Дисертації з теми "Water pollutant"

Karakalpakstan, Uzbekistan, has faced water scarcity and low water during several years as a consequence of Uzbekistan’s extensive irrigation of cotton fields. The environmental status of the Mejdurechye Reservoir, which is the largest in the lower Amudarya Delta, is therefore of great local importance. This thesis quantifies pollutant mass flows through the reservoir, concidering for instance salt, DDT and Lindane (HCH). Surface water flow paths through Mejdurechye Reservoir are also conceptualized in order to provide suggestions for future a possible monitoring program.

Results show that chloride concentrations have decreased during July 2007-2008 with at least 10% in spite of a large specific evaporation and a reservoir volume reduction of at least 60%. The most important implication of this is that pollutants in the reservoir cannot have been subject of evapoconcentration during this period. DDT and Lindane have on the other hand increased with up to 50000% in concentration and 20000% mass compared to measurements dating back to 2002. A rough age estimation of DDT shows that the DDT has been mobilized recently. The results of this thesis may prove valuable when forming environmental policy plans and setting up future monitoring programs.

This study developed a comprehensive research methodology for identification and quantification of sources responsible for pollutant build-up and wash-off from urban road surfaces. The study identified soil and asphalt wear, and non-combusted diesel fuel as the most influential sources for metal and hydrocarbon pollution respectively. The study also developed mathematical models to relate contributions from identified sources to underlying site specific factors such as land use and traffic. Developed mathematical model will play a key role in urban planning practices, enabling the implementation of effective water pollution control strategies.

Karakalpakstan, Uzbekistan, has faced water scarcity and low water during several years as a consequence of Uzbekistan’s extensive irrigation of cotton fields. The environmental status of the Mejdurechye Reservoir, which is the largest in the lower Amudarya Delta, is therefore of great local importance. This thesis quantifies pollutant mass flows through the reservoir, concidering for instance salt, DDT and Lindane (HCH). Surface water flow paths through Mejdurechye Reservoir are also conceptualized in order to provide suggestions for future a possible monitoring program. Results show that chloride concentrations have decreased during July 2007-2008 with at least 10% in spite of a large specific evaporation and a reservoir volume reduction of at least 60%. The most important implication of this is that pollutants in the reservoir cannot have been subject of evapoconcentration during this period. DDT and Lindane have on the other hand increased with up to 50000% in concentration and 20000% mass compared to measurements dating back to 2002. A rough age estimation of DDT shows that the DDT has been mobilized recently. The results of this thesis may prove valuable when forming environmental policy plans and setting up future monitoring programs.

Landfill is continued to be the most common approach to solid waste disposal. On contrary, landfill practice is still common with increase in water pollution due to leaching of pollutants.Leachate generation from landfill can be defined into two phases, firstly soluble salt produced due to aerobic decomposition or acetogenic phase and secondly methane and carbon dioxide due to anaerobic decomposition or methanogenic phase.Characterization of landfill leachate is used in design to achieve low hydraulic conductivity or decrease permeability as leachate percolating through the waste strata and most important is used to predict level of pollutant in leachate which depend on factors such as temperature, precipitation and waste age. It is therefore crucial for landfill design to take into consideration of factors affecting leachate quality.The purpose of this research is to develop a correlation relationship of factors affecting leachate quality to predict pollutants from landfill which are determined by temperature, precipitation and waste age. The objective of this research is to determine, based the relationship developed and calibration of data obtained from literature review, the optimization of design that reduce pollutants in leachate generated from landfill taking into consideration of basic factors of temperature, precipitation and waste age of landfill.Results of the study revealed that there is a good correlation of pollutants leaching from landfill to the factors of temperature, precipitation and waste age. Higher pollutant concentration is found in average age landfill than the mature age landfill site mainly due to transition from acetogenic phase to methanogenic phase of pollutant decomposition. It is also anticipated that as carbonaceous organic matter decrease in leachate, nitrogeneous organic matter removal is activated in the mature landfill.Using Multiple Regression Analysis Method, mathematic model known as Pollutant Prediction Model is developed to correlate relationship of pollutants to factor affecting leachate quality in the landfill site in terms of temperature, precipitation and waste age.

The risk to groundwater quality following a sub-surface spillage of immiscible pollutants such as oil, petroleum and other organic chemicals is an increasingly potent threat, through escalating industrial application of such pollutants. This study significantly enhances the understanding of the flow of immiscible pollutants within soil, through field scale investigations to define the spatial variability and extent of a contaminated area and the development of a comprehensive framework for the analysis of oil pollutant migration. This study represents a first attempt by researchers to analyse oil pollutant migration on a wide range of scales, from pore- to field-level. The research shows that quantity of pollutant is a critical factor in determining the extent of oil migration. Permeability and porosity of the sample material are also important secondary factors. High permeability assists the migration of oil pollutants. Soils with a high porosity allow the pollutant to migrate vertically under the influence of gravity, whereas soils with low porosity induce lateral oil migration, as the oil spreads from the point of injection. A Jull scale field study using contrasting soil types determines that oil migration is approximately symmetrical about the point of injection. Experimental data is used to establish modelling capabilities for the characterisation of pollutant migration. Modelling is undertaken at two levels. The first consists of the development of simple Gaussian equations based upon observations of oil glomuses. The glomus approach, newly developed in this work, can be compared to a fractal model, with the glomuses observed in each of the different scales studied.

Biofiltration systems like rain gardens and bioswales are an important tool for capturing and infiltrating polluted runoff, but little data exists on their efficiencies within Mediterranean climates. A two-year study initiated in 2015 investigated water retention and pollutant loading and retention in the Ballona Creek Rain Garden (BCRG). This 300 by 3 m biofiltration system was constructed by The Bay Foundation in 2011 along Ballona Creek in Culver City, Los Angeles County, California. The purpose of the garden was to capture and infiltrate runoff from light industrial and commercial operations bordering the Creek, thus reducing pollutants entering this waterway and flowing into Santa Monica Bay 9 km downstream. During storm events, runoff enters the garden via five inlets, and when filled, flows into the creek via two outlets. The goal of this study was to sample flows and pollutant concentrations in runoff entering and leaving the garden and then integrate these to calculate mass loading estimates. Flows were measured at all inlets and outlets using 90° V-notch weirs outfitted with Hobo water level sensors to produce hydrographs. The following pollutants were measured at all flowing inlets and outlets two to three times per storm depending on its duration and intensity: fecal indicator bacteria (E. coli and enterococci), total suspended solids, metals (copper, zinc, and lead), and semivolatile hydrocarbons (polyaromatic hydrocarbons, diesel hydrocarbons, and motor oil hydrocarbons). The summation of load method was used to calculate the mass of contaminants entering and leaving the garden for each storm event, and their percent capture within the garden. The BCRG was very effective at infiltrating runoff and sequestering pollutants. The garden’s infiltration rates ranged from 73% to 100% (with 100% for many of the smaller storms

In the design of urban drainage systems, synthetic design storms are commonly used to predict the peak flow rate in sewer systems and such storms are usually based on local intensity-duration frequency curves or design storm profiles. To estimate the quality of storm flow, the UPM Manual (1994) has highlighted the development of detailed and sophisticated simulation models to estimate the pollutographs, that is, the temporal variation in the concentration of pollutants in urban drainage systems. The data requirements of these models are quite onerous, and as a consequences implified models like SIMPOL have been developed. This model predicts the BOD at 1 hour time intervals and is based on the representation of the sewer system by a series of tanks. This approach may be considered satisfactory for the prediction of accumulative pollution over an annual series of events but for the prediction of acute effects, for example, the first foul flush, the temporal variation in the concentration pollutants in sewer flow is required. There is a need therefore to describe the change in pollution over a much smaller time interval than that proposed in SIMPOL and this is particularly so when consideration is given to the comparison of the design and control options which may be proposed, for example, the real time control of storage tanks to retain the first flush of pollutants. The work outlined in this thesis presents an alternate simple methodology to estimate the pollutographs corresponding to a particular storm event. The work is based on the results of the measured pollutographs recorded on the WRc sewer quality archive (1987) from two catchments at Great Harwood and Clayton-le- Moors in the North West of England. The relationships for the shape of the pollutograph were obtained by the direct comparison of the observed pollutographs. The peak TSS concentrations were obtained by a detailed regression analysis of the observed peak TSS concentrations, the antecedent dry weather period and the hydrological parameters of maximum rainfall intensity, average rainfall intensity and storm duration. These parameters were then related to the shape of the pollutograph and the results of this methodology were shown to satisfactorily reproduce results for the catchments considered. For practical applications, the suggested procedure provides a methodology to calibrate the design pollutographs for any catchment from a limited number of monitored storm events and to utilise these together with time series storms to assist in the performancea ssessmenat nd selectiono f alternative design options. The work has the limitation that it is catchment specific but as more information for different catchments becomes available, it may be possible to establish standard pollutographs for application to a wide range of catchment conditions.

Storm water quality can have a significant impact on receiving water bodies. The chief recipients of these impacts are aquatic life in the receiving water body and downstream water users. Over the last few decades, legislation, regulations, institutions and facilities have evolved to recognize the impact of urban storm water on receiving streams. This increased emphasis has caused contaminants in storm water to be identified as a major concern. This developing concern has generated an increased interest in the water quality of our streams and lakes and emphasized the need for more monitoring efforts. With the passage of the National Pollutant Discharge Elimination System (NPDES) Phase II requirements, small municipalities are responsible for storm water impacts on receiving waters within their jurisdiction. For the purposes of NPDES Phase II requirements, small municipalities are identified as these municipalities that are typically composed of 10,000 but less than 100,000 in population. The purpose of this dissertation is to develop a manual for use by the staff of small municipalities in meeting the requirements prescribed by changes initiated in the NPDES Phase II regulations. Attempts were made to comply with these requirements within a very limited manpower and budget framework and to develop procedures that would allow for permit compliance using testing equipment that was both reliable and robust. The users' manual provides valuable guidance in the establishment of a knowledge base for characterization of the watersheds selected for study. Chapter 3 of the dissertation contains a users' manual, designed for use by municipal staff members in their efforts to comply with the NPDES Phase II requirements. Using the techniques and equipment capabilities developed during the writing of the users' manual a characterization of three watersheds within Denton County, Texas was developed. Non-storm water samples were taken from each of the streams and a baseline analysis was established. The three watersheds represented agricultural, suburban and urban settings. Storm water samples were obtained from multiple storms within all three watersheds and data analysis used to determine the character and impact of urban runoff. Determination of the constituents for analysis was based on monitoring requirements of the NPDES Phase I and II requirements for owners and operators of municipal separate storm sewer systems (MS4) and on the Texas Pollutant Discharge Elimination System (TPDES) Multi-Sector General Permit (MSGP). The three watersheds were determined to have multiple statistically significant differences for some parameters between their Base Flows and Storm Flows. The impact of urban runoff on the receiving waters of these three drainage systems was clearly demonstrated throughout the testing period.

