Submitted in fulfillment of the requirements Of the degree of Masters in applied science: Biotechnology, Durban University of Technology, Durban, South Africa, 2016. / Anaerobic dark fermentation is an efficient biological process to produce hydrogen from waste material. In South Africa, this technology has not been explored adequately to extract energy from biological wastes. Within the KwaZulu Natal region of South Africa, the sugar industry is a prominent venture that produces mass quantities of sugarcane bagasse amongst other waste products. This by-product can be an ideal source of substrate for biohydrogen generation. In this study, sugarcane bagasse was used as the main substrate for biohydrogen production by anaerobic fermentation using sewage sludge as the inoculum. Different pre-treatment methods were employed to maximize the release of fermentable sugars from the lignocellulosic biomass. Among the different pre-treatment methods employed, the maximum sugar yield (294.4 mg/g) was achieved with 0.25% H2SO4 for 60 minutes at 121°C. Prior to inoculation, the sewage sludge was also subjected to thermal pre-treatment to eliminate methanogens. Thermal pre-treatment of inoculum sludge for 30 min was effective in eliminating methanogens. Fluorescence in situ hybridization was used to positively identify the hydrogen producing bacteria present before and after treatment. The pre-treated substrate and inoculum was integrated into a dark fermentation process to further optimize the effect of pH, substrate to biomass, iron and magnetite nanoparticles on hydrogen production. The maximum hydrogen production (1.2 mol/mol glucose) was achieved at a pH range of 5-6, a substrate to biomass ratio of 3.5, and iron and magnetite nanoparticle concentration of 200 mg/L. Microbial analysis using quantitative polymerase chain reaction has confirmed the dominance of Clostridium spp. in the reactor. The highest hydrogenase gene activity (number of copies of hydrogenase gene expression/ng DNA) was recorded in the reactor supplemented with magnetite nanoparticles with lowest being in the raw sludge. There was a direct positive correlation between the hydrogenase gene copy number and the hydrogen yield obtained at different reactor conditions. Scanning electron microscopy was a useful to visually analyse the interaction of microorganisms with activated sludge. This study highlights the significance of anaerobic microorganisms from waste sludge being able to utilize agricultural waste material to produce biohydrogen which could be further scaled up for continuous hydrogen production. In addition, statistical tools used to predict the possible sugar (Design of experiments) and hydrogen yields (Gompertz model) produced would be helpful in saving time during full-scale operation of biohydrogen producing reactors. / M

Submitted in fulfillment of the requirements for the degree of Doctorate of Technology: Biotechnology, Durban University of Technology, Durban, South Africa, 2014. / All over the world concerns have been raised over the possible adverse effects that may occur when exposed to chemicals that have the potential to interfere and affect the endocrine system. The concern is directed at both humans and wildlife. There is still a lack of public awareness regarding Endocrine Disrupting Chemicals (EDCs) and the harmful effects on humans and wildlife. It has only been within the last decade that South Africa began the actual task for proper management and control for water and wastewater quality. There are many ways to detect these EDCs all of which are very laborious and most of the cases these EDCs are either in the pico or nano gram per litre range, too minute for many methods to detect effectively; so therefore the research project aimed to use rapid and sensitive techniques to determine the quickest means to detect the very low concentrations of theses EDCs. Two techniques were researched, i.e., Enzyme Linked immunoassays (ELISAs) and Radio-immunoassays (RIAs). The research study thus assessed the solid phase extraction (SPE) technique for total recovery of hormones; the ELISA and RIA techniques for rapid detection of natural (estrone (E1), estradiol (E2) and estriol (E3) and synthetic ethinylestradiol (EE2) by validating the precision and reproducibility . These techniques were then applied to determine hormone EDC removal first at laboratory scale investigations and then applied to full scale wastewater treatment plants (WWTP) with different configurations in order to deduce removal efficiency of each type of plant. The next phase assessed the toxicity of individual and combined estrogen standards as well as the toxicity in the WWTPs and classify and to determine if there was a correlation between hormone concentration and toxicity in final effluents. The assessment of the SPE and the immunoassay procedures (ELISA AND RIA) using standards and controls found that both these assays can be utilised to quantify hormone estrogens in wastewater. The small sample volume required reduced the labour time and application of the procedure made it cost effective and reliable techniques. The intra-assay and inter-assay validation procedures as well as the standard recoveries confirmed reproducibility and precision of the immunoassays. The % CV were <10% for both the intra-assay and inter-assay validations. The laboratory scale investigations included the operation of a modified Ludzak-Ettinger (MLE) process which enabled control and manipulation over the operational parameters in order to establish how certain parameters influenced the removal of hormone EDCs. One such parameter that was manipulated was the sludge retention time (SRT). The MLE tests showed that the SRTs definitely have an effect on the removal of hormones from the influent as well as the overall performance of