Clogging in subsurface-flow treatment wetlands:occurrence and contributing factors

Clogging is a major operational and maintenance issue associated with the use of subsurface flow wetlands for wastewater treatment, and can ultimately limit the lifetime of the system. This review considers over two decades of accumulated knowledge regarding clogging in both vertical and horizontal subsurface flow treatment wetlands. The various physical, chemical and biological factors responsible for clogging are identified and discussed. The occurrence of clogging is placed into the context of various design and operational parameters such as wastewater characteristics, upstream treatment processes, intermittent or continuous operation, influent distribution, and media type. This information is then used to describe how clogging develops within, and subsequently impacts, common variants of subsurface flow treatment wetland typically used in the U.S., U.K., France and Germany. Comparison of these systems emphasized that both hydraulic loading rate and solids loading rate need to be considered when designing systems to operate robustly, i.e. hydraulic overloading makes horizontal-flow tertiary treatment systems in the U.K. more susceptible to clogging problems than vertical-flow primary treatment systems in France. Future research should focus on elucidating the underlying mechanisms of clogging as they relate to the design, operation, and maintenance of subsurface flow treatment wetlands. © 2010 Elsevier B.V.

Determination of vertical and horizontal pathways of injected fresh wastewater into a deep saline aquifer (Florida, USA) using natural chemical tracers

Two deep-well injection sites in south Florida, USA, inject an average of 430 million liters per day (MLD) of treated domestic fresh wastewater into a deep saline aquifer 900 m below land surface. Elevated levels of NH3 (highest concentration 939 µmol) in the overlying aquifer above ambient concentrations (concentration less than 30 µmol) were evidence of the upward migration of injected fluids. Three pathways were distinguished based on ammonium, chloride and bromide ratios, and temperature. At the South District Wastewater Treatment Plant, the tracer ratios showed that the injectate remained chemically distinct as it migrated upwards through rapid vertical pathways via density-driven buoyancy. The warmer injectate (mean 28°C) retained the temperature signal as it vertically migrated upwards; however, the temperature signal did not persist as the injectate moved horizontally into the overlying aquifers. Once introduced, the injectate moved slowly horizontally through the aquifer and mixed with ambient water. At the North District Wastewater Treatment Plant, data provide strong evidence of a one-time pulse of injectate into the overlying aquifers due to improper well construction. No evidence of rapid vertical pathways was observed at the North District Wastewater Treatment Plant.

Emergence and Fate of Siloxanes in Waste Streams: Release Mechanisms, Partitioning and Persistence in Three Environmental Compartments

Siloxanes are widely used in personal care and industrial products due to their low surface tension, thermal stability, antimicrobial and hydrophobic properties, among other characteristics. Volatile methyl siloxanes (VMS) have been detected both in landfill gas and biogas from anaerobic digesters at wastewater treatment plants. As a result, they are released to gas phase during waste decomposition and wastewater treatment. During transformation processes of digester or landfill gas to energy, siloxanes are converted to silicon oxides, leaving abrasive deposits on engine components. These deposits cause increased maintenance costs and in some cases complete engine overhauls become necessary. The objectives of this study were to compare the VMS types and levels present in biogas generated in the anaerobic digesters and landfills and evaluate the energetics of siloxane transformations under anaerobic conditions. Siloxane emissions, resulting from disposal of silicone-based materials, are expected to increase by 29% within the next 10 years. Estimated concentrations and the risk factors of exposure to siloxanes were evaluated based on the initial concentrations, partitioning characteristics and persistence. It was determined that D4 has the highest risk factor associated to bioaccumulation in liquid and solid phase, whereas D5 was highest in gas phase. Additionally, as siloxanes are combusted, the particle size range causes them to be potentially hazardous to human health. When inhaled, they may affix onto the alveoli of the lungs and may lead to development of silicosis. Siloxane-based COD-loading was evaluated and determined to be an insignificant factor concerning COD limits in wastewater. Removal of siloxane compounds is recommended prior to land application of biosolids or combustion of biogas. A comparison of estimated costs was made between maintenance practices for removal of siloxane deposits and installation/operation of fixed-bed carbon absorption systems. In the majority of cases, the installation of fixed-bed adsorption systems would not be a feasible option for the sole purpose of siloxane removal. However they may be utilized to remove additional compounds simultaneously.