The main focus of urban stormwater runoff disposal has traditionally been to provide structurally-sound drainage systems to carry runoff from many different surfaces without considering water quality at outfall. This has contributed to the decline of water quality in rivers and lakes and other receiving bodies. According to Lord (1987), "stormwater management is primarily concerned with limiting future flood damages and environmental impacts due to development, where as flood control aims at reducing the extent of flooding that occurs under current conditions". Recent developments in stormwater pollutant trap (SPTs), which are generally end-of-the-line devices designed to capture and store gross pollutants, for subsequent removal and disposal.During the last few decades, use of SPTs as a source of collecting and removing pollutants from stormwater (which carries many different types of chemicals and nonchemical pollutants that contaminates our rivers, lakes and other receiving bodies) has increased considerably. Wide-ranging efforts and attempts have been made in both academic and industrial research to improve the quality of stormwater by improving the use of gross pollutant traps (GPTs – known as hydrodynamic separators) by utilising and improving available experimental and modelling techniques. The use of vortex phenomena has always been a challenging problem and available data is rare and complicated in the literature. This research focuses on detailed investigation by experimental means. The generated vortex in this experiment is created in a cylindrical chamber above the level of a cylindrical screening basket. In addition, the research analyses the processes involved in this separation technique.One scale model of a Versa Trap (Type A) was experimentally analysed to investigate and establish the relationship between headloss and flow rate and hydraulic characteristics of a weir in a diversion weir pit. The Versa trap Type A storm pollutant traps are usually used as off-line traps in city and urban areas to capture and store debris – especially those which are captured from surfaces such as rooftops, paved streets, highways, parking lots, lawns, and paved and gravelled roads (Allison et al., 1998). The Versa Trap Type A utilises an upstream diversion weir pit to divert the design treatment flow (DTF) into the treatment chamber. Treated flow returns to the diversion pit downstream of the weir, where it re-enters the drainage system. Peak flow in excess of the DTF bypasses the SPT over the weir into the pipeline downstream.It has been demonstrated that the aggregate of all flows of three months average recurrence interval (ARI) and less represented the majority (up to 97.5%) of the total flow generated by a stormwater drainage catchment (Works, 2006). There is some conjecture as to the veracity of the ‘first flush’ theory, which holds that most of the pollutants in the catchments are transported during the first flush of the storm event (Lee et al., 2007). However, it is generally accepted that SPTs should be sized so as to treat only a portion of the peak flow, with excess flows bypassing the trap. The three month ARI peak flow is commonly taken as appropriate for establishing the minimum DTF required of the SPT.The measurement of headloss across a scale model of a VT Type A storm pollutant trap at a range of flow rates through the SPT, provide data from which a mathematical relationship between flow rate and the headloss cab be established for the device.The resultant relationship then can be used in another part of the experiment to establish the hydraulic characteristics of a weir across a cylindrical chamber, as used for the upstream diversion weir pit in conjunction with the Type A VT range of SPTs. By varying the weir height in a scale model of a diversion weir pit and measuring the flow rates associated with headlosses determined from the previously established relationship, the relationship between weir height and diverted flow can be established. This allows the designer to specify the weir height required to divert the flow rate associated with a specific peak flow or treatment flow of SPT design.Two main characteristics which determine the performance of a gross pollutant trap are trapping efficiency and required maintenance. The trapping efficiency is defined as the portion of the total mass of gross pollutant transported by stormwater that is retained by the trap. A low trapping efficiency means that gross pollutants pass through the trap and reach downstream waters. A poorly-maintained trap will be inefficient at trapping pollutants and is also a potential source of pollutants as trapped materials break down.The experiment parts of this project were tested at Curtin University of Technology’s Hydraulic Laboratory. To replicate typical in-situ conditions, the VT Type A was tested for 0, 22, 33, 44, 55, 66 and 77% simulated blocked screen conditions for trapping efficiency. Data analysis has demonstrated that the headloss increases in proportion to flow rates and screen blockage condition. The results were scaled up to provide data on the full range of unit sizes. This research describes the testing and scaling methodologies in detail, with graphical representation of headloss and other hydraulic parameters at various conditions. The study’s findings have capabilities to optimise any other types of stormwater treatment systems. These types of traps’ are used in commercial and residential environment.This experiment is in continuation of the experiment which was conducted by Muhammad Ismail on industrial gross pollutant traps using double basket to trap the debris for industrial application.Also another good reference for pollutant build up and wash off modelling of impervious surfaces in Perth area, is done by Saadat Ashraf in his PhD thesis. For more information refer to references.

Many different stormwater control measures (SCMs) can be implemented in order to mitigate issues with polluted stormwater flows into receiving water bodies.  The treatment function of  SCMs is commonly based on the removal of particles by sedimentation, thereby also removing pollutants associated with particles. In recent years, more attention has been given to characterizing and understanding of different particle size fractions and their association with pollutants commonly found in stormwater. It has become increasingly clear that the smaller sized particles are very important pollutant transporters and should be considered when designing and implementing SCMs. However, the settling velocities for smaller sized particles are very low and may not be effectively removed in existing SCMs. One treatment process with a proven ability to enhance sedimentation is coagulation/flocculation, widespread in water and wastewater treatment, but with very few accounts of it being used in a stormwater context. This thesis aims to investigate the treatability of stormwater with a coagulation/flocculation process. This includes the determination of operating conditions, the dominating coagulation mechanism and the reduction efficiency of stormwater related pollutants. The objectives of the thesis were achieved in laboratory tests treating stormwater in a jar-testing procedure. An initial screening of primary coagulants and flocculant aids was conducted using an urban snowmelt mixture. Five of the chemicals were then selected for an extended testing regime which was setup up to determine the operating conditions where maximal turbidity reduction was attained by measuring the pH, conductivity, alkalinity and zeta-potential over the tested doses for each coagulant. Criteria used for chemical selection included high turbidity reduction, low dose requirement and low pH/alkalinity impacts. Charge reversal was observed at positive zeta-potential indicating that the dominating coagulation mechanism was charge neutralization. The content of turbidity/total suspended solids, total organic carbon, total metals and hydrocarbons by >90%. Dissolved copper was reduced by 40% on average, and the reduction rates for dissolved zinc were varying with up to a 300% increase, presumably due to changes in pH, leading to a higher mobility. Changes in the particle size distribution after coagulation/flocculation as compared to sedimentation indicated an effect on the size fraction corresponding to smaller particles. The performance of the coagulation/flocculation process was also tested on road runoff collected from a central road in Luleå with a high traffic intensity. Two coagulants were tested, iron chloride and pre-hydrolyzed aluminum chloride. Reduction rates for the total metal fraction were >90% on average for both coagulants, but for the dissolved metal fractions differences could be observed between the coagulants with the iron chloride resulting in higher reductions for dissolved chrome (57% compared to 34%) and copper (47% compared to 30%). Both products increased the dissolved fractions of nickel and zinc due to lower final pH.

This thesis details methodology to estimate urban stormwater quality based on a set of easy to measure physico-chemical parameters. These parameters can be used as surrogate parameters to estimate other key water quality parameters. The key pollutants considered in this study are nitrogen compounds, phosphorus compounds and solids. The use of surrogate parameter relationships to evaluate urban stormwater quality will reduce the cost of monitoring and so that scientists will have added capability to generate a large amount of data for more rigorous analysis of key urban stormwater quality processes, namely, pollutant build-up and wash-off. This in turn will assist in the development of more stringent stormwater quality mitigation strategies. The research methodology was based on a series of field investigations, laboratory testing and data analysis. Field investigations were conducted to collect pollutant build-up and wash-off samples from residential roads and roof surfaces. Past research has identified that these impervious surfaces are the primary pollutant sources to urban stormwater runoff. A specially designed vacuum system and rainfall simulator were used in the collection of pollutant build-up and wash-off samples. The collected samples were tested for a range of physico-chemical parameters. Data analysis was conducted using both univariate and multivariate data analysis techniques. Analysis of build-up samples showed that pollutant loads accumulated on road surfaces are higher compared to the pollutant loads on roof surfaces. Furthermore, it was found that the fraction of solids smaller than 150 ìm is the most polluted particle size fraction in solids build-up on both roads and roof surfaces. The analysis of wash-off data confirmed that the simulated wash-off process adopted for this research agrees well with the general understanding of the wash-off process on urban impervious surfaces. The observed pollutant concentrations in wash-off from road surfaces were different to pollutant concentrations in wash-off from roof surfaces. Therefore, firstly, the identification of surrogate parameters was undertaken separately for roads and roof surfaces. Secondly, a common set of surrogate parameter relationships were identified for both surfaces together to evaluate urban stormwater quality. Surrogate parameters were identified for nitrogen, phosphorus and solids separately. Electrical conductivity (EC), total organic carbon (TOC), dissolved organic carbon (DOC), total suspended solids (TSS), total dissolved solids (TDS), total solids (TS) and turbidity (TTU) were selected as the relatively easy to measure parameters. Consequently, surrogate parameters for nitrogen and phosphorus were identified from the set of easy to measure parameters for both road surfaces and roof surfaces. Additionally, surrogate parameters for TSS, TDS and TS which are key indicators of solids were obtained from EC and TTU which can be direct field measurements. The regression relationships which were developed for surrogate parameters and key parameter of interest were of a similar format for road and roof surfaces, namely it was in the form of simple linear regression equations. The identified relationships for road surfaces were DTN-TDS:DOC, TP-TS:TOC, TSS-TTU, TDS-EC and TSTTU: EC. The identified relationships for roof surfaces were DTN-TDS and TSTTU: EC. Some of the relationships developed had a higher confidence interval whilst others had a relatively low confidence interval. The relationships obtained for DTN-TDS, DTN-DOC, TP-TS and TS-EC for road surfaces demonstrated good near site portability potential. Currently, best management practices are focussed on providing treatment measures for stormwater runoff at catchment outlets where separation of road and roof runoff is not found. In this context, it is important to find a common set of surrogate parameter relationships for road surfaces and roof surfaces to evaluate urban stormwater quality. Consequently DTN-TDS, TS-EC and TS-TTU relationships were identified as the common relationships which are capable of providing measurements of DTN and TS irrespective of the surface type.