sewage treatment. The 10 day SRT proved that longer SRTs will definitely aid in the removal of hormones and possibly other EDCs in raw sewage. During the 10 day SRT the influent hormone concentrations (E1: 59.11 ng/L, E2: 61.40 ng/L) were almost double than the influent hormone concentrations (E1: 26.46 ng/L, E2: 27.60 ng/L) during the 5 day SRT, which impacted on the removal efficiency. The 5 day SRT had an overall average E2 and E1 removal of 78.11% and 81.71% respectively while the 10 day SRT had average E2 and E1 removal of 91.24 % and 80.56% respectively. The 24 hour batch test provided evidence of the reversible metabolism of the E2 hormone. This was seen by the rapid decrease of E2 and the rapid increase of E1 in less than 3 hours, which proved that E2 can be metabolized in to E1. An average reduction of 94.44% of E2 was seen after 5 hours and after 10 hours was no longer detected. After 13 hours E1 could no longer be detected. This finding also provided clarity as to the lower percentage removal of E1 during the 10 day SRT of the MLE process. The Vibrio fischeri biotox method implemented was the most economic and easiest way to conduct the toxicity tests. The validation of the test used a 52.9 mg/L K2Cr2O7 standard which provided a Cr (VI) concentration of 18.7 mg/L in the final test suspension which is the theoretical effective concentration causing 50% inhibition (EC50). This specific concentration of the Cr (VI) exhibited an EC50 at 20.08 mg/L. The toxicity investigations of the individual and mixed hormone standards revealed that at the 10 ng/L concentration the individual E2 standard had the highest percentage inhibition (%INH) of 45.99% after the 30 minute contact time (T30), and when this standard was further diluted to 5 and 1 ng/L also showed higher % INH (26.04 and 23.66 %INH, respectively) than the individual EE2 standard (21.92 %INH) at 10 ng/L. . According to the toxicity classification system and after interpretation of the data, all the hormone standards were classified as Class II as they all exhibited slight acute toxicity. The 10 ng/L E2 standard had Toxicity Units (TU) of 0.8 which was close to the Class III level; however when it was in a mixture with E1 and E3, the TU was much lower (0.6 TU). The synthetic EE2 hormone also showed slight acute toxicity and had the lowest TU of 0.4. The application of the above mentioned techniques to full scale WWTPs with different configurations showed different removal efficiencies. The WWTPs ranged from the most primary consisting of just oxidation ponds to biological trickling filters, to biological nutrient removal (BNR) to conventional activated sludge (AS) plants. Removal rates ranged from 29% to 96% for E2, 0% to 89% for E1 and 0% to 100% for EE2. The overall ranking of the WWTPs from the most efficient to least efficient in terms of hormone removal were as follows: Plant E (91%) = Plant D (before UF) (91%) > Plant B (east side) (88%) > Plant B (west side) (77%) > Plant C (east side) (71%) > Plant D (after UF) (57%) > Plant A (56%) > Plant C (west side) (12%). Using the Vibrio fischeri method to evaluate the reduction of toxicity in WWTPs C, D and E proved effective. It was seen immediately after secondary biological treatment in the clarifier effluent the toxicity was reduced. Plants C, D and E had reduced the toxicities by 100, 80 and 97 % immediately after secondary biological treatment, while after the addition of the Chlorine disinfectant in the final stage of treatment the toxicity increased having %INH of 99.9, 15.7 and 99.9 respectively. In conclusion the SPE can be used as an extraction procedure for hormones in wastewater and the immunoassays can be used as rapid techniques for quantification of hormone EDCs in wastewater. The ELISA technique proved to be the slightly superior to the RIA in terms of facilities required. The laboratory scale procedures proved that some hormones can be oxidised to other hormones and therefore longer sludge retention times may be required to improve the removal. The study of the different WWTPs configuration showed that plant configuration and operational parameters impact the removal of hormone EDCs. The composition of the influent received by the plant also has an effect on the removal, i.e., whether it’s industrial, domestic or a mixture of both. Results concluded that plants which have either mixing and/or aeration with activated sludge and longer SRTs of more than 10 days have a higher rate of hormone removal than those plants with shorter SRTs and that the activated sludge processes were capable of reducing the toxicity of the influent. Overall results indicated that hormone EDCs are indeed being discharged with the effluents from WWTPs in South Africa. However whether the concentrations left in the final effluents will still have an adverse effect on the aquatic life is a question that still remains unanswered. The aquatic ecosystems are inevitably being polluted with these EDCs and their breakdown products. / D

The purpose of this study was to focus attention on the physiology of the bdellovibrio-host interaction and to determine the metabolic requirements for this reaction. Since bdellovibrio is an aerobic organism, direct measurements of respiration, turbidity, and viable cell counts are reliable indications of the metabolic activity of the cells. It was determined that the metabolic requirements for the parasitic interaction are constituents from either metabolically active host cells or cells which are capable of at least some metabolic activity. The nutritional requirements of host-independent bdellovibrios suspended in buffer are not met by the presence or absence of viable or nonviable Enterobacter aegnes. Unlike the HD bdellovibrios, the HI bdellovibrios lack the ability to make economical use of their self-digesting processes.