Identifying the Structure and Fate of Wastewater Derived Organic Micropollutants by High-resolution Mass Spectrometry

Human activities represent a significant burden on the global water cycle, with large and increasing demands placed on limited water resources by manufacturing, energy production and domestic water use. In addition to changing the quantity of available water resources, human activities lead to changes in water quality by introducing a large and often poorly-characterized array of chemical pollutants, which may negatively impact biodiversity in aquatic ecosystems, leading to impairment of valuable ecosystem functions and services. Domestic and industrial wastewaters represent a significant source of pollution to the aquatic environment due to inadequate or incomplete removal of chemicals introduced into waters by human activities. Currently, incomplete chemical characterization of treated wastewaters limits comprehensive risk assessment of this ubiquitous impact to water. In particular, a significant fraction of the organic chemical composition of treated industrial and domestic wastewaters remains uncharacterized at the molecular level. Efforts aimed at reducing the impacts of water pollution on aquatic ecosystems critically require knowledge of the composition of wastewaters to develop interventions capable of protecting our precious natural water resources.

The goal of this dissertation was to develop a robust, extensible and high-throughput framework for the comprehensive characterization of organic micropollutants in wastewaters by high-resolution accurate-mass mass spectrometry. High-resolution mass spectrometry provides the most powerful analytical technique available for assessing the occurrence and fate of organic pollutants in the water cycle. However, significant limitations in data processing, analysis and interpretation have limited this technique in achieving comprehensive characterization of organic pollutants occurring in natural and built environments. My work aimed to address these challenges by development of automated workflows for the structural characterization of organic pollutants in wastewater and wastewater impacted environments by high-resolution mass spectrometry, and to apply these methods in combination with novel data handling routines to conduct detailed fate studies of wastewater-derived organic micropollutants in the aquatic environment.

In Chapter 2, chemoinformatic tools were implemented along with novel non-targeted mass spectrometric analytical methods to characterize, map, and explore an environmentally-relevant “chemical space” in municipal wastewater. This was accomplished by characterizing the molecular composition of known wastewater-derived organic pollutants and substances that are prioritized as potential wastewater contaminants, using these databases to evaluate the pollutant-likeness of structures postulated for unknown organic compounds that I detected in wastewater extracts using high-resolution mass spectrometry approaches. Results showed that application of multiple computational mass spectrometric tools to structural elucidation of unknown organic pollutants arising in wastewaters improved the efficiency and veracity of screening approaches based on high-resolution mass spectrometry. Furthermore, structural similarity searching was essential for prioritizing substances sharing structural features with known organic pollutants or industrial and consumer chemicals that could enter the environment through use or disposal.

I then applied this comprehensive methodological and computational non-targeted analysis workflow to micropollutant fate analysis in domestic wastewaters (Chapter 3), surface waters impacted by water reuse activities (Chapter 4) and effluents of wastewater treatment facilities receiving wastewater from oil and gas extraction activities (Chapter 5). In Chapter 3, I showed that application of chemometric tools aided in the prioritization of non-targeted compounds arising at various stages of conventional wastewater treatment by partitioning high dimensional data into rational chemical categories based on knowledge of organic chemical fate processes, resulting in the classification of organic micropollutants based on their occurrence and/or removal during treatment. Similarly, in Chapter 4, high-resolution sampling and broad-spectrum targeted and non-targeted chemical analysis were applied to assess the occurrence and fate of organic micropollutants in a water reuse application, wherein reclaimed wastewater was applied for irrigation of turf grass. Results showed that organic micropollutant composition of surface waters receiving runoff from wastewater irrigated areas appeared to be minimally impacted by wastewater-derived organic micropollutants. Finally, Chapter 5 presents results of the comprehensive organic chemical composition of oil and gas wastewaters treated for surface water discharge. Concurrent analysis of effluent samples by complementary, broad-spectrum analytical techniques, revealed that low-levels of hydrophobic organic contaminants, but elevated concentrations of polymeric surfactants, which may effect the fate and analysis of contaminants of concern in oil and gas wastewaters.

Taken together, my work represents significant progress in the characterization of polar organic chemical pollutants associated with wastewater-impacted environments by high-resolution mass spectrometry. Application of these comprehensive methods to examine micropollutant fate processes in wastewater treatment systems, water reuse environments, and water applications in oil/gas exploration yielded new insights into the factors that influence transport, transformation, and persistence of organic micropollutants in these systems across an unprecedented breadth of chemical space.