Municipal separate storm sewer system (MS4) permittees face costly obligations to reduce pollutant loadings needed to achieve waste load allocations (WLAs) and meet total maximum daily loads (TMDLs). Street sweeping is potentially an effective BMP since streets exist throughout urban watersheds, often are directly connected to the storm sewer, and are found to contain an abundance of contaminants. Although pollutant removal from street sweeping has been evaluated for decades, an understanding of the impact on water quality in receiving streams is elusive. Due to numerous variables, the large number of samples necessary to measure impact in receiving streams may never be obtained. In response, modeled pollutant removal efficiencies based on frequency of sweeping have been recommended to the Chesapeake Bay Program, but these results are suspect. Alternatively, the amount of swept material has emerged as a method to quantify reductions. A sampling study was conducted to measure pollutants in swept material. The study identified the fraction of material susceptible to transport in runoff based on timing of sweeping in relation to runoff events. Based on observed pollutant concentration associations with particle size, the study results in estimates of pollutant concentrations for the fraction of material susceptible to downstream transport, dependent on duration since the last rainfall and type of surface swept, whether the area is a streets or a parking lot. Pollutant loadings and required reductions to achieve the Chesapeake Bay WLAs for various land use sample areas are computed for an average year. Modeled removal efficiencies and results from the sampling study were employed to assess impacts from street sweeping. Modeled efficiencies predict significantly lower impact than measurements of pollutants susceptible to runoff in swept material. Modeled loadings are inconsistent with measurements of swept materials and the rigorous sweeping frequency required for modeled removal efficiency credit appears to be unnecessary.
Doctor of Philosophy

Bibliography :leaves 158-171. A monitoring program, funded by the South Australian government (through the former MFP Development Corporation), was established to monitor the quality and quantity of storm water entering and leaving the wetland. This study formed part of the funded program. Simple regression models were developed; and will assist in the monitoring of performance of the wetland to alleviate the pollutant load into the Barker Inlet.

PMPSgLig-NaMMT nanocomposites were prepared from methacryloxypropyltrimethoxysilane (MPS), lignocellulose and montmorillonite clay. The potential enhancement of organic pollutant adsorption capabilities of PMPSgLig-NaMMT nanocomposite from water through functionalization was investigated. PMPSgLig-NaMMT was functionalized by esterification and etherification using different methods so as to increase the surface hydrophobicity of the material and hence improve its compatibility with the target pollutants. Specific chemical routes specially tailored for PMPSgLig-NaMMT were established for functionalization mostly based on the common esterification (Fischer esterification) and etherification (Williamson‟s etherification) reactions. In the functionalization methods, factors such as pH environment, nanocomposite composition, nature of functionalization moiety, and use of or absence of solvents and their variations were studied. FT-IR, XRD, SEM and TGA were used to characterize the synthesized and functionalized nanoadsorbents. The techniques showed successful functionalization via esterification and etherification methods albeit to different extents, with clear retention of the material‟s original structure though there were signs of degradation with some methods. Characterization was supported by adsorption studies to validate implications and draw conclusions. The use of 1,10-phenathroline as a model organic pollutant in water in the adsorption studies showed that adsorbents conformed to monolayer adsorption following pseudo-second order kinetics for adsorption of organic pollutants accurately represented. Most importantly the studies revealed the significant impact of the nanocomposite composition on the overall absorbent performance. Adsorption studies also showed that functionalization via esterification methods gave rise to better adsorbents.

Riverine environments are stressed and damaged by anthropogenic actions, with chemical contamination a key factor, identified as potentially adversely impacting the aquatic network. Standardised Organisation for Economic Co-Operation and Development (OECD) tests are used to establish biodegradation rates of chemicals in the environment, however these tests are conducted in unrealistic conditions deficient of environmental realism. Increasing the environmental realism of OECD tests has the capacity improve prediction of chemical persistence and identify potential for damage to the environment. Moreover, the interactions between bedform, microbial biofilm communities and chemical biodegradation at the sediment-water interface are not considered in OECD tests. The current project explored the effects of bed-form characteristics on biofilm development and the consequences of sediment on biodegradation at the sediment-water interface. Novel flume systems were designed, constructed and used to develop methodologies to investigate the impact of bed form on hyporheic exchange. River water and sediment were sampled from a stretch of the River Dene (Wellesbourne, UK) and used as microbial inocula in chemical biodegradation studies using a series of specially designed re-circulating flume systems and ex-situ bottle experiments. Flume experimentation quantified the rate of microbial community development, topographical location and effective depth penetration on sediment beds within artificial watercourses, whilst simultaneously identifying the impact that this biofilm development possessed on hyporheic exchange. The effects of light and inoculum source on para-nitrophenol (PNP) biodegradation were also determined following OECD regulatory test protocols in an attempt to evaluate the realism of chemical biodegradation tests. Experimental data showed that microbial development varied on different sediment bed profiles, and that biofilms significantly reduced the rate of hyporheic exchange on small (0.5 mm), but not large (2.0 mm) sediment particle size bed materials. Additionally, this study found that light inhibited PNP degradation in all tests and that sediment sieving utilised in OECD tests decreased rates of biodegradation of PNP. This project revealed the importance of microbial biofilms in determining hyporheic exchange. However, further experimental work is recommended to investigate hyporheic exchange in heterogeneous sediments, whilst developing more inclusive approaches for chemical risk management by Regulatory bodies.

Urban traffic and climate change are two phenomena that have the potential to degrade urban water quality by influencing the build-up and wash-off of pollutants, respectively. However, limited knowledge has made it difficult to establish any link between pollutant buildup and wash-off under such dynamic conditions. In order to safeguard urban water quality, adaptive water quality mitigation measures are required. In this research, pollutant build-up and wash-off have been investigated from a dynamic point of view which incorporated the impacts of changed urban traffic as well as changes in the rainfall characteristics induced by climate change. The study has developed a dynamic object classification system and thereby, conceptualised the study of pollutant build-up and wash-off under future changes in urban traffic and rainfall characteristics. This study has also characterised the buildup and wash-off processes of traffic generated heavy metals, volatile, semi-volatile and non-volatile hydrocarbons under dynamic conditions which enables the development of adaptive mitigation measures for water quality. Additionally, predictive frameworks for the build-up and wash-off of some pollutants have also been developed.

The most significant human impacts on the hydrological system are due to land-use change. The conversion of land to agricultural, mining, industrial, or residential uses significantly alters the hydrological characteristics of the land surface and modifies pathways and rates of water flow. If this occurs over large or critical areas of a catchment, it can have significant short and long-term impacts, on the quality of water. While there are methods available to quantify the pollutants in surface water, methods of linking non-point source pollution to water quality at catchment scale are lacking. Therefore, the research presented in this thesis investigated modelling techniques to estimate the effect of land-cover type on water quality. The main goal of the study was to contribute towards improving the understanding of how different land-covers in an urbanizing catchment affect surface water quality. The aim of the research presented in this thesis was to explain how the quality of surface runoff varies on different land-cover types and to provide guidelines for minimizing water pollution that may be occurring in the Kuils-Eerste River catchment. The research objectives were
(1) to establish types and spatial distribution of land-cover types within the Kuils-Eerste River catchment, (2) to establish water quality characteristics of surface runoff from specific land-cover types at the experimental plot level, (3) to establish the contribution of each land-cover type to pollutant loads at the catchment scale. Land-cover characteristics and water quality were investigated using GIS and Remote Sensing tools. The application of these tools resulted in the development of a land-cover map with 36 land classifications covering the whole catchment. Land-cover in the catchment is predominantly agricultural with vineyards and grassland covering the northern section of the catchment. Vineyards occupy over 35% of the total area followed by fynbos (indigenous vegetation) (12.5 %), open hard rock area (5.8 %), riparian forest (5.2 %), mountain forest 
 