A research report submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in partial fulfilment of the requirements for the degree of Master of Science in Engineering, 2016 / The aim of this research was to reduce heavy metal and sulfate content of acid mine drainage (AMD) through the methods of passive filtration by combining permeable concrete and organic materials. This was to achieve a low cost, yet effective temporary treatment method for rural/poor communities who are affected by AMD. The acids are filtered through layers of alternating pervious concrete and biological composting layers. The concrete layers target removal of heavy metals such as iron, manganese, potassium, and magnesium, etc. through precipitation as well as reduce sulfate content to a small degree along with total dissolved solids. The concrete layers also aid in raising the pH of the AMD to more acceptable levels. The biological layers achieve sulfate remediation through the metabolism of sulfatereducing- bacteria (SRB). This process however required time and the organic layers were thus thicker and less permeable than the concrete layers in order to allow seepage to take place at a reduced rate. A wide variation of composting layers were tested, including cow manure, chicken manure, sawdust, straw, zoo manure, and leaf compost to find an optimum mix of materials which allows for the greatest sulfate reduction through sulfate reducing bacteria in the shortest possible time. Short as well as Long-term testing of rigs was undertaken to establish effectiveness, limitations and lifespan of the filtration systems. AMD from a mine in the Mpumalanga coal fields with exceptionally high sulfate content was used to test effectiveness of the organic materials over a short period of time. With long term testing conducted with a synthetic AMD, due to limited supply from the mine. The short term testing yielded removal of sulfates in the order of 56% when using kraal manure as the biological reagent mixed with sawdust for added organic carbon. The mix percentages by volume were 80%Sawdust to 20%manure and this setup was able to achieve the 56% removal of sulfates within 14 days. The filter also successfully raised the pH to 8 while removing a significant portion of heavy metals. The long term tests showed complete (100%) remediation of sulfates after a period of approximately sixty days. The tests are continuing to determine their finite lifespan and limitations. The results show promise for using the technology as a low cost, temporary measure to protect locally impacted groundwater, especially for isolated and/or rural communities while a permanent long term solution is sought.

