As indústrias químicas são consideradas como o segmento industrial que gera os efluentes mais perigosos ao meio ambiente. Em virtude das concentrações expressivas de poluentes, tanto orgânicos quanto inorgânicos, os efluentes dessas indústrias podem interferir na atividade da biomassa de estações de tratamento de efluentes (E.T.E.), diminuindo sua eficiência e gerando efluentes tratados, porém em desacordo com a legislação pertinente. Para prevenir tais efeitos, o recebimento de efluentes industriais em E.T.E.s pode ser precedido por pré-tratamento, dentre os quais, o biológico, otimizado pela adição de microrganismos com capacidade de degradar poluentes. Foram isolados microrganismos com capacidade de degradar os compostos identificados como responsáveis pela toxicidade do efluente final da E.T.E.: benzeno, clorofórmio, 1,2-dicloroetano, pentaclorofenol, tricloroeteno, tolueno e p-xileno. Foram realizados testes de bioaumentação para pré tratar o efluente industrial, que foram avaliados através de ensaios físico-químicos e de toxicidade aguda para Vibrio fischeri e Daphnia similis. Os resultados obtidos demonstraram que o pré tratamento reduziu a toxicidade do efluente final da estação de tratamento. / Chemical industries are considered the industrial sector that generates the most dangerous effluents to the environment. Due to the high pollutant concentration, either organics or inorganics, the chemical industries effluents may interferer in the biomass activity in wastewater treatment plants (WWTP), what may reduce its efficiency and generate treated effluents in disagreement to the concerned law. In order to prevent such effects, the industrial effluents disposal in WWTPs can be preceded by biological pretreatment, which can be optimized by adding microorganisms capable of pollutants degradation. Microorganism strains that are able to degrade the compounds identified as the responsible for toxicity levels in the WWTP final effluent: benzene, chloroform, 1,2-dichloroethane, pentachlorophenol, trichloroethene, tolune and p-xylene were isolated. Bioaugmentation tests aiming the chemical effluent pretreatment were performed and they were evaluated through physical-chemical analysis and acute toxicity tests for Vibrio fischeri and Daphnia similis. The results showed that the industrial effluent pretreatment reduced the toxicity levels in the WWTP final effluent.

Membrane fouling, which is caused by deposition/adsorption of foulants on the surface or within membrane pores, still remains a bottleneck that hampers the widespread application of membrane bioreactor (MBR) technology for wastewater treatment. Recently membrane surface modification has proved to be a useful method in water/wastewater treatment to improve the surface hydrophilicity of membranes to obtain higher water fluxes and to reduce fouling. In this study, membrane modification was investigated by depositing a thin film of same thickness of TiO2 on the surface of an ultrafiltration alumina membrane. Various thin-film deposition (TFD) methods were employed, i.e. electron-beam evaporation, sputter and atomic layer deposition (ALD), and a comparative study of the methods was conducted to assess fouling inhibition performance in a lab-scale anaerobic MBR (AnMBR) fed with synthetic municipal wastewater. Thorough surface characterization of all modified membranes was carried out along with clean water permeability (CWP) tests and fouling behavior by bovine serum albumin (BSA) adsorption tests. The study showed better fouling inhibition performance of all modified membranes; however the effect varied due to different surface characteristics obtained by different deposition methods. As a result, ALD-modified membrane showed a superior status in terms of surface characteristics and fouling inhibition performance in AnMBR filtration tests. Hence ALD was determined to be the best TFD method for alumina membrane surface modification for this study. ALD-modified membranes were further characterized to determine an optimum thickness of TiO2-film by applying different ALD cycles. ALD treatment significantly improved the surface hydrophilicity of the unmodified membrane. Also ALD-TiO2 modification was observed to reduce the surface roughness of original alumina membrane, which in turn enhanced the anti-fouling properties of modified membranes. Finally, a same thickness of ALD-TiO2 and ALD-SnO2 modified membranes were tested for alginate fouling inhibition performance in a dead-end constant-pressure filtration system. This is the first report on the application of SnO2-modified ceramic membrane for testing its alginate fouling potential; which was determined to be nearly-same for both modified membranes with a negligible amount of difference. This revealed SnO2 as a potential future anti-foulant to be tested for membrane modification/fabrication for application in water/wastewater treatment systems.