(5 %), dense scrub (4.4 %), and improved grassland (3.6 %). The residential area covers about 14 %. Roads cover 3.4 % of the total area. Surface runoff is responsible for the transportation of large quantities of pollutants that affect the quality of water in the Kuils-Eerste River catchment. The different land-cover types and the distribution and concentration levels of the pollutants are not uniform. Experimental work was conducted at plot scale to understand whether land-cover types differed in their contributions to the concentration of water quality attributes emerging from them. Four plots each with a length of 10 m to 12 m and 5 m width were set up. Plot I was set up on open grassland, Plot II represented the vineyards, Plot III covered the mountain forests, and Plot IV represented the fynbos land-cover. Soil samples analyzed from the experimental plots fell in the category of sandy soil (Sa) with the top layer of Plot IV (fynbos) having loamy sand (LmSa). The soil particle sizes range between fine sand (59.1 % and 78.9 %) to coarse sand (between 7 % and 22 %). The content of clay and silt was between 0.2 % and 2.4 %. Medium sand was between 10.7 % and 17.6 %. In terms of vertical distribution of the particle sizes, a general decrease with respect to the size of particles was noted from the top layer (15 cm) to the bottom layer (30 cm) for all categories of the particle sizes. There was variation in particle size with depth and location within the experimental plots.Two primary methods of collecting water samples were used
grab sampling and composite sampling. The quality of water as represented by the samples collected during storm events during the rainfall season of 2006 and 2007 was 
used to establish  
water quality characteristics for the different land-cover types. The concentration of total average suspended solids was highest in the following land-cover types, cemeteries (5.06 mg L^-1), arterial roads/main roads (3.94 mg L^-1), low density residential informal squatter camps (3.21 mg L^-1) and medium density residential informal townships (3.21 mg L^-1). Chloride concentrations were high on the following land-cover types, recreation grass/ golf course (2.61 mg L^-1), open area/barren land (1.59 mg L^-1), and improved grassland/vegetation crop (1.57 mg L^-1). The event mean concentration (EMC) values for NO₃-N were high on commercial mercantile (6 mg L^-1) and water channel (5 mg L^-1). The total phosphorus concentration mean values recorded high values on improved grassland/vegetation crop (3.78 mg L^-1), medium density residential informal townships (3mgL^-1) and low density residential informal squatter camps (3 mg L^-1). Surface runoff may also contribute soil particles into rivers during rainfall events, particularly from areas of disturbed soil, for example areas where market gardening is taking place. The study found that different land cover types contributed differently to nonpoint source pollution. A GIS model was used to estimate the diffuse pollution of five pollutants (chloride, phosphorus, TSS, nitrogen and NO₃-N) in response to land cover variation using water quality data. The GIS model linked land cover information to diffuse nutrient signatures in response to surface runoff using the Curve Number method and EMC data were developed. Two models (RINSPE and N-SPECT) were used to estimate nonpoint source pollution using various GIS databases. The outputs from the GIS-based model were compared with recommended water quality standards. It was found that the RINSPE model gave accurate results in cases where NPS pollution dominate the total pollutant inputs over a given land cover type. However, the N-SPECT model simulations were too uncertain in cases where there were large numbers of land cover types with diverse NPS pollution load. All land-cover types with concentration values above the recommended national water quality standard were considered as areas that needed measures to mitigate the adverse effects of nonpoint pollution. The expansion of urban areas and agricultural land has a direct effect on land cover types within the catchment. The land cover changes have adverse effect which has a potential to contribute to pollution.

Accurate and reliable estimations are the most important factors for the development of efficient stormwater pollutant mitigation strategies. Modelling is the primary tool used for such estimations. The general architecture of typical modelling approaches is to replicate pollutant processes along with hydrologic processes on catchment surfaces. However, due to the lack of understanding of these pollutant processes and the underlying physical parameters, the estimations are subjected to gross errors. Furthermore, the essential requirement of model calibration leads to significant data and resource requirements. This underlines the necessity for simplified and robust stormwater pollutant estimation procedures. The research described in this thesis primarily details the extensive knowledge developed on pollutant build-up and wash-off processes. Knowledge on both build-up and wash-off were generated by in-depth field investigations conducted on residential road and roof surfaces. Additionally, the research describes the use of a rainfall simulator as a tool in urban water quality research. The rainfall simulator was used to collect runoff samples from small-plot surfaces. The use of a rainfall simulator reduced the number of variables which are common to pollutant wash-off. Pollutant build-up on road and roof surfaces was found to be rapid during the initial time period and the rate reduced when the antecedent dry days increase becoming asymptote to a constant value. However, build-up on roofs was gradual when compared to road surfaces where the build-up on the first two days was 66% of the total build-up. Though the variations were different, it was possible to develop a common replication equation in the form of a power function for build-up for the two surface types with a as a multiplication coefficient and b as a power coefficient. However, the values for the two build-up equation coefficients, a, and b were different in each case. It was understood that the power coefficient b varies only with the surface type. The multiplication coefficient varies with a range of parameters including land-use and traffic volume. Additionally, the build-up observed on road surfaces was highly dynamic. It was found that pollutant re-distribution occurs with finer particles being removed from the surface thus allowing coarser particles to build up. This process results in changes to the particle size composition of build-up. However, little evidence was noted of re-distribution of pollutants on roof surfaces. Furthermore, the particulate pollutants in both road and roof surfaces were high in adsorption capacity. More than 50% of the road and more than 60% of the roof surface particulates were finer than 100 μm which increases the capacity to adsorb other pollutants such as heavy metals and hydrocarbons. In addition, the samples contained a significant amount of DOC which would enhance the solubility of other pollutants. The wash-off investigations on road and roof surfaces showed a high concentration of solid pollutants during the initial part of events. This confirmed the occurrence of the 'first flush' phenomenon. The observed wash-off patterns for road and roof surfaces were able to be mathematically replicated using an exponential equation. The exponential equation proposed is a modified version of an equation proposed in past research. The modification was primarily in terms of an additional parameter referred to as the 'capacity factor' (CF). CF defines the rainfall's ability to mobilise solid pollutants from a given surface. It was noted that CF varies with rainfall intensity, particle size distribution and surface characteristics. Additional to the mathematical replication of wash-off, analysis further focused on understanding the physical processes governing wash-off. For this, both particle size distribution and physicochemical parameters of wash-off pollutants were analysed. It was noted that there is little variation in the particle size distribution of particulates in wash-off with rainfall intensity and duration. This suggested that particle size is not an influential parameter in wash-off. It is hypothesised that the particulate density and adhesion to road surfaces are the primary criteria that govern wash-off. Additionally, significantly high pollutant contribution from roof surfaces was noted. This justifies the significance of roof surfaces as an urban pollutant source particularly in the case of first flush. This dissertation further describes a procedure to translate the knowledge created on pollutant build-up and wash-off processes using small-plots to urban catchment scale. This leads to a simple and robust urban water quality estimation tool. Due to its basic architecture, the estimation tool is referred to as a 'translation procedure'. It is designed to operate without a calibration process which would require a large amount of data. This is done by using the pollutant nature of the catchment in terms of buildup and wash-off processes as the basis of measurements. Therefore, the translation procedure is an extension of the current estimation techniques which are typically complex and resource consuming. The use of a translation procedure is simple and based on the graphical estimation of parameters and tabular form of calculations. The translation procedure developed is particularly accurate in estimating water quality in the initial part of runoff events.

Accurate and reliable estimations are the most important factors for the development of efficient stormwater pollutant mitigation strategies. Modelling is the primary tool used for such estimations. The general architecture of typical modelling approaches is to replicate pollutant processes along with hydrologic processes on catchment surfaces. However, due to the lack of understanding of these pollutant processes and the underlying physical parameters, the estimations are subjected to gross errors. Furthermore, the essential requirement of model calibration leads to significant data and resource requirements. This underlines the necessity for simplified and robust stormwater pollutant estimation procedures. The research described in this thesis primarily details the extensive knowledge developed on pollutant build-up and wash-off processes. Knowledge on both build-up and wash-off were generated by in-depth field investigations conducted on residential road and roof surfaces. Additionally, the research describes the use of a rainfall simulator as a tool in urban water quality research. The rainfall simulator was used to collect runoff samples from small-plot surfaces. The use of a rainfall simulator reduced the number of variables which are common to pollutant wash-off. Pollutant build-up on road and roof surfaces was found to be rapid during the initial time period and the rate reduced when the antecedent dry days increase becoming asymptote to a constant value. However, build-up on roofs was gradual when compared to road surfaces where the build-up on the first two days was 66% of the total build-up. Though the variations were different, it was possible to develop a common replication equation in the form of a power function for build-up for the two surface types with a as a multiplication coefficient and b as a power coefficient. However, the values for the two build-up equation coefficients, a, and b were different in each case. It was understood that the power coefficient b varies only with the surface type. The multiplication coefficient varies with a range of parameters including land-use and traffic volume. Additionally, the build-up observed on road surfaces was highly dynamic. It was found that pollutant re-distribution occurs with finer particles being removed from the surface thus allowing coarser particles to build up. This process results in changes to the particle size composition of build-up. However, little evidence was noted of re-distribution of pollutants on roof surfaces. Furthermore, the particulate pollutants in both road and roof surfaces were high in adsorption capacity. More than 50% of the road and more than 60% of the roof surface particulates were finer than 100 μm which increases the capacity to adsorb other pollutants such as heavy metals and hydrocarbons. In addition, the samples contained a significant amount of DOC which would enhance the solubility of other pollutants. The wash-off investigations on road and roof surfaces showed a high concentration of solid pollutants during the initial part of events. This confirmed the occurrence of the 'first flush' phenomenon. The observed wash-off patterns for road and roof surfaces were able to be mathematically replicated using an exponential equation. The exponential equation proposed is a modified version of an equation proposed in past research. The modification was primarily in terms of an additional parameter referred to as the 'capacity factor' (CF). CF defines the rainfall's ability to mobilise solid pollutants from a given surface. It was noted that CF varies with rainfall intensity, particle size distribution and surface characteristics. Additional to the mathematical replication of wash-off, analysis further focused on understanding the physical processes governing wash-off. For this, both particle size distribution and physicochemical parameters of wash-off pollutants were analysed. It was noted that there is little variation in the particle size distribution of particulates in wash-off with rainfall intensity and duration. This suggested that particle size is not an influential parameter in wash-off. It is hypothesised that the particulate density and adhesion to road surfaces are the primary criteria that govern wash-off. Additionally, significantly high pollutant contribution from roof surfaces was noted. This justifies the significance of roof surfaces as an urban pollutant source particularly in the case of first flush. This dissertation further describes a procedure to translate the knowledge created on pollutant build-up and wash-off processes using small-plots to urban catchment scale. This leads to a simple and robust urban water quality estimation tool. Due to its basic architecture, the estimation tool is referred to as a 'translation procedure'. It is designed to operate without a calibration process which would require a large amount of data. This is done by using the pollutant nature of the catchment in terms of buildup and wash-off processes as the basis of measurements. Therefore, the translation procedure is an extension of the current estimation techniques which are typically complex and resource consuming. The use of a translation procedure is simple and based on the graphical estimation of parameters and tabular form of calculations. The translation procedure developed is particularly accurate in estimating water quality in the initial part of runoff events.