M.Sc., Faculty of Science, University of the Witwatersrand, 2011 / Contamination of water bodies by heavy metals and metalloids is an established problem and several studies have been conducted to deal with it. South Africa is amongst those countries whose water systems are most affected as a result of intensive mining activities. This research was dedicated to the development of insoluble chelating polymers for use as adsorbents to abstract heavy metal ions from mining and industrial wastewater. Branched polyethylenimine (PEI), well known for its metal chelating potential, was cross linked by epichlorohydrin in order to convert it into a water-insoluble form. The water-insoluble property gives the advantage of being used in situ and a possibility of regeneration and re-use, making it a more feasible and cost-effective method. Its surface was also modified for selective removal of specifically-targeted heavy metal and metalloid ions. The binding affinity of the synthesized materials to heavy metal and metalloid ions has been determined as well as their ability to be regenerated for reuse. These processes demonstrated that cross-linked polyethylenimine (CPEI) exhibited good complexation ability with high affinity to Cr and some divalent metal ions such as Fe, Zn, and Ni. On the other hand, it showed very poor ability to bind oxo-anions such as SeO32- and AsO2- which has been attributed to the unavailability of suitable functional groups to interact with these ions. The observed order of complexation was: Cr > Zn> Fe >> Ni > Mn > Pb >> As > U > Se. The phosphonated polyethylenimine (PCPEI) showed high selectivity for As, Mn and uranyl ions. The observed order of removal was: U > Mn> Ni > Zn > As >> Cr > Pb > Fe >> Hg > Se; whereas the suffocated polyethylenimine (SCPEI) exhibited high affinity to Se, and Hg. The observed order of adsorption was: Hg > Se >> U > Zn >Pb > Ni >> As > Cr > Fe. v The adsorption behaviour of these polymeric materials involved more than one mechanism such as complexation, normal surface charge exchange, and anion replacement and all these mechanisms are governed by the functional groups. The nitrogen atom on the chelating group (-NH) in the cross-linked polyethylenimine; the phosphorus atom on the chelating group (-PO3H2) in phosphonated cross-linked polyethylenimine; and sulphur atom on the chelating group (-SO3H) in suffocated cross-linked polyethylenimine act as Lewis bases and donate electrons to metal cations which are considered Lewis acids. The existence of the chelating groups in SCPEI and PCPEI facilitate the removal of oxo-anions through anion replacement since they exist as bases in solution and hence cannot be electron acceptors. Thus, the expected mechanism is the normal anion replacement. This mechanism can explain the high removal of Se by SCPEI since Se has similar chemical behaviour as sulphur and are in the same group in the periodic table. As such they can easily replace each other. Sulphur is released from the polymer into the solution by replacing the selenium ions in the polymer. Similar behaviour occurs between phosphorus in PCPEI and arsenic ions as As and P belong to the same group in the periodic table and hence have similarities in their chemical behaviour. The Langmuir and Freundlich isotherm models were used to interpret the adsorption nature of the metal ions onto synthesized polymers. The Freundlich isotherm was found to best fit and describe the experimental data describing the adsorption process of metal and metalloid ions onto the synthesized polymeric materials The kinetic rates were modelled using the pseudo first-order equation and pseudo second-order equation. The pseudo second-order equation was found to explain the adsorption kinetics most effectively implying chemisorption. vi The thermodynamic study of the adsorption of metals and metalloids by the synthesized CPEI, PCPEI and SCPEI resulted in high activation energies > 41 KJ mol-1 which confirm chemisorption as a mechanism of interaction between adsorbate and adsorbent. So far, the developed polymeric materials showed good results and have potential to be applied successfully for remediation of heavy metal-polluted waters, and they have potential for use in filter systems for household use in communities that use borehole water impacted by mining and industrial waste waters. The desorbed metals can be of use to metal processing industries.

This thesis presents a model which estimates energy and cost savings that can be realized by implementing Energy Conservation Measures (ECMs) at mechanically aerated wastewater treatment plants (WWTPs) in southeast Florida. Historical plant monitoring data is used to estimate savings achieved by implementing innovative aeration technologies which include : 1) Fine Bubble DIffusers ; 2) Single-Stage Turbo Blowers ; 3) Automatic Dissolved Oxygen (DO) Control. Key assumptions for modeling performance of each technology are researched and discussed, such as trends in the future cost of electricity, efficiency of blowers, and practical average DO levels for each scenario. Capital cost estimates and operation maintenance (O&M) costs are estimated to complete life-cycle cost and payback analyses. The benefits are quantified on an individual and cumulative basis, to identify which technologies are cost-beneficial. The results demonstrate that levels of payback of 20 years or less are available at the three WWTPs studied. / by Eric Stanley. / Thesis (M.S.C.S.)--Florida Atlantic University, 2012. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2012. Mode of access: World Wide Web.