Evaluation of semi-passive treatment technologies for septic lagoon capacity expansion

In Canada, increases in rural development has led to a growing need to effectively manage the resulting municipal and city sewage without the addition of significant cost- and energy- expending infrastructure. Storring Septic Service Limited is a family-owned, licensed wastewater treatment facility located in eastern Ontario. It makes use of a passive waste stabilization pond system to treat and dispose of waste and wastewater in an environmentally responsible manner. Storring Septic, like many other similar small-scale wastewater treatment facilities across Canada, has the potential to act as a sustainable eco-engineered facility that municipalities and service providers could utilize to manage and dispose of their wastewater. However, it is of concern that the substantial inclusion of third party material could be detrimental to the stability and robustness of the pond system. In order to augment the capacity of the current facility, and ensure it remains a self-sustaining system with the capacity to safely accept septage from other sewage haulers, it was hypothesized that pond effluent treatment could be further enhanced through the incorporation of one of three different technology solutions, which would allow the reduction of wastewater quality parameters below existing regulatory effluent discharge limits put in place by Ontario’s Ministry of the Environment and Climate Change (MOECC). Two of these solutions make use of biofilm technologies in order to enhance the removal of wastewater parameters of interest, and the third utilizes the natural water filtration capabilities of zebra mussels. Pilot-scale testing investigated the effects of each of these technologies on treatment performance under both cold and warm weather operation. This research aimed to understand the important mechanisms behind biological filtration methods in order to choose and optimize the best treatment strategy for full-scale testing and implementation. In doing so, a recommendation matrix was elaborated provided with the potential to be used as a universal operational strategy for wastewater treatment facilities located in environments of similar climate and ecology.

Microbial phylogenetic and functional responses within acidified wastewater communities exhibiting enhanced phosphate uptake

Acid stimulated accumulation of insoluble phosphorus within microbial cells is highly beneficial to wastewater treatment but remains largely unexplored. Using single cell analyses and next generation sequencing, the response of active polyphosphate accumulating microbial communities under conditions of enhanced phosphorus uptake under both acidic and aerobic conditions was characterised. Phosphorus accumulation activities were highest under acidic conditions (pH 5.5 > 8.5), where a significant positive effect on bioaccumulation was observed at pH 5.5 when compared to pH 8.5. In contrast to the Betaproteobacteria and Actinobacteria dominated enhanced biological phosphorus removal process, the functionally active polyP accumulators at pH 5.5 belonged to the Gammaproteobacteria, with key accumulators identified as members of the families Aeromonadaceae and Enterobacteriaceae. This study demonstrated a significant enrichment of key polyphosphate kinase and exopolyphosphatase genes within the community metagenome after acidification, concomitant with an increase in P accumulation kinetics.

Produção de biopolímeros por culturas microbianas mistas selecionadas

Com a realização deste trabalho, pretendeu-se efetuar uma seleção de culturas mistas em reatores semi-descontínuos (SBR) com capacidade de acumulação de polihidroxialcanoatos (PHA). Para a seleção de culturas foram utilizados inóculos provenientes de diferentes Estações de Tratamento de Águas Residuais (ETAR) e ácidos orgânicos voláteis (AOV) como fonte de carbono. Foram testadas diferentes condições como a proveniência do inóculo, as cargas orgânicas aplicadas e a seleção de culturas utilizando soro de queijo. Verificaram-se elevadas remoções da CQO (acima de 90%) em grande parte dos ensaios realizados, apresentando uma acumulação de PHA por parte de algumas espécies de bactérias presentes. Ocorreu o aparecimento de microrganismos filamentosos com capacidade de acumulação de PHA em alguns ensaios, levando a serem testadas como culturas acumuladoras de PHA. A estabilidade das culturas mistas não foi atingida, mesmo havendo ensaios com 80 dias de operação. Efetuaram-se ensaios de acumulação de PHA em reatores descontínuos, utilizando as culturas selecionadas anteriormente em reatores SBR, com AOV provenientes da acidificação anaeróbia de diferentes resíduos (Fração Orgânica dos Resíduos Sólidos Urbanos - FORSU e Soro de Queijo). Verificou-se uma melhor acumulação por parte das culturas selecionadas com soro de queijo, na qual a quantidade de polímero acumulado triplicou.

