulfide. For smaller scale systems to be financially attractive the hydrogen sulfide needs to be removed inexpensively, allowing for more flexibility in engine choice for electricity generation. In this work, the solid by-products from the anaerobic digestion process were used to create activated carbon, which has a high capacity for hydrogen sulfide. Not only does the carbon adsorb hydrogen sulfide, it allows for the surface oxidation of hydrogen sulfide to elemental sulfur and sulfate. Since the sulfur is in a beneficial form for fertilizer use, and there are no chemicals added to create the carbon, the spent sulfur-containing carbon can be land applied, eliminating any spent carbon disposal costs.

KB-1 is an anaerobic Dehalococcoides-containing microbial culture used industrially to bioremediate sites impacted with chlorinated solvents. The culture is typically grown at pH 7. However, lower pH is often encountered and therefore the effect of pH was investigated. Both sudden and stepwise decreases in pH from 7 to 6 and 5.5 were investigated over a period of 450 days. An electron balance was also calculated to look at the flow of electrons for dechlorination. More than 95% of the reducing equivalents went towards methanogenesis and acetogenesis. Select microorganisms were compared by quantitative Polymerase Chain Reaction. It was found that lower rates of dechlorination correspond to low Dehalococcoides numbers and that different methanogens were enriched on different electron donors.