Thesis (MTech (Environmental Management))--Cape Peninsula University of Technology, 2017. / ¹Odour nuisance is increasingly becoming one of the major environmental problems in various countries across the world, especially odour associated with wastewater (Alfonsin et al., 2015; Schlegelmilch et al., 2005; Gostelow et al., 2001). As a result, the management of odour from Wastewater Treatment Works (WWTW) has become one of the environmental challenges besetting these facilities in recent times. The dispersion of odour across the physical boundary of wastewater treatment facilities presents not only negative environmental impacts to the natural environment, but also constitute a nuisance to surrounding populations. The Athlone (WWTW) located in the urban City of Cape Town with high demographics and adjacent to sensitive communities is thus not immune to poor air quality associated with WWTW activities (Walton, 2005). The population growth due to rural-urban migration has further put severe pressure on the facility and thus worsening the odour problem in the area. As a result, complaints have been received by the City Council from the surrounding communities over the last 20 years. In response to these complaints, the management of the WWTW introduced an odour management system with a particular focus on the use of a biotrickling filter coupled with the use of odour masking sprays. This management intervention was adopted in order to control the odour emitted to the atmosphere from the facility (WWTW). While these measures are said to reduce the prevalence of odour to the surrounding environment, it was, however, not clear whether or not such management interventions have reduced odour emitted from the treatment plant. This research was premised on two postulations as an approach to analyse the effect of the odour management plan adopted by the Athlone WWTW’s management and these are: 1) the perceived experience of odour by the adjacent neighbouring communities and, 2) the understanding of the inherent atmospheric dynamics (such as wind velocity, atmospheric stability, inversion layer and ventilation) which influence odour dispersal in the area. The research project argues that these two factors should be taken into account to ensure that the management of odour is sustainable. It is within this background that the research aimed at assessing the management of odour at the Athlone WWTW and to find out, if at all, the inherent local atmospheric conditions in the area and views of the surrounding communities are incorporated into the management of odour from the plant. The methodological design adopted in the study was case study approach. However, the atmospheric data (wind speed and direction) was obtained from the South African Weather Service (SAWS). These variables were analysed qualitatively and experimentally by the use of wind diagrams to provide insight on 2atmospheric stability conditions, surface inversion and topographical properties, and how these phenomenon influences odour dispersion. The study also reviewed previous odour management reports produced by the Althone WWTW management. This type of data was finally supported by data collected from the community by means of a community survey, face-to-face in-depth interviews and qualitative observation. Some major findings from the study revealed that the local weather of Athlone influences the dispersion of odour – facilitating dispersion in the summer through high wind velocities, while impeding dispersion during winter due to the presence of atmospheric stability conditions. Prevailing odours in this community has led to a general feeling of displeasure amongst community members especially since the management of the treatment plan does not include the local community in the decision-making process. In spite of these, the facility’s management approach was found to be more of a response driven nature even though it is ranked as a high-risk facility.