South Africa (SA) currently faces a major pollution problem from mining impacted water, including acid rock drainage (ARD), as a consequence of the mining activities upon which the economy has been largely built. The environmental impact of ARD has been further exacerbated by the country's water scarce status. Increasingly scarce freshwater reserves require the preservation and strategic management of the country's existing water resources to ensure sustainable water security. In SA, the primary focus on remediation of ARDcontaminated water has been based on established active technologies. However, these approaches are costly, lead to secondary challenges and are not always appropriate for the remediation of lower volume discharges. Mostly overlooked, ARD discharges from diffuse sources, associated with the SA coal mining industry, have a marked impact on the environment, similar to those originating from underground mine basins. This is due to the large number of deposits and their broad geographic distribution across largely rural areas of SA. Semi-passive ARD treatment systems present an attractive alternative treatment approach for diffuse sources, with lower capital and operational costs than active systems as well as better process control and predictability than traditional passive systems. These semi-passive systems typically target sulphate salinity through biological sulphate reduction catalysed by sulphate reducing bacteria (SRB). These anaerobic bacteria reduce sulphate, in the presence of a suitable electron donor, to sulphide and bicarbonate. However, the hydrogen sulphide product generated is highly toxic, unstable, easily re-oxidised and poses a significant threat to the environment and human health, so requires appropriate management. An attractive strategy is the reduction of sulphate to sulphide, followed by its partial oxidation to elemental sulphur, which is stable and has potential as a value-added product. A promising approach to achieve partial oxidation is the use of sulphide oxidising bacteria (SOB) in a floating sulphur biofilm (FSB). These biofilms develop naturally on the surfaces of sulphide rich wastewater streams. Its application in wastewater treatment and the feasibility of obtaining high partial oxidation rates in a linear flow channel reactor (LFCR) has been described. The use of a floating sulphur biofilm overcomes many of the drawbacks associated with conventional sulphide oxidation technologies that are costly and require precise operational control to maintain oxygen limiting conditions for partial oxidation. In the current study a hybrid LFCR, incorporating a FSB with biological sulphate reduction in a single reactor unit, was developed. The integration of the two biological processes in a single LFCR unit was successfully demonstrated as a ‘proof of concept'. The success of this system relies greatly on the development of discrete anaerobic and microaerobic zones, in the bulk liquid and at the airliquid interface, that facilitate sulphate reduction and partial sulphide oxidation, respectively. In the LFCR these environments are established as a result of the hydrodynamic properties associated with its design. Key elements of the hybrid LFCR system include the presence of a sulphate-reducing microbial community immobilised onto carbon fibres and the rapid development of a floating sulphur biofilm at the air-liquid interface. The floating sulphur biofilm consists of a complex network of bacterial cells and deposits of elemental sulphur held together by an extracellular polysaccharide matrix. During the Initial stages of FSB development, a thin transparent biofilm layer is formed by heterotrophic microorganisms. This serves as ‘scaffolding' for the subsequent attachment and colonisation of SOB. As the biofilm forms at the air-liquid interface it impedes oxygen mass transfer into the bulk volume and creates a suitable pH-redox microenvironment for partial sulphide oxidation. Under these conditions the sulphide generated in the bulk volume is oxidised at the surface. The biofilm gradually thickens as sulphur is deposited. The produced sulphur, localised within the biofilm, serves as an effective mechanism for recovering elemental sulphur while the resulting water stream is safe for discharge into the environment. The results from the initial demonstration achieved near complete reduction of the sulphate (96%) at a sulphate feed concentration of 1 g/L with effective management of the generated sulphide (95-100% removal) and recovery of a portion of the sulphur through harvesting the elemental sulphur-rich biofilm. The colonisation of the carbon microfibres by SRB ensured high biomass retention within the LFCR. This facilitated high volumetric sulphate reduction rates under the experimental conditions. Despite the lack of active mixing, at a 4-day hydraulic residence time, the system achieved volumetric sulphate reduction rates similar to that previously shown in a continuous stirred-tank reactor. The outcome of the demonstration at laboratory scale generated interest to evaluate the technology at pilot scale. This interest necessitated further development of the process with a particular focus on evaluating key challenges that would be experienced at a larger scale. A comprehensive kinetic analysis on the performance of the hybrid LFCR was conducted as a function of operational parameters, including the effect of hydraulic residence time, temperature and sulphate loading on system performance. Concurrently, the study compared the utilisation of lactate and acetate as carbon source and electron donor as well as the effect of reactor configuration on system performance. Comparative assessment of the performance between the original 2 L LFCR and an 8 L LFCR variant that reflected the pilot scale design with respect