This study discusses the monitoring requirements of an effluent credit trading system that allows point source discharges to purchase effluent reductions by financing agricultural nonpoint source best management practices. It describes the results of a national survey of existing trading programs that assessed how each program determines nonpoint source baseline pollutant discharges, pollutant reductions attributable to best management practices, verification of best management practice(s) installation and maintenance activities, and how often this verification is performed. This study surveyed the nonpoint source discharge monitoring programs of several of the successful effluent credit trading systems in the U.S. It documents and discusses specific characteristics of nonpoint source pollutant discharge monitoring strategies. Finally, this thesis compares trading program discharge monitoring characteristics to the current Virginia Cost-Share nonpoint source monitoring program. The goal of this study is to recommend elements of a nonpoint source discharge monitoring strategy to the Commonwealth of Virginia that can be used in a trading program of its own. The study shows that the majority of existing effluent credit trading programs use watershed models and land use evaluation algorithms to indirectly monitor nonpoint source pollutant discharges on a watershed basis rather than relying on empirical sampling and analysis activities for individual farms of fields. Monitoring takes a variety of forms to provide the diverse information necessary to indirectly determine nonpoint source discharges. Most trading programs monitoring strategies are no more comprehensive than agricultural cost-share programs even though many stakeholders believe that a trading programâ s monitoring activities should be exact enough to determine contributions from individual nonpoint sources to support the payments for individual activities. This objection is a barrier to the acceptance of trading programs by the public. A Virginia trading program must enhance its agricultural best management practice cost-share program monitoring practices to track nonpoint source discharges from individual farms or fields to be accepted and successful.
Master of Engineering

Stormwater runoff is one of the leading causes of water quality impairment in the U.S. Bioretention systems are ecologically engineered to treat stormwater pollution and offer exciting opportunities to provide local climate change resiliency by reducing peak runoff rates, and retaining/detaining storm volumes, yet implementation is outpacing our understanding of the underlying physical, biological, and chemical mechanisms involved in pollutant removal. Further, we do not know how performance will be affected by increases in precipitation, which are projected to occur in the northeastern U.S. as a result of climate change, or if these systems could act as a source or sink for greenhouse gas emissions. This research examines the design, construction, and development of monitoring methods for bioretention research, using the University of Vermont (UVM) Bioretention Laboratory as a case study. In addition, this research evaluates mobilization patterns and pollutant loads from road surfaces during the "first flush" of runoff, or the earlier part of a storm event. Finally, this research analyzes the comparative pollutant removal performance of bioretention systems on a treatment by treatment basis. At the UVM Bioretention Laboratory, eight lined bioretention cells were constructed with monitoring infrastructure installed at the entrance and at the subterranean effluent. A conventional, sand and compost based, bioretention soil media was compared to a proprietary media engineered to remove phosphorus, called Sorbtive Media™, under simulated increases in precipitation. Two drought tolerant vegetation mixes, native to the northeast, were compared for sediment and nutrient retention. Each treatment was sampled for soil gas emissions to determine if it was a source or a sink. The monitoring infrastructure designs used in this research allowed for the effective characterization of pollutant mass loads entering and exiting bioretention. Cumulative mass loads from stormwater were found to be highest for total suspended solids, followed by total Kjeldahl nitrogen, nitrate, non-labile phosphorus and soluble reactive phosphorus, in descending order by mass. Total suspended solids, total Kjeldahl nitrogen, and non-labile phosphorus mass were well retained by all bioretention treatments. However, the compost amendment in the conventional soil media was found to release labile nitrogen and phosphorus, far surpassing the mass loads in stormwater. When compared with conventional media, Sorbtive Media™ was highly effective at removing labile phosphorus and was also found to enhance nitrate removal. Systems containing deep-rooted vegetation (Panicum virgatum) were found to be particularly effective at retaining both labile and non-labile constituents. Overall, none of the bioretention treatments were found to be a significant source of N2O and were small sinks for CH4 in most treatments.

Thesis (Ph. D.) -- University of Maryland, College Park, 2007.
Thesis research directed by: Civil Engineering. Title from t.p. of PDF. Includes bibliographical references. Published by UMI Dissertation Services, Ann Arbor, Mich. Also available in paper.

Appropriately constructed pollutant export models can help set management priorities for catchments, identify critical pollutant source areas, and are important tools for developing and evaluating economically viable ways of minimising surface water pollution.¶ This thesis presents a comparison, an evaluation and an integration of models for predicting the export of environmental pollutants, in particular sediment, through river systems. A review of the capabilities and limitations of current water quality modelling approaches is made. Several water quality and quantity modelling approaches are applied and evaluated in the catchment of the upper Murrumbidgee River.¶ The IHACRES rainfall-runoff model and a simple hydrologic routing model are applied with the aim of developing a capacity to predict streamflow at various catchment scales and to enable integration with other pollutant load estimation techniques. Methods for calculating pollutant loads from observed pollutant concentration and modelled streamflow data are also investigated. Sediment export is estimated using these methods over a 10-year period for two case study subcatchments. Approaches for water quality sampling are discussed and a novel monitoring program using rising stage siphon samplers is presented. Results from a refinement of the Sediment River Network model in the upper Murrumbidgee catchment (SedNet-UM) are presented. The model provides a capacity to quantify sediment source, transport and to simulate the effects of management change in the catchment. The investigation of the model includes rigorous examination of the behaviour of the model through sensitivity assessment and comparison with other sediment modelling studies. The major conclusion reached through sensitivity assessment was that the outputs of the model are most sensitive to perturbation of the hydrologic parameters of the model.¶ The SedNet-UM application demonstrates that it is possible to construct stream pollutant models that assist in prioritising management across catchment scales. It can be concluded that SedNet and similar variants have much potential to address common resource management issues requiring the identification of the source, propagation and fate of environmental pollutants. In addition, incorporating the strengths of a conceptual rainfall-runoff model and the semi-distributed SedNet model has been identified as very useful for the future prediction of environmental pollutant export.

Water companies are continually adopting catchment management as a way of improving the quality of raw water prior to treatment. The catchments from which raw water is abstracted are often heterogeneous which regularly presents multiple pollutant issues and variability in the spatial distribution of pollutant-contributing areas. For catchment management to be effective, it is crucial that water companies select and target appropriate interventions at multi-pollutant high risk areas. Within this thesis a conceptual framework is developed to disaggregate and compare multiple pollutant risks in drinking water catchments to aid water companies in this decision making process. A review of pollutant processes highlights links between pollutants often mitigated using catchment management and therefore confirms the feasibility for a multi- pollutant framework. Criteria were developed with water industry catchment management professionals to determine framework requirements. No current framework or model fully meets these criteria.

The research presented in the thesis develops an approach for the estimation and mapping of pollutant spreading in catchments and the associated uncertainty and risk of pollution. The first step in the approach is the quantification and mapping of statistical and geographical distributions of advective solute travel times from pollutant input locations to downstream recipients. In the second step the travel time distributions are used to quantify and map the spreading of specific pollutants and the related risk of water pollution. In both steps, random variability of transport properties and processes is accounted for within a probabilistic framework, while different scenarios are used to account for statistically unquantifiable uncertainty about system characteristics, processes and future developments. This scenario approach enables a transparent analysis of uncertainty effects that is relatively easy to interpret. It also helps identify conservative assumptions and pollutant situations for which further investigations are most needed in order to reduce the uncertainty. The results for different investigated scenarios can further be used to assess the total risk to exceed given water quality standards downstream of pollutant sources. Specific thesis results show that underestimation of pollutant transport variability, and in particular of those transport pathways with much shorter than average travel times, may lead to substantial underestimation of pollutant spreading in catchment areas. By contrast, variations in pollutant attenuation rate generally lead to lower estimated spreading than do constant attenuation conditions. A scenario of constant attenuation rate and high travel time variability, with a large fraction of relatively short travel times, therefore appears to be a reasonable conservative scenario to use when information is lacking for more precise determination of actual transport and attenuation conditions.

A finite volume, shock-capturing scheme is used to solve the shallow water equations on unstructured triangular meshes. The conditions are characterised by: slow flow velocities (up to 1m/s), long time scale (around 10 days), and large domains (50-100km across). Systematic verification is carried out by comparing numerical with analytical results, and by comparing parameter variation in the numerical scheme with perturbation analysis, and good agreement is found. It is the first time a shock-capturing scheme has been applied to slow flows in Moreton Bay. The scheme is used to simulate transport of a pollutant in Moreton Bay, to the east of the city of Brisbane, Australia. Tidal effects are simulated using a sinusoidal time-dependent boundary condition. An advection equation is solved to model the path of a contaminant that is released in the bay, and the effect of tide and wind on the contaminant is studied. Calibration is done by comparing numerical results with measurements made at a study site in Moreton Bay. It is found that variation in the wind speed and bed friction coefficients changes the solution in the way predicted by the asymptotics. These results vary according to the shape of the bathymetry of the domain: in shallower areas, flow is more subject to shear and hence changes in wind speed or bed friction had a greater effect in adding energy to the system. The results also show that the time-dependent boundary condition reproduces the tidal effects that are found on the Queensland coast, i.e. semi-diurnal with amplitude of about 1 metre, to a reasonable degree. It is also found that the simulated path of a pollutant agrees with field measurements. The computer model means different wind speeds and directions can be tested which allows management decisions to be made about which conditions have the least damaging effect on the area.