by Chan Chui Man. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2006. / Includes bibliographical references (leaves 83-94). / Abstracts in English and Chinese. / Acknowledgements --- p.i / Abstract --- p.ii / 摘要 --- p.iii / Contents --- p.iv / List of Figures --- p.ix / List of Plates --- p.xi / List of Tables --- p.xii / List of Abbreviations --- p.xiv / Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Di(2-ethylhexyl)phthalate (DEHP) --- p.1 / Chapter 1.1.1 --- The chemical class of DEHP: Phthalate ester --- p.1 / Chapter 1.1.2 --- Characteristics of DEHP --- p.3 / Chapter 1.1.3 --- Sources of releases and environmental concentration --- p.4 / Chapter 1.1.4 --- Persistence of DEHP --- p.5 / Chapter 1.1.5 --- Routes of exposure --- p.6 / Chapter 1.1.6 --- Toxicity of DEHP --- p.7 / Chapter 1.1.6.1 --- Acute toxicity --- p.7 / Chapter 1.1.6.2 --- Chronic toxicity --- p.8 / Chapter 1.1.6.2.1 --- Adverse effects on reproduction system --- p.8 / Chapter 1.1.6.2.2 --- Carcinogenicity --- p.9 / Chapter 1.1.6.2.3 --- Developmental toxicity --- p.9 / Chapter 1.1.6.2.4 --- Endocrine disruption --- p.10 / Chapter 1.1.6.2.5 --- Hepatotoxicity --- p.10 / Chapter 1.1.7 --- Regulations --- p.10 / Chapter 1.2 --- Treatment of DEHP --- p.11 / Chapter 1.2.1 --- Conventional treatment technologies --- p.11 / Chapter 1.2.1.1 --- Physical method --- p.11 / Chapter 1.2.1.1.1 --- Adsorption --- p.11 / Chapter 1.2.1.1.2 --- Sonolysis --- p.12 / Chapter 1.2.1.2 --- Photochemical method --- p.13 / Chapter 1.2.1.2.1 --- Photocatalytic oxidation (PCO) --- p.13 / Chapter 1.2.1.3 --- Biological method --- p.13 / Chapter 1.2.1.3.1 --- Biodegradation --- p.13 / Chapter 1.2.1.3.2 --- Sewage treatment process --- p.14 / Chapter 1.2.2 --- Integrated treatment method in the present study --- p.15 / Chapter 1.2.2.1 --- Biosorption --- p.15 / Chapter 1.2.2.1.1 --- Definition of biosorption --- p.15 / Chapter 1.2.2.1.2 --- Advantages of biosorption --- p.16 / Chapter 1.2.2.1.3 --- Chitinous materials as biosorbents --- p.16 / Chapter 1.2.2.1.4 --- Advantages of using chitinous materials as biosorbents --- p.17 / Chapter 1.2.2.1.5 --- Modeling of biosorption --- p.19 / Chapter 1.2.2.2 --- PCO --- p.21 / Chapter 1.2.2.2.1 --- Definition of PCO --- p.21 / Chapter 1.2.2.2.2 --- Mechanism of PCO --- p.23 / Chapter 1.2.2.2.3 --- Advantages of PCO --- p.25 / Chapter 2 --- Objectives --- p.27 / Chapter 3 --- Materials and methods --- p.28 / Chapter 3.1 --- Materials --- p.28 / Chapter 3.1.1 --- Adsorbate --- p.28 / Chapter 3.1.2 --- Biosorbents --- p.28 / Chapter 3.1.2.1 --- Pretreatment of biosorbents --- p.29 / Chapter 3.1.3 --- Photocatalytic reactor --- p.29 / Chapter 3.1.4 --- Photocatalyst --- p.30 / Chapter 3.1.5 --- Electron scavenger --- p.31 / Chapter 3.2 --- Methods --- p.31 / Chapter 3.2.1 --- Determination of DEHP concentration --- p.31 / Chapter 3.2.2 --- Batch biosorption experiment --- p.32 / Chapter 3.2.2.1 --- Screening of biosorbents --- p.33 / Chapter 3.2.2.2 --- Optimization of biosorption conditions --- p.33 / Chapter 3.2.2.2.1 --- Effect of biosorbent concentration --- p.33 / Chapter 3.2.2.2.2 --- Effect of initial pH --- p.33 / Chapter 3.2.2.2.3 --- Effect of biosorption time --- p.34 / Chapter 3.2.2.2.4 --- Effect of temperature --- p.34 / Chapter 3.2.2.2.5 --- Effect of agitation rate --- p.34 / Chapter 3.2.2.2.6 --- Effect of initial DEHP concentration --- p.34 / Chapter 3.2.2.2.7 --- "Combinational effect of initial pH, chitin A concentration and initial DEHP concentration" --- p.35 / Chapter 3.2.3 --- Extraction of adsorbed DEHP from chitin A --- p.35 / Chapter 3.2.3.1 --- Screening of extraction agents --- p.36 / Chapter 3.2.3.2 --- Determination of extraction time --- p.36 / Chapter 3.2.4 --- Batch PCO experiment --- p.36 / Chapter 3.2.4.1 --- Optimization of PCO conditions --- p.38 / Chapter 3.2.4.1.1 --- Effect of reaction time --- p.38 / Chapter 3.2.4.1.2 --- Effect of UV-A intensity --- p.38 / Chapter 3.2.4.1.3 --- Effect of TiO2 concentration --- p.38 / Chapter 3.2.4.1.4 --- Effect of H2O2 concentration --- p.38 / Chapter 3.2.4.1.5 --- Effect of initial pH --- p.39 / Chapter 3.2.4.1.6 --- Combinational effect of H2O2 concentration and initial pH --- p.39 / Chapter 3.2.4.1.7 --- Effect of concentration factor --- p.39 / Chapter 3.2.4.2 --- Identification of intermediates/products of DEHP --- p.39 / Chapter 3.2.4.3 --- Evaluation for the toxicity of DEHP and the intermediates/products by the Microtox® test --- p.40 / Chapter 4 --- Results --- p.42 / Chapter 4.1 --- Batch biosorption experiment --- p.42 / Chapter 4.1.1 --- Screening of biosorbents --- p.42 / Chapter 4.1.2 --- Optimization of biosorption conditions --- p.42 / Chapter 4.1.2.1 --- Effect of biosorbent concentration --- p.42 / Chapter 4.1.2.2 --- Effect of initial pH --- p.42 / Chapter 4.1.2.3 --- Effect of biosorption time --- p.46 / Chapter 4.1.2.4 --- Effect of temperature --- p.46 / Chapter 4.1.2.5 --- Effect of agitation rate --- p.46 / Chapter 4.1.2.6 --- Effect of initial DEHP concentration --- p.46 / Chapter 4.1.2.7 --- "Combinational effect of initial pH, chitin A concentration and initial DEHP concentration" --- p.51 / Chapter 4.1.2.8 --- Summary of biosorption conditions before and after