to aspect ratio was conducted. Pseudo-steady state kinetics was assessed based on carbon source utilisation, volumetric sulphate reduction, sulphide removal efficiency and elemental sulphur recovery. Additionally, the hybrid LFCR provided a unique synergistic environment for studying the co-existence of the sulphate reducing (SRB) and sulphide oxidising (SOB) microbial communities. The investigation into the microbial ecology was performed using 16S rRNA amplicon sequencing. This enabled the community structure and the relative abundance of key microbial genera to be resolved. These results were used to examine the link between process kinetics and the community dynamics as a function of hydraulic residence time. Results from this study showed that both temperature and volumetric sulphate loading rate, the latter mediated through both sulphate concentration in the feed and dilution rate, significantly influenced the kinetics of biological sulphate reduction. Partial sulphide oxidation was highly dependent on the availability and rate of sulphide production. Volumetric sulphate reduction rates (VSRR) increased linearly as hydraulic residence time (HRT) decreased. The optimal residence time was determined to be 2 days, as this supported the highest volumetric sulphate reduction rate (0.21 mmol/L.h) and conversion (98%) with effective sulphide removal (82%) in the 2 L lactate-fed LFCR. Lactate as a sole carbon source proved effective for achieving high sulphate reduction rates. Its utilisation within the process was highly dependent on the dominant metabolic pathway. The operation at high dilution rates resulted in a decrease in sulphate conversion and subsequent increase in lactate metabolism toward fermentation. This was attributed to the competitive interaction between SRB and fermentative bacteria under varying availability of lactate and concentrations of sulphate and sulphide. Acetate as a sole carbon source supported a different microbial community to lactate. The lower growth rate associated with acetate utilising SRB required longer start-up period and was highly sensitive to operational perturbations, especially the introduction of oxygen. However, biomass accumulation over long continuous operation led to an increase in performance and system stability. Microbial ecology analysis revealed that a similar community structure developed between the 2 L and 8 L lactate-fed LFCR configurations. This, in conjunction with the kinetic data analysis, confirmed that the difference in aspect ratio and scale had minimal impact on process stability and that system performance can be reproduced. The choice of carbon source selected for distinctly different, highly diverse microbial communities. This was determined using principle co-ordinate analysis (PCoA) which highlighted the variation in microbial communities as a function of diversity and relative abundance. The SRB genera Desulfarculus, Desulfovibrio and Desulfomicrobium were detected across both carbon sources. However, Desulfocurvus was found in the lactate-fed system and Desulfobacter in acetate-fed system. Other genera that predominated within the system belonged to the classes Bacteroidetes, Firmicutes and Synergistetes. The presence of Veillonella, a lactate fermenter known for competing with SRB, was detected in the lactate-fed systems. Its relative abundance corresponded well with the lactate fermentation and oxidation performance, where an apparent shift in the dominant metabolic pathway was observed at high dilution rates. Furthermore, the data also revealed preferential attachment of selective SRB onto carbon microfibers, particularly among the Desulfarculus and Desulfocurvus genera. The microbial ecology of the floating sulphur biofilm was consistent across both carbon sources. Key sulphur oxidising genera detected were Paracoccus, Halothiobacillus and Arcobacter. The most dominant genera present in the FSB were Rhizobium, well-known nitrogen fixing bacteria, and Pannonibacter. Both genera are members of the class Alphaproteobacteria, a well-known phylogenetic grouping in which the complete sulphur-oxidising, sox, enzyme system is highly conserved. An aspect often not considered in the operation of these industrial bioprocess systems is the microbial community dynamics within the system. This is particularly evident within biomass accumulating systems where the proliferation of non-SRB over time can compromise the performance and efficiency of the process. Therefore, the selection and development of robust microbial inoculums is critical for overcoming the challenges associated with scaling up, particularly with regards to start-up period, and long-term viability of sulphate reducing bioreactor systems. In the current study, long-term operation demonstrated the robustness of the hybrid LFCR process to maintain relatively stable system performance. Additionally, this study showed that process performance can be recovered through re-establishing suitable operational conditions that favor biological sulphate reduction. The ability of the system to recover after being exposed to multiple perturbations, as explored in this study, confirms the resilience and long-term viability of the hybrid process. A key feature of the hybrid process was the ability to recover the FSB intermittently without compromising biological sulphate reduction. The current research successfully demonstrated the concept of the hybrid LFCR and characterised sulphate reduction and sulphide oxidation performance across a range of operating conditions. This, in conjunction with a clearer understanding of the complex microbial ecology, illustrated that the hybrid LFCR has potential as part of a semi-passive approach for the remediation of low volume sulphate-rich waste streams, critical for treatment of diffuse ARD sources.