Emergence and fate of siloxanes in waste streams: Release mechanisms, partitioning and persistence in three environmental compartments

Siloxanes are widely used in personal care and industrial products due to their low surface tension, thermal stability, antimicrobial and hydrophobic properties, among other characteristics. Volatile methyl siloxanes (VMS) have been detected both in landfill gas and biogas from anaerobic digesters at wastewater treatment plants. As a result, they are released to gas phase during waste decomposition and wastewater treatment. During transformation processes of digester or landfill gas to energy, siloxanes are converted to silicon oxides, leaving abrasive deposits on engine components. These deposits cause increased maintenance costs and in some cases complete engine overhauls become necessary. ^ The objectives of this study were to compare the VMS types and levels present in biogas generated in the anaerobic digesters and landfills and evaluate the energetics of siloxane transformations under anaerobic conditions. Siloxane emissions, resulting from disposal of silicone-based materials, are expected to increase by 29% within the next 10 years. Estimated concentrations and the risk factors of exposure to siloxanes were evaluated based on the initial concentrations, partitioning characteristics and persistence. It was determined that D4 has the highest risk factor associated to bioaccumulation in liquid and solid phase, whereas D5 was highest in gas phase. Additionally, as siloxanes are combusted, the particle size range causes them to be potentially hazardous to human health. When inhaled, they may affix onto the alveoli of the lungs and may lead to development of silicosis. Siloxane-based COD-loading was evaluated and determined to be an insignificant factor concerning COD limits in wastewater. ^ Removal of siloxane compounds is recommended prior to land application of biosolids or combustion of biogas. A comparison of estimated costs was made between maintenance practices for removal of siloxane deposits and installation/operation of fixed-bed carbon absorption systems. In the majority of cases, the installation of fixed-bed adsorption systems would not be a feasible option for the sole purpose of siloxane removal. However they may be utilized to remove additional compounds simultaneously.^

Solvent regeneration of activated carbon mixed-matrix membranes for the removal of micropollutants from wastewater

The constantly increasing demand of clean water has become challenging to deal with over the past years, water being an ever more precious resource. In recent times, the existing wastewater treatments had to be integrated with new steps, due to the detection of so-called organic micropollutants (OMPs). These compounds have been shown to adversely affect the environment and possibly human health, even when found in very low concentrations. In order to remove OMPs from wastewater, one possible technique is a hybrid process combining filtration and adsorption. In this work, polyethersulfone multi-channel mixed-matrix membranes with embedded powdered activated carbon (PAC) were tested to investigate the membrane’s adsorption and desorption performance. Micropollutants retention was analyzed using the pharmaceutical compounds diclofenac (DCF), paracetamol (PARA) and carbamazepine (CBZ) in filtration mode, combining the PAC adsorption process with the membrane’s ultrafiltration. Desorption performance was studied through solvent regeneration, using seven different solvents: pure water, pure ethanol, mixture of ethanol and water in different concentration, sodium hydroxide and a mixture of ethanol and sodium hydroxide. Regeneration experiments were carried out in forward-flushing. At first regeneration efficiency was investigated using a single-solute solution (diclofenac in water). The mixture Ethanol/Water (50:50) was found to be the most efficient with long-term retention of 59% after one desorption cycle. It was, therefore, later tested on a membrane previously loaded with a multi-solute solution. Three desorption cycles were performed after which, retention (after 30 min) reached values of 87% for PARA and 72% for CBZ and 55% for DCF, which indicates decent regenerability. A morphological analysis on the membranes confirmed that, in any case, the regeneration cycles did not affect either the membranes’ structure, or the content and distribution of PAC in the matrix.

Trends and strategies of ozone application in environmental problems

Efforts presented by the scientific community in recent years towards the development of numerous green chemical processes and wastewater treatment technologies are presented and discussed. In the light of these approaches, environmentally friendly technologies, as well as the key role played by the well-known advanced oxidation processes, are discussed, giving special attention to the ones comprising ozone applications. Fundamentals and applied aspects dealing with ozone technology and its application are also presented.