optimization --- p.54 / Chapter 4.2 --- Extraction of adsorbed DEHP from chitin A --- p.54 / Chapter 4.2.1 --- Screening of extraction agents --- p.54 / Chapter 4.2.2 --- Determination of extraction time --- p.55 / Chapter 4.3 --- Batch PCO experiment --- p.56 / Chapter 4.3.1 --- Optimization of PCO conditions --- p.56 / Chapter 4.3.1.1 --- Effect of reaction time --- p.56 / Chapter 4.3.1.2 --- Effect of UV-A intensity --- p.57 / Chapter 4.3.1.3 --- Effect of TiO2 concentration --- p.59 / Chapter 4.3.1.4 --- Effect of H2O2 concentration --- p.60 / Chapter 4.3.1.5 --- Effect of initial pH --- p.61 / Chapter 4.3.1.6 --- Combinational effect of H2O2 concentration and initial pH --- p.62 / Chapter 4.3.1.7 --- Effect of CF --- p.63 / Chapter 4.3.1.8 --- Summary of PCO conditions before and after optimization --- p.63 / Chapter 4.3.2 --- Identification of intermediates/products of DEHP --- p.64 / Chapter 4.3.3 --- Evaluation for the toxicity of DEHP and the intermediates/products by the Microtox® test --- p.66 / Chapter 5 --- Discussion --- p.68 / Chapter 5.1 --- Batch biosorption experiment --- p.68 / Chapter 5.1.1 --- Screening of biosorbents --- p.68 / Chapter 5.1.2 --- Optimization of biosorption conditions --- p.69 / Chapter 5.1.2.1 --- Effect of biosorbent concentration --- p.69 / Chapter 5.1.2.2 --- Effect of initial pH --- p.69 / Chapter 5.1.2.3 --- Effect of biosorption time --- p.70 / Chapter 5.1.2.4 --- Effect of temperature --- p.71 / Chapter 5.1.2.5 --- Effect of agitation rate --- p.71 / Chapter 5.1.2.6 --- Effect of initial DEHP concentration --- p.71 / Chapter 5.1.2.7 --- "Combinational effect of initial pH, chitin A concentration and initial DEHP concentration" --- p.73 / Chapter 5.2 --- Extraction of adsorbed DEHP from chitin A --- p.74 / Chapter 5.2.1 --- Screening of extraction agents --- p.74 / Chapter 5.2.2. --- Determination of extraction time --- p.74 / Chapter 5.3 --- Batch PCO experiment --- p.74 / Chapter 5.3.1 --- Optimization of PCO conditions --- p.74 / Chapter 5.3.1.1 --- Effect of reaction time --- p.74 / Chapter 5.3.1.2 --- Effect of UV-A intensity --- p.74 / Chapter 5.3.1.3 --- Effect of TiO2 concentration --- p.75 / Chapter 5.3.1.4 --- Effect of H2O2 concentration --- p.75 / Chapter 5.3.1.5 --- Effect of initial pH --- p.76 / Chapter 5.3.1.6 --- Combinational effect of H2O2 concentration and initial pH --- p.77 / Chapter 5.3.1.7 --- Effect of CF --- p.77 / Chapter 5.3.2 --- Identification of intermediates/products of DEHP --- p.78 / Chapter 5.3.3 --- Evaluation for the toxicity of DEHP and the intermediates/products by the Microtox test --- p.79 / Chapter 6 --- Conclusions --- p.80 / Chapter 7 --- References --- p.83

Penicillium ochro-chloron (ATCC strain # 36741), a filamentous fungus with the capability for removing copper ions from aqueous solutions, was studied as a possible biological trap (biotrap) for remediation of heavy metal contaminants in industrial wastewaters. This research demonstrated that in shake flasks the fungus removed copper from surrogate wastewater with 100mg/L copper contamination by as much as 99%. These results did not translate to the bioreactor configuration of a packed bed column, as channeling occurred through the bed, shown by conductivity tracer studies. A fluidized bed configuration was studied and resulted in copper removal of 97%, with a capacity of 149 mg[Cu]/g dry weight biomass, under the conditions of 50% dissolved oxygen. For dissolved oxygen concentrations below the critical oxygen concentration for the fungus (20% saturation) there was minimal copper removal. Mixing studies in the fluidized bed reactor showed that the system was diffusion limited. Mathematical modeling using first order kinetics associated with diffusion limited reactions resulted in rate constants for Cu 2+ uptake of approximately 0.031 h -1 , which were dependent on the dissolved oxygen concentration. Modeling of the reaction with a second order kinetic equation showed that there are possibly factors regulating copper uptake besides oxygen. Electron microscopy showed that in some instances the copper removed was retained as large porous spherical extracellular precipitates. Energy Dispersive X-ray (EDX) analysis has shown similar complexes to be copper phosphate precipitates (Crusberg, 1994). Removal of heavy metal contaminants from wastewater discharge is a necessity for many industries, due to environmental concerns and federal regulations. The use of a biological system for the removal and recycling of heavy metals could prove more economical than currently used physio-chemical processes.