Constructed wetlands (CW) and soil aquifer treatment (SAT) represent natural wastewater treatment systems (NWTSs). The high costs of conventional wastewater treatment techniques encourage more studies to investigate lower cost treatment methods which make these appropriate for developing and also in developed countries. The main objective of this research was to investigate the removals of nutrients and organic micropollutants (OMPs) through SAT, CW and the CW-SAT hybrid system. CWs are an efficient technology to purify and remove different nutrients as well as OMPs from wastewater. They removed most of the dissolved organic matter (DOC), total nitrogen (TN), ammonium and phosphate. Furthermore, CWs aeration could be used as one of the alternatives to reduce CWs footprint by around 10%. The vegetation in CWs plays an essential role in the treatment especially for nitrogen and phosphate removals, it is responsible for the removal of 15%, 55%, 38%, and 22% for TN, dissolved organic nitrogen (DON), nitrate and phosphate, respectively. CWs achieved a very high removal for some OMPs; they attenuated acetaminophen, caffeine, fluoxetine and trimethoprim (>90%) under different redox conditions. Moreover, it was found that increasing temperature (up to 36 C) could enhance the removals of atenolol, caffeine, DEET and trimethoprim by 17%, 14%, 28% and 45%, respectively. On the other hand, some OMPs, were found to be removed by vegetation such as: acetaminophen, caffeine, fluoxetine, sulfamethoxazole, and trimethoprim. Moreover, atenolol, caffeine, fluoxetine and trimethoprim, showed high removal (>80%) through SAT system. It was also found that, temperature increasing and using primary instead of secondary effluent could enhance the removal of some OMPs. The CWs performance study showed that these systems are adapted to the prevailing extreme arid conditions and the average percent removals are about, 88%, 96%, 98%, 98% and 92%, for COD, BOD and TSS, ammonium and phosphate, respectively. Additionally, the natural hybrid system (CW-SAT) can provide an effective treatment technology of reclaimed water for replenishing aquifers and subsequent reuse. This hybrid system embodied the performance advantages of both processes and exhibits a high potential for removal of OMPs, nutrients, metals as well as pathogens, bacteria and viruses.