[ES] Como parte de los métodos de asimilacíon de datos, los métodos basados en conjuntos han ganado popularidad en hidrogeología dada su capacidad para manejar grandes cantidades de datos observados simultáneamente. Recientemente, se ha comenzado a emplear este método para la identificacíon de fuentes de contaminacíon en casos sintéticos. Basándonos en estos trabajos anteriores, hemos dado un paso adelante evaluando su rendimiento en experimentos de tanque de laboratorio. La tesis se puede dividir en cuatro partes. En la primera parte, el filtro de Kalman de conjuntos con reinicio (r-EnKF) se utiliza para la identificacíon espacio-temporal de una fuente puntual de contaminantes en un experimento en tanque de laboratorio, junto con la identificacíon de la posicíon y longitud de una placa vertical insertada en el tanque que modifica la geometría del sistema. Los resultados muestran que el r-EnKF es capaz de identificar tanto la fuente como los parámetros relacionados con la geometría del acuífero. La segunda parte muestra una aplicacíon del filtro de Kalman de conjuntos con anamorfosis normal y reinicio (NS-EnKF) y con inflacíon de la covarianza en un experimento de laboratorio con conductividad heterogénea. El método se prueba primero utilizando un caso sintético que imita el experimento del tanque para establecer el número mínimo de miembros del conjunto y la mejor técnica para evitar el colapso del filtro. Luego, su aplicacíon a los datos del tanque muestra que el NS-EnKF con reinicio puede beneficiarse de la inflacíon de Bauser para reducir el tama ñ o del conjunto y llegar a una buena identificacíon conjunta tanto de la fuente de contaminantes como de la heterogeneidad espacial de las conductividades. En la tercera parte, el filtro de Kalman de conjuntos suavizado con asimilacíon múltiple de datos (ES-MDA) se emplea para la identificacíon simultánea de una fuente de contaminantes y la distribucíon espacial de la conductividad hidráulica utilizando el r-EnKF como punto de referencia. El resultado muestra que el ES-MDA puede superar al r-EnKF, marginalmente, para el caso sintético específico analizado con el mismo consumo de CPU, y puede funcionar mucho mejor que el r-EnKF a cambio de un mayor costo de CPU. La cuarta y última parte investiga el rendimiento del ES-MDA en un problema de identificacíon de una inyeccíon de contaminante que varía en el tiempo. Se analiza la influencia de diferentes intervalos de observacíon y esquemas de inflacíon de la covarianza en la determinacíon de la curva de inyeccíon. El resultado muestra que el ES-MDA funciona muy bien en la identificacíon de la curva de inyeccíon cuando la discretizacíon de la misma no es muy alta, pero encuentra problemas de fluctuacíon en los casos con discretizaciones altas. La frecuencia con la que se muestrean los datos de observacíon es un factor influyente, mientras que el número de iteraciones o los métodos de inflacíon de la covarianza tienen menos efecto.
[CA] Com a part dels mètodes d'assimilació de dades, els mètodes basats en conjunts han guanyat popularitat en hidrogeologia donada la seua capacitat per a manejar grans quantitats de dades observades simultàniament. Recentment, s'ha començat a emprar aquest mètode per a la identificació de fonts de contaminació en casos sintètics. Basant-nos en aquests treballs anteriors, hem fet un pas avant avaluant el seu rendiment en experiments de tanc de laboratori. La tesi es pot dividir en quatre parts.En la primera part, el filtre de Kalman de conjunts amb reinici (r-EnKF) s'utilitza per a la identificació espaciotemporal d'una font puntual de contaminants en un experiment en tanc de laboratori, juntament amb la identificació de la posició i longitud d'una placa vertical inserida en el tanc que modifica la geometria del sistema. Els resultats mostren que el r-EnKF és capaç d'identificar tant la font com els paràmetres relacionats amb la geometria de l'aqüífer. La segona part mostra una aplicació del filtre de Kalman de conjunts amb anamorfosis normal i reinici (NS-EnKF) i amb inflació de la covariància en un experiment de laboratori amb conductivitat heterogènia. El mètode es prova primer utilitzant un cas sintètic que imita l'experiment del tanc per a establir el nombre mínim de membres del conjunt i la millor tècnica per a evitar el col·lapse del filtre. Després, la seua aplicació a les dades del tanc mostra que el NS-EnKF amb reinici pot beneficiar-se de la inflació de Bauser per a reduir la grandària del conjunt i arribar a una bona identificació conjunta tant de la font de contaminants com de l'heterogeneïtat espacial de les conductivitats. En la tercera part, el filtre de Kalman de conjunts suavitzat amb assimilació múltiple de dades (ES-MDA) s'empra per a la identificació simultània d'una font de contaminants i la distribució espacial de la conductivitat hidràulica utilitzant el r-EnKF com a punt de referència. El resultat mostra que l'ES-MDA pot superar al r-EnKF, marginalment, per al cas sintètic específic analitzat amb el mateix consum de CPU, i pot funcionar molt millor que el r-EnKF a canvi d'un major cost de CPU. La quarta i última part investiga el rendiment de l'ES-MDA en un problema d'identificació d'una injecció de contaminant que varia en el temps. S'analitza la influència de diferents intervals d'observació i esquemes de inflació de la covariància en la determinació de la corba d'injecció. El resultat mostra que l'ES-MDA funciona molt bé en la identificació de la corba d'injecció quan la discretització no és massa alta, però troba problemes de fluctuació amb discretitzacions massa fines. La freqüència amb la qual es mostregen les dades d'observació és un factor influent en aquesta aplicació, mentre que el nombre d'iteracions o els mètodes d'inflació de la covariància tenen menys efecte.
[EN] As part of the data assimilation methods, the ensemble-based methods have gained popularity in hydrogeology given their ability to deal with huge amounts of observed data simultaneously. More recently, researchers have started to employ these methods to deduce contamination source information in synthetic cases. Based on these previous work, we take a step further to evaluate their performance in sandbox experiments. The main objective of this thesis is to verify the capacity of the ensemble-based methods in identifying contaminant sources and complex geological heterogeneity. The thesis could be divided into four parts. In the first part, the restart ensemble Kalman filter (r-EnKF) is used for the spatiotemporal identification of a point contaminant source in a sandbox experiment, together with the identification of the position and length of a vertical plate inserted in the sandbox that modifies the geometry of the system. The results show that the r-EnKF is capable of identifying both contaminant source information and aquifer-geometry-related parameters. The second part shows an application of the restart normal-score ensemble Kalman filter (NS-EnKF) with covariance inflation in a heterogenous conductivity laboratory experiment. The method is first tested using a synthetic case that mimics the sandbox experiment to establish the minimum number of ensemble members and the best technique to prevent filter collapse. Then, its application to the sandbox data shows that the restart NS-EnKF can benefit from Bauser's inflation to reduce the ensemble size and to arrive to a good joint identification of both the contaminant source and the spatial heterogeneity of conductivities. In the third part, the ensemble smoother with multiple data assimilation (ES-MDA) is employed for the simultaneous identification of a contaminant source and the spatial distribution of hydraulic conductivity while using the r-EnKF as a benchmark. The outcome shows that the ES-MDA is able to outperform the r-EnKF, marginally, for the specific synthetic case analyzed with almost the same CPU consumption, and it can perform far better than the r-EnKF just with a cost of larger CPU usage. The forth and last part investigates the performance of the ES-MDA in a time-varying release history identification problem. The influence of different observation intervals and inflation factor schemes on the determination of the release curve are discussed. The outcome shows that the ES-MDA performs great in recovering release history when the history curve is discretized in not too many steps, and that it fails when the discretization is large. The frequency at which observation data are sampled is an influential factor in this application, while the number of iterations or the inflation scheme have less effect.
Thanks to the institutions that financed my studies. The support to carry out my work was received from the Spanish Ministry of Economy and Competitiveness through project CGL2014-59841-P, and from the Spanish Ministry of Education, Culture and Sports through a fellowship for the mobility of professors in foreign research and higher education institutions to my supervisor, reference PRX17/00150
Chen, Z. (2020). Stochastic Identification of Pollutant Sources in Aquifers by the Ensemble Kalman Filter [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/160628
TESIS

Pollutants follow various subsurface and surface water pathways from sources within a catchment to its outlet and may cause detrimental effects on downstream water quality and ecosystems. Along their different transport pathways through a catchment, pollutants may be attenuated subject to different physical and biogeochemical processes. In this thesis, physical process effects on such catchment-scale pollutant transport and attenuation, resulting coastal pollutant loading and its efficient abatement are investigated. For this purpose, pollutant transport-attenuation is modeled both generically using a Lagrangian Stochastic Advective-Reactive (LaSAR) approach and site specifically for the Swedish Norrström basin using the GIS-based dynamic nitrogen transport-attenuation model POLFLOW. Furthermore, the role of such modeling for catchment-scale pollutant abatement is also investigated by use of economic optimization modeling. Results indicate that appropriate characterization of catchment-scale solute transport and attenuation processes requires accurate quantification of the specific solute pathways from different sources in a catchment, through the subsurface and surface water systems of the catchment, to the catchment outlet. The various physical processes that act on solute transported along these pathways may be quantified appropriately by use of relevant solute travel time distributions for each water subsystem that the pathways cross through the catchment. Such distributions capture the physical solute travel time variability from source to catchment outlet and its effects on reactive pollutant transport. Results of this thesis show specifically that neglect of such physical solute travel time variability in large-scale models of nitrogen transport and attenuation in catchments may yield misleading model estimates of nitrogen attenuation rates. Results for nitrogen abatement optimization in catchments further indicate that inefficient solutions for coastal nitrogen load reduction may result from simplifying physical transport assumptions made in different catchment-scale nitrogen transport-attenuation models. Modeling of possible future nitrogen management scenarios show also that slow nitrogen transport and reversible mass transfer processes in the subsurface water systems of catchments may greatly delay and temporally redistribute coastal nitrogen load effects of inland nitrogen source abatement over decades or much longer. Achievement of the national Swedish environmental objective to reduce the anthropogenic coastal nitrogen loading by 30% may therefore require up to a 40% reduction of both point sources, for achieving a fast coastal load response, and diffuse sources, for maintaining the coastal load reduction also in the long term.
QC 20100908

The river Göta Älv reaches between Vänern and Gothenburg and is the main raw water source for Gothenburg that supplies about 700 000 people with water. To protect and maintain a high water quality, continuously samples and water analyses are made throughout the river. In 1998 a protection area was founded between surte and Lärjeholm where the raw water intake is. This was made to increase the awareness of the importance to protect the water. However, there is a lot of contribution of untreated stormwater to Göta Älv within the protection area.