Orientador: Eduardo Luiz de Oliveira / Banca: Giselda Passos Giafferis / Banca: Ilza Machado Kaiser / Resumo: Esta pesquisa visa o tratamento de águas residuárias através de Sistemas de Alagados Construídos (Westlands) de fluxo subsuperficial e escoamento horizontal. O principal objetivo deste sistema é a remoção da matéria orgânica, uma vez que, a matéria carbonácea presente no esgoto é degradada, tanto aerobicamente por microorganismos que estão aderidos nas raízes das mocrófitas quanto, anaerobicamente pelas bactérias aderidas no substrato do leito filtrante. A estação de tratamento de esgoto por Alagados Construídos está localizada na cidade de Bauru-SP e trata o esgoto produzido pela Moradia Estudantil e pelo Campus do Departamento de Educação Física da Universidade Estadual Paulista "Júlio de Mesquita Filho" (UNESP). Para uma melhor condição de estudo são utilizadoas três sistemas de leitos com 9m de comprimento por 4,5m de largura e 0,80m de profundidado e inclinação de 1%. Os leitos foram compostos por diferentes substratos: o primeiro, preenchido com brita nº 1, brita nº 3 e areia grossa, o segundo preenchido pedrisco, poliestireno expandido (isopor) moído e reciclado e areia grossa, e o terceiro com brita nº 3 e areia grossa. Com o uso desses diferentes substratos foi possível avaliar em duas etapas de análise, qual deles apresenta os melhores resultados e condições para o tratameto de águas residuárias. A eficiência média de remoção de DBO foi de 85,6% para o leito de brita, 84,2% para o leito de isopor e 85,4% para o leito de areia. A remoção de fosfato teve média de eficiência de 53,3% para o leito de brita, 9,6% para o leito de isopor e 89% para o leito de areia. Para o nitrogênio total Kjeldahl a eficiência média de remoção foi de 7,7% para o leito de brita, 77,0% para o leito de isopor e 75,3% para o leito de areia. No geral todo o sistema se mostrou eficiente para o tratamento de águas residuárias, porém o leito de isopor se destacar por se tratar de um material alternativo e reciclado / Abstract: This research aims at the wastewater treatment systems using constructed wetlands of subsurface flow and horizontal flow. The main objective of this system is the removal of organic matter, since the carbonaceous matter present in the sewage is dedraded, both aerobically by microorganisms which are adhered on the roots of macrophytes, anaerobically by bacteria adhered to the substrate of the filter bed. The sewage treatment plant by Constructed Westlands is located in the city of Bauru, SP, and treats the sewage produced by the student's home and Deparment of Physical Education, Universidade Estadual Paulista "Julio de Mesquita Filho" (UNESP). For a better quality studies are used three-bed systems with 9m long by 4.5m wide and 0.80m depth and inclination of 1%. The beds were made up of different substrates: the first, filled with gravel nº 1, nº3 crushed stone and sand, the second filled with gravel, expanded polystyrene (Stryrofoam) and recycled crushed and coarse sand, gravel and the third paragraph 3 and coarse sand. Using these substrates could be assessed in two stages of analysis, which one gives the best results and conditions for the treatment of wastewater. The average efficiency of BOD removal was 85.6% for the bed of crushed rock, 84.2% for the foam bed and 85.4% for the sand bed. The removal efficiency phosphate averaged 53.3% for the gravek bed, the bed to 9.6% of polystyrene and 89% for the sand bed. For the Kjeldahl nitrogen removal efficiency was an average of 75.7% for the bed of gravel, 77.0% for the bed of Styrodom and 75.3% for the sand bed. In general the whole system is efficient for the treatment of wastewater, byr the bed of Styrofoam stand out because it is an alternative material and recycled / Mestre