The current global water crisis in addition to continues contamination of natural water bodies with harmful organic micropollutants (OMPs) have driven the development of new water treatment technologies that allow the efficient removal of such compounds. Among a long list of OMPs, antibiotics are considered as top priority pollutants to be treated due to their great resistance to biological treatments and their potential to develop bacterial resistance. Different approaches, such as membrane-based and advance oxidation processes have been proposed to alleviate or minimize antibiotics discharge into aquatic environments. However most of these processes are costly and generate either matrices with high concentration of OMPs or intermediate products with potentially greater toxicity or persistence. Therefore, this thesis proposes the study of an anaerobic membrane bioreactor (AnMBR) for the treatment of synthetic municipal wastewater containing sulfamethoxazole (SMX), a world widely used antibiotic. Besides the general evaluation of AnMBR performance in the COD removal and biogas production, this research mainly focuses on the SMX removal and its degradation pathway. Thus 5 SMX quantification was performed through solid phase extraction-liquid chromatography/mass spectrometry and the identification of its transformation products (TPs) was assessed by gas chromatography/mass spectrometry technique. The results achieved showed that, working under optimal conditions (35°C, pH 7 and ORP around -380 to -420 mV) and after a biomass adaptation period (maintaining 0.85 VSS/TSS ratio), the AnMBR process provided over 95% COD removal and 95-98% SMX removal, while allowing stable biogas composition and methane production (≈130 mL CH4/g CODremoved). Kinetic analysis through a batch test showed that after 24 h of biological reaction, AnMBR process achieved around 94% SMX removal, indicating a first order kinetic reaction with K= 0.119, which highlights the high degradation capacity of the anaerobic bacteria. Along the AnMBR process, 7 TPs were identified and possible degradation pathways were proposed. At low influent SMX concentrations (<10ppb), the only TPs detected was (1) Benzene sulfonamide N-Butyl. However, as the influent SMX concentration increased, it was possible to identify (2) Sulfanilamide, (3) Sulfisomidine and (4) 4-Aminothiophenol. Further degradation of compounds 2, 3 and 4 were detected after 9 hours of biological reaction in a batch test, producing three new intermediate products: (5) Aniline, (6) 4-Pyrimidinamine, 2,6-dimethyl and (7) Acetamide, N-(4-mercaptophenyl). Most of the detected TPs present a less complex structure than SMX, which can be associates with a lower toxicity.

Conventional wastewater treatment plants are able to reduce contaminant loads within regulations but do not take into account emerging contaminants. Antibiotic resistance genes and antibiotic resistant bacteria have been shown to survive wastewater treatment and remain detectable in effluents. The safety of treated wastewaters is crucial, otherwise unregulated and unmitigated emerging contaminants pose risks to public health and impede wastewater reuse. This dissertation aimed to further understanding of emerging microbial threats, and tested two natural and low-cost tools for their mitigation: sunlight, and bacteriophages. A wastewater bacterial isolate, named E. coli PI-7, which is highly antibiotic resistant, carries the novel antibiotic resistance gene New Delhi metallo-beta-lactamase NDM-1 gene, and displays pathogenic traits, was chosen to model responses to the treatments. Results found that solar irradiation was able to achieve a 5-log reduction in E. coli PI-7 numbers within 12 hours of exposure. However, the results also emphasized the risks from emerging microbial contaminants since E. coli PI-7, when compared with a non-pathogenic strain E. coli DSM1103 that has less antibiotic resistance, showed longer survival under solar irradiation. In certain instances, E. coli PI-7 persisted for over 6 hours before starting to inactivate, exhibited complex stress resistance gene responses, and activated many of its concerning pathogenicity and antibiotic resistance traits. However, upon solar irradiation, gene expression results obtained from both E. coli strains also showed increased susceptibility to bacteriophages. Hence, bacteriophages were coupled with solar irradiation as an additional mitigation strategy. Results using the coupled treatment found reduced cell-wall and extracellular matrix production in E. coli PI-7. DNA repair and other cellular defense functions like oxidative stress responses were also impeded, rendering E. coli PI-7 more susceptible to both stressors and successfully hastening the onset of its inactivation. Overall, the dissertation is built upon the need to develop strategies to further mitigate risks associated with emerging microbial contaminants. Solar irradiation and bacteriophages demonstrate potential as natural and low-cost mitigation strategies. Sunlight was able to achieve significant log-reductions in tested E. coli numbers within a day’s exposure. Bacteriophages were able to overwhelm E. coli PI-7’s capacity to resist solar inactivation while not affecting the indigenous microbiota.