Göteborg Water and Sewage Works commissioned this thesis where two areas, Tagene industrial area and Kärra residential area, with untreated stormwater outlets within the protection area are studied. The areas have been divided according to surface composition with different rates of pollutant contribution. Then the stormwater flow and the contribution of pollutants was simulated with the model SEWSYS. The future aim is that the model will be able to simulate the contribution of pollutants for a variety of rains, for the whole protection area.

SEWSYS (Sewer System) is built in MATLAB/Simulink and consists of three modules, a stormwater module, a sanitary wastewater module and a treatment plant module. This project only includes the stormwater module. The model simulates the stormwater flow and the pollutants total phosphorous, total nitrogen, copper, zinc, lead, cadmium and polycyclic aromatic hydrocarbons (PAH). Samples and analysis for the two areas has been carried out for another thesis work during the same period. The results from those analyses have been used for the model settings for the areas.

Simulations have been performed to adjust the model and evaluate its ability to describe the stormwater flow and the pollutant contribution within the areas. The amount of stormwater and the runoff are well simulated by the model. However, the measured and analysed data has not been enough to get reliable simulations over the pollutant contribution. Further development of the model is necessary. Generally the model simulates lower values compared to measured values, especially in the industrial area. For a more general understanding over how SEWSYS works for the two areas, simulations were carried out on a yearly basis. Those simulations have been compared with general data for stormwater pollutants. Even though the results from the simulations have shown lower values than the measured values, the model shows clearly that the contribution of pollutants from the industrial site is greater than the contribution from the residential site.

Göta Älv sträcker sig från Vänern ner till Göteborg och är Göteborgs huvudsakliga råvattentäkt som försörjer ca 700 000 personer med vatten dagligen. För att säkra råvattenkvaliteten görs kontinuerliga provtagningar utmed älven. Dessutom beslutade Länsstyrelsen 1998 om ett skyddsområde med skyddsföreskrifter för avrinningsområdet mellan Surte i norr till vattenintaget vid Lärjeholm i söder. Ett mål med skyddsområdet är att det ska öka medvetenheten hos boende och de som är verksamma inom området om behovet att värna om vårt vatten. Dock leds det på flera ställen ut orenat dagvatten till älven inom skyddsområdet.

Examensarbetet är ett uppdrag av Göteborgs Va-verk där två områden med orenade dagvattenutsläpp till Göta Älv studeras, Tagene industriområde samt Kärra bostadsområde. Dessa områden har karterats och dagvattenflödet samt föroreningsbelastningen från dagvattnet har simulerats med modellen SEWSYS. Målet på lång sikt är att modellen ska kunna användas för att simulera föroreningsbelastningen vid olika regn för hela skyddsområdet.

Modellen SEWSYS (Sewer System) är uppbyggd i MATLAB/Simulink och bygger på tre moduler, en dagvattenmodul, en spillvattenmodul och en reningsverksmodul. För detta projekt har endast delen för dagvatten använts. Modellen simulerar dagvattenflödet och behandlar föroreningarna totalfosfor, totalkväve, koppar, zink, bly, kadmium samt polycykliska aromatiska kolväten (PAH). I ett examensarbete parallellt med detta har provtagning och analyser av föroreningar för de båda områdena ägt rum och dessa värden ligger till grund för inställningen av modellen.

Simuleringar har utförts för att anpassa modellen samt utvärdera dess förmåga att beskriva dagvattenflödet och föroreningsbelastningen inom de aktuella områdena. Simuleringarna visar att avrinningen och dagvattenflödet simuleras bra av modellen. Det har dock visat sig att de gjorda mätningarna inte har varit tillräckliga som underlag för att få en tillförlitlig beskrivning av föroreningsbelastningen och vidare utveckling är nödvändig. Detta gäller särskilt i industriområdet där modellen generellt simulerar för låga föroreningsmängder. För en mer allmän uppfattning av SEWSYS modellen för de två områdena, har även simuleringar på årsbasis utförts och jämförts med schablonhalter för dagvattenföroreningar. Trots att simuleringsvärdena har legat lägre än de uppmätta värdena på föroreningsmängderna har det gått att visa att industriområdet bidrar till högre föroreningsbelastning än bostadsområdet på recipienten Göta Älv.

This research developed mathematical models to generate reliable future rainfall data in small spatial and temporal scales, and used them to estimate future floods and water quality scenarios. Outcomes of the study suggested a substantial increase in the occurrences and the extent of future floods and the amount of pollutant that they carry. Outcomes will be highly valued in future-proofing urban flood mitigation measures and water sensitive urban design infrastructure.

Increased reactive nitrogen from human activities negatively affects surface water (SW) quality. The hyporheic zone, where SW and groundwater interact, possesses unique biogeochemical conditions that can attenuate contaminants (e.g., denitrification), including mixing-dependent reactions that require components from both water sources. Previous research has explored mixing-dependent denitrification in the hyporheic zone but did not address the effects of varying SW depth as would occur from storms, tides, dam operation, and varying seasons. We simulated steady and unsteady hyporheic flow and transport through a riverbed dune using MODFLOW and SEAM3D, and varied SW depth, degree of sediment heterogeneity, amplitude and frequency of sinusoidal fluctuations, among others to determine these effects. We found that increasing steady state surface water depth from 0.1 to 1.0 m increased non-mixing dependent aerobic respiration by 270% and mixing-dependent denitrification by 78% in homogeneous sediment. Heterogeneous hydraulic conductivity fields yielded similar results, with increases in consumption due to variation in correlation length and variance of less than 5%. Daily SW fluctuation, including variation of amplitude, period, and sinusoidal versus instantaneous changes had significantly less impact than longer-term trends in SW depth. There is potential for the hyporheic zone to attenuate NO3- in upwelling groundwater plumes. Restoration efforts may be able to maximize the potential for mixing-dependent reactions in the hyporheic zone by increasing residence times.
Master of Science

The major objective of this study is to investigate simplified risk assessment models for pollutant leaching to and migration across groundwater. Data for this study were gathered through bibliographic research and experts’ advice. Three European countries were selected for this investigation: Italy, United Kingdom and Walloon Region. In the first part, the procedures are compared from a theoretical point of view. The Thesis then identifies the tools used by countries and applies them on a synthetic and real case. A sensitivity analysis is performed as well. The cases have highlighted differences in terms of decision-making and shown which parameters mostly affect results.Basing on the results of this research, it can be concluded that all the countries perform Concentration based risk assessment relying on simplified analytical equations and that the way of assessing risk is quite similar. Major differences could be noticed in the choice of factors and relative adjustments for modelling leaching in the vadose zone and in the way to obtain the remedial objectives. Types of solutions for modelling the transport of contaminant across groundwater differ as well. The synthetic case study brings to light some noticeable aspects. Firstly the difficulty in choosing parameters, particularly for the saturated zone, so as to respect the mass balance between saturated and unsaturated condition. Secondly, the fact that some factors, used by countries to simplify the movement of pollutants (i.e. dilution factor), actually have a great influence on results. Therefore their physical consistency and reliability should be further investigated by comparing results of traditional RA tools with numerical models. Finally, the sensitivity analysis has shown that Mass flux approaches may bring additional contribution to the way the presence of Risk is assessed and that research should evolve in this direction.

Le dépôt chimique en phase vapeur assisté par plasma est appliqué pour préparer des couches minces amorphes de TiO2 à basse température. Un recuit à 300 °C pendant un temps minimum de 4,5 h permet de former la phase cristalline anatase. Les principales caractéristiques de ces couches minces comme leur structure cristalline, leur microstructure, leur largeur de bande interdite et leur hydrophilie de surface, sont déterminées. Leurs performances fonctionnelles comme photocatalyseurs sont d'abord examinées selon le test breveté par Pilkington, consistant à éliminer sous irradiation UV de l'acide stéarique préalablement adsorbé sur les couches de TiO2 ici déposées sur des plaquettes de silicium. Des membranes M100 (couche continue de TiO2) et M800 (couche de TiO2 couvrant les grains de support) sont préparées sur les couches de surface macroporeuses de supports poreux en alumine, de tailles moyennes de pores respectives, 100 nm et 800 nm. Ces membranes sont testées en condition "statique", avec la diffusion d'un soluté organique dilué dans l'eau. Pour le bleu de méthylène, on montre que la quantité de composé détruit par unité de surface de membrane et par unité de temps est égale à 2 × 10-8 mol m-2 s-1 pour la membrane M100 et 1 × 10-8 mol m-2 s- 1 pour la membrane M800. Ces membranes sont également testées dans des conditions "dynamiques", à savoir en procédé baromembranaire, avec deux configurations différentes (couche photocatalytique du côté de l'alimentation ou du côté du perméat) et trois composés organiques différents (bleu de méthylène, acide orange 7 et phénol). La modélisation du procédé (adsorption et réaction photocatalytique) est finalement réalisée à partir des données expérimentales disponibles
Plasma-enhanced chemical vapor deposition is applied to prepare amorphous TiO2 thin films at low temperature. Post-annealing at 300 °C for minimal staying time 4.5 h is required to form crystalline anatase phase. Characteristics of the TiO2 thin films including crystalline structure, microstructure, band gap and surface hydrophilicity, are determined. Functional performance of these anatase thin films as photocatalysts is first examined with patented Pilkington assessment by removing, under UV irradiation, stearic acid initially adsorbed on TiO2 layers here deposited on silicon wafers. Membranes M100 (TiO2 continuous layer) and M800 (TiO2-skin on support grain) are prepared on the macroporous top layer of porous alumina supports with an average pore size of 100 nm and 800 nm, respectively. These membranes are tested in “static” condition under the effect of diffusion of an organic solute in water. For Methylene Blue it is shown that the quantity of destroyed compound per unit of membrane surface area and per unit of time is equal to 2×10−8 mol m-2 s-1 for M100 and 1×10−8 mol m-2 s-1 for M800. These membranes are also tested in “dynamic” conditions, i.e. pressure-driven membrane processes, with two different configurations (photocatalytic layer on the feed side or on the permeate side) and three different organics (Methylene Blue, Acid Orange 7 and phenol). Process modelling (adsorption and photocatalysis reaction) is finally carried out from the available experimental outputs