Aplicações de cromatografia líquida de alta eficiência para o estudo de poluentes orgânicos emergentes

Emerging organic pollutants (EOP) include many environmental contaminants based on commercial products such as pharmaceuticals, personal care products, detergents, gasoline, polymers, etc. EOP may be candidates for future regulation as they offer potential risk to environmental and human health due to their continual entrance into the environment and to the fact that even the most modern wastewater treatment plants are not able to totally transform / remove these compounds. High performance liquid chromatography is recommended to separate emerging organic pollutants with characteristics of high polarity and low volatility, especially pharmaceuticals, from environmental matrices.

Investigation of the mass transfer processes during the desalination of water containing phenol and sodium chloride by electrodialysis

Oxidation processes are used in wastewater treatment when conventional processes are not effective due to the presence of recalcitrant organic contaminants, like phenol. However, the presence of ionic compounds associated with organic pollutants may retard the oxidation. In this work the transport of species contained in an aqueous solution of phenol containing sodium chloride was evaluated in an electrodialysis (ED) system. An experimental study was carried out in which the influence of the process variables on the phenol loss and sodium chloride removal was investigated. Experiments were also performed without current, in order to determine the phenol transfer due to diffusion. The phenol and salt concentration variations in the ED compartments were measured over time, using dedicated procedures and an experimental design to determine the global characteristic parameters. A phenomenological approach was used to relate the phenol, salt and water fluxes with the driving forces (concentration and electric potential gradients). Under ED conditions, two contributions were pointed out for the phenol transport, i.e. diffusion and convection, this latter coming from the water flux due to electroosmosis related to the migration of salts. The fitting of the parameters of the transport equations resulted in good agreement with the experimental results over the range of conditions investigated. (c) 2008 Elsevier B.V. All rights reserved.

Optimal synthesis of Fenton reactor networks for phenol degradation

There is an increasing need to treat effluents contaminated with phenol with advanced oxidation processes (AOPs) to minimize their impact on the environment as well as on bacteriological populations of other wastewater treatment systems. One of the most promising AOPs is the Fenton process that relies on the Fenton reaction. Nevertheless, there are no systematic studies on Fenton reactor networks. The objective of this paper is to develop a strategy for the optimal synthesis of Fenton reactor networks. The strategy is based on a superstructure optimization approach that is represented as a mixed integer non-linear programming (MINLP) model. Network superstructures with multiple Fenton reactors are optimized with the objective of minimizing the sum of capital, operation and depreciation costs of the effluent treatment system. The optimal solutions obtained provide the reactor volumes and network configuration, as well as the quantities of the reactants used in the Fenton process. Examples based on a case study show that multi-reactor networks yield decrease of up to 45% in overall costs for the treatment plant. (C) 2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Miniaturized structures for removal or selection of particles from liquid flow

The aim of this work was the development of miniaturized structures useful for retention and/or selection of particles and viscous substances from a liquid flow. The proposed low costs structures are similar to macroscopic wastewater treatment systems, named baffles, and allow disassemble. They were simulated using FEMLAB 3.2b package and manufactured in acrylic with conventional tools. Tests for retention or selection of particles in water or air and viscous fluids in water were carried out. Either in air or water particles with 50 mu m diameter will be retained but not with 13 mu m diameter. In aqueous flow, it is also possible the retention of viscous samples, such as silicone 350 cSt. The simulated results showed good agreement with experimental measurements. These miniaturized structures can be useful in sample pretreatment for chemical analysis and microorganism manipulation. (C) 2007 Elsevier B.V. All rights reserved.

CALCINED SLUDGE SINTERING EVALUATION BY HEATING MICROSCOPY THERMAL ANALYSIS

Aiming the use of the sewage sludge produced in one of the largest Brazilian wastewater treatment stations as a raw material for the ceramic industry, the sintering process of the ashes produced from its calcination was evaluated by heating microscopy thermal analysis (HMTA). From the microprocessed images, a method was developed to obtain HMTA dimensional change curves as a function of temperature, equivalent to those usually obtained from dilatometers or by thermomechanical analysis (TMA). The final product after sintering at 1050 degrees C, characterized by X-ray fluorescence spectrometry, scanning electron microscopy and X-ray dispersive energy, indicates the presence of a vitreous phase containing phosphorus, which explains the good sintering properties of the studied calcined sludge, as shown from its HMTA dimensional change curve.