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第22785号 / 農博第2428号 / 新制||農||1081(附属図書館) / 学位論文||R2||N5305(農学部図書室) / 京都大学大学院農学研究科地域環境科学専攻 / (主査)教授 藤原 正幸, 教授 村上 章, 教授 中村 公人 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

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Content: The wastewater of leather industry contains pollution loads which includes anionic contaminants such as chloride, sulfate and phosphate. Different treatment technologies for tannery wastewater have been investigated. Adsorption is a promising technique due to its greater selectivity, simple operation, faster regeneration kinetics and high uptake capacity even at trace levels. In the present study, Mg-Al and Zn-Al Layered Double Hydroxides were synthesized by the co-precipitation method at variable pH through a semi-batch system. The prepared material was characterized by XRD, BET surface area determination, TGDTA and FTIR. The chloride, sulfate and phosphate adsorption properties onto Mg-Al and Zn-Al Layered Double Hydroxides from aqueous solutions were evaluated. The adsorption experiments of chloride, sulfate and phosphate were investigated through batch studies at initial concentrations of 100 mg/L of these anions as NaCl, K2SO4 and KH2PO4, respectively. The experiments were carried out separately for each anionic specie by mixing 10 ml of solution with 1 g/L of adsorbent for 5 h. Mixing was performed on a thermostatic shaker at 200 rpm and at room temperature (25 °C). The effect of co-existing anions on the adsorption capacity were also analyzed. After ion adsorption, chloride, sulfate and phosphate concentrations were measured by ion chromatography. The results showed a removal ratio for Mg-Al Layered Double Hydroxide of 24% and 51% for sulfate and phosphate, respectively, while chloride was not removed from the solution. For the adsorbent Zn-Al Layered Double Hydroxide, the removal ratio of sulfate, phosphate and chloride reached 12.76 %, 69.07 % and 6.34%, respectively. Take-Away: Both adsorbents exhibited a satisfactory removal ratio of phosphate. Therefore, Mg–Al and Zn–Al LDHs can be used as effective adsorbents for phosphate removal from industrial wastewaters.

Wastewater compose an environmental risk as it contains high levels of nutrients, including phosphorus. Wastewater treatment plants (WWTPs) reduce phosphorus by using coagulants that precipitate soluble phosphate into metal phosphate, which is separated by settling. Coagulant flow is regulated by a control strategy, typically feedforward or feedback control. Feedforward is based on incoming wastewater disturbances whereas feedback control uses outgoing process values. Incoming phosphate is hard to measure and can be estimated using soft sensors. Modelling control strategies can help decide which strategy that is most suitable. Models describing phosphorus removal are Activated Sludge Model, ASM2d, and primary clarifier model. ASM2d models phosphorus precipitation and the primary clarifier model settling of particles. Tivoli WWTP faces challenges to reach effluent requirements of phosphorus. The wastewater flows through an equalisation tank, Regnbågen, before being pumped to Tivoli. Particulate matter settles in Regnbågen, which is removed by reducing the water level in Regnbågen. This rapidly increases incoming particulate load to Tivoli.Tivoli’s current control strategy is feedforward proportional to suspended solids. It is suspected, that this strategy overdose coagulant during the emptying of Regnbågen. The purpose of this thesis was to find the optimal control strategy for phosphorus precipitation at Tivoli WWTP, by using a model-based approach. Control strategies modelled are; feedforward, feedback and these two control strategies combined. Additional issues resolved are 1) calibration of a model that predicts the effect of chemical dosage on effluent phosphorus concentration from the primary clarifier, 2) calibrationof a soft sensor, 3) determination of which control strategy that is most suitable. ASM2d and a primary clarifier model were used to create a model describing chemical phosphorus removal. The calibration matches measured phosphate concentration, but underestimate peaks. The primary clarifier model was calibrated by minimising load differences for phosphate and total suspended solids, and was calibrated satisfyingly. A simplified soft sensor was constructed, described by a linear relationship between phosphate and pH. Three disturbances for feedforward control were analysed; measured phosphate, the soft sensors estimation of phosphate and Tivoli’s current controlstrategy. The optimal control strategy was found through a multi-criteria analysis. The optimal control strategy is the combined control strategy, when feedforward is proportional to incoming measured phosphate. The performance of all analysed feedforward disturbances were significantly improved when combined with feedback control. Furthermore, consequential errors are distinct when the soft sensor miss-predictincoming phosphate concentration. If the phosphate concentration cannot be correctly measured/estimated, feedback control alone has the best performance.