Gravel filters are potentially a low cost, low maintenance water treatment solution. They require no mechanical or electrical parts and can operate without the addition of chemicals or the need for close supervision. As such, they are an appropriate technology for treating road runoff as a component of Sustainable urban Drainage Systems (SuDS) and as an initial stage of drinking water treatment in rural areas. However, the processes by which pollutant particles are removed in gravel filters are poorly understood and practical experience shows that many filters fail long before their expected design life is reached. For this reason gravel filters are little used for drinking water treatment and, when they are incorporated into SuDS, their removal efficiency and maintenance requirements are unpredictable. The aim of this thesis was to better understand particle removal processes and the implications for gravel filter design. This was achieved through a combination of lab-based experiments and numerical modelling. • The change in conservative tracer transport characteristics with pollutant particle accumulation was assessed through column experiments. • The spatial heterogeneity of particle accumulation was measured by collecting 3D data with magnetic resonance imaging (MRI). Multiple scans of filters allowed the temporal evolution of particle accumulation to be assessed. A method for processing the raw MRI data to yield the change in 3D pore geometry was developed, assessed and applied. • A simple method for extracting and comparing pore network characteristics at different stages of particle accumulation was applied to the MRI derived geometry. • Direct modelling of the 3D MRI pore geometry with the open source software OpenFOAM allowed correlation of flow velocities with particle accumulation at each point in the pore network. Lagrangian particle tracking was used to simulate the transport of a conservative tracer through the filter. Key findings were that spatial heterogeneity in particle accumulation was influenced by both initial pore geometry and the temporal evolution of the pore network with accumulation. This was attributed to the formation of high velocity preferential flow paths that were evident in both the 3D MRI data and the numerical model of that data. Pore networks exhibited a decrease in connectivity with accumulation and this was mirrored by a decrease in the volume of the filter that was accessible to a conservative tracer. Conclusions of this thesis are that MRI is a useful tool for non-invasively assessing the spatial variability of clogging in gravel filters and, when combined with numerical modelling of the pore geometry, for establishing the link between pore velocity and particle removal. The formation of preferential flow paths is detrimental to the pollutant removal efficiency of a filter and could explain why many filters fail to produce good quality effluent well before their physical pollutant storage capacity is reached.

The pollution of streams and rivers is a growing concern, and environmental guidance increasingly suggests stream restoration to improve water quality. �Solute retention in off channel storage zones such as hyporheic zones and floodplains is typically necessary for significant reaction to occur. �Yet the effects of two common restoration techniques, in stream structures and inset floodplains, on solute retention have not been rigorously compared. �We used MIKE SHE to model hydraulics and solute transport in the channel, inset floodplain, and hyporheic zone of a 2nd order stream. �We varied hydraulic conditions (winter baseflow, summer baseflow, and storm flow), geology (hydraulic conductivity), and stream restoration design parameters (inset floodplain length, and presence of in stream structures). �In stream structures induced hyporheic exchange during summer baseflow with a low groundwater table (~20% of the year), while floodplains only retained solutes during storm flow conditions (~1% of the year). �Flow through the hyporheic zone increased linearly with hydraulic conductivity, while residence times decreased linearly. �Flow through inset floodplains and residence times in both the channel and floodplains increased non linearly with the fraction of bank with floodplains installed. �The fraction of stream flow that entered inset floodplains was one to three orders of magnitude higher than that through the hyporheic zone, while the residence time and mass storage in the hyporheic zone was one to five orders of magnitude larger than that in floodplain segments. �Our model results suggest that in stream structures and inset floodplains are complementary practices.
Master of Science

Organic contaminants from industrial and/or domestic effluents may be harmful to humans directly or indirectly by degrading the quality of the aquatic environment. Consequently these contaminants must be reduced to levels that are not harmful to humans and the environment before disposal. Chemical, physical and biological methods exist for the removal of these pollutants from effluents. Among the available chemical methods, heterogeneous photocatalytic oxidation has been found particularly effective in removing a large number of persistent organics in water. In this study, photocatalytic degradation was explored for the removal of reactive azo-dye (textile dye), triclocarban (disinfectant), clopyralid (herbicide) and three endocrine disrupting compounds (EDCs) (estrone, 17ß-estradiol and 17α-ethinylestradiol) from synthetic effluents. The major factors affecting the photocatalytic processes including the initial concentration of the target compounds, the amount of catalyst, the light intensity, the type of catalyst, the electron acceptor, the irradiation time and the pH were studied. Other oxidation techniques including (O3, H2O2, UV) were also studied. Generally UV light is used in combination with titanium dioxide, as photocatalyst, to generate photoinduced charge separation leading to the creation of electron-hole pairs. The holes act as electron acceptors hence the oxidation of organics occur at these sites. These holes can also lead to the formation of hydroxyl radicals which are also effective oxidants capable of degrading the organics. The results obtained in this study indicated that photolysis (i.e. UV only) was found to have no effect on the degradation of reactive azo-dye (RO16). However, complete photocatalytic degradation of 20 mg/L (3.24×10-2 mM) RO16 was achieved in 20 minutes in the presence of 1g/L TiO2 Degussa P25 at pH 5.5. Comparison between various types of catalysts (i.e. Degussa P25, VP Aeroperl, Hombifine N) gave varied results but Degussa P25 was the most effective photocatalyst hence it was selected for this study. For RO16 the optimum catalyst concentration was 0.5 g/L TiO2 with initial concentration of 20 mg/L RO16. It was found that the disappearance of RO16 satisfactorily followed the pseudo first-order kinetics according to Langmuir-Hinshelwood (L-H) model. The rate constant was k= 0.0928 mol/min. Photodegradation of TCC was studied in 70%v acetonitrile: 30%v water solutions. UV light degraded TCC effectively and the reaction rates increased with decreasing initial concentration of TCC. UV/TiO2 gave unsatisfactory degradation of triclocarban (TCC) since only 36% were removed in 60 minutes with initial concentration of TCC 20 mg/L. The degradation of clopyralid and the EDCs was studied using three oxidation systems UV/TiO2, UV/H2O2 and O3. Complete degradation of clopyralid (3,6-DCP) was achieved with UV/TiO2 in about 90 minutes at an optimum catalyst concentration of 1g/L. Zero-order kinetics was found to describe the first stage of the photocatalytic reaction in the concentration range 0.078-0.521 mM. At pH 5 the rate constant was 2.09×10-6-4.32×10-7 M.s-1.Complete degradation of all the three EDCs was achieved with UV/H2O2 in 60 minutes at catalyst concentration of (2.94×10-2 M). On the other hand complete degradation of the EDCs was achieved in just 2 minutes with ozonation. For high concentration EDCs, TiO2/UV gave low efficiency of degradation as compared with ozone and H2O2/UV. First-order kinetics was found to describe the photocatalytic reaction of the EDCs.
Education Service Department of the Libyan Government

京都大学
0048
新制・課程博士
博士(工学)
甲第22767号
工博第4766号
新制||工||1745(附属図書館)
京都大学大学院工学研究科都市環境工学専攻
(主査)教授 米田 稔, 教授 清水 芳久, 准教授 松井 康人
学位規則第4条第1項該当
Doctor of Philosophy (Engineering)
Kyoto University
DFAM

Organic contaminants from industrial and/or domestic effluents may be harmful to humans directly or indirectly by degrading the quality of the aquatic environment. Consequently these contaminants must be reduced to levels that are not harmful to humans and the environment before disposal. Chemical, physical and biological methods exist for the removal of these pollutants from effluents. Among the available chemical methods, heterogeneous photocatalytic oxidation has been found particularly effective in removing a large number of persistent organics in water. In this study, photocatalytic degradation was explored for the removal of reactive azo-dye (textile dye), triclocarban (disinfectant), clopyralid (herbicide) and three endocrine disrupting compounds (EDCs) (estrone, 17ß-estradiol and 17α-ethinylestradiol) from synthetic effluents. The major factors affecting the photocatalytic processes including the initial concentration of the target compounds, the amount of catalyst, the light intensity, the type of catalyst, the electron acceptor, the irradiation time and the pH were studied. Other oxidation techniques including (O3, H2O2, UV) were also studied. Generally UV light is used in combination with titanium dioxide, as photocatalyst, to generate photoinduced charge separation leading to the creation of electron-hole pairs. The holes act as electron acceptors hence the oxidation of organics occur at these sites. These holes can also lead to the formation of hydroxyl radicals which are also effective oxidants capable of degrading the organics. The results obtained in this study indicated that photolysis (i.e. UV only) was found to have no effect on the degradation of reactive azo-dye (RO16). However, complete photocatalytic degradation of 20 mg/L (3.24×10-2 mM) RO16 was achieved in 20 minutes in the presence of 1g/L TiO2 Degussa P25 at pH 5.5. Comparison between various types of catalysts (i.e. Degussa P25, VP Aeroperl, Hombifine N) gave varied results but Degussa P25 was the most effective photocatalyst hence it was selected for this study. For RO16 the optimum catalyst concentration was 0.5 g/L TiO2 with initial concentration of 20 mg/L RO16. It was found that the disappearance of RO16 satisfactorily followed the pseudo first-order kinetics according to Langmuir-Hinshelwood (L-H) model. The rate constant was k= 0.0928 mol/min. Photodegradation of TCC was studied in 70%v acetonitrile: 30%v water solutions. UV light degraded TCC effectively and the reaction rates increased with decreasing initial concentration of TCC. UV/TiO2 gave unsatisfactory degradation of triclocarban (TCC) since only 36% were removed in 60 minutes with initial concentration of TCC 20 mg/L. The degradation of clopyralid and the EDCs was studied using three oxidation systems UV/TiO2, UV/H2O2 and O3. Complete degradation of clopyralid (3,6-DCP) was achieved with UV/TiO2 in about 90 minutes at an optimum catalyst concentration of 1g/L. Zero-order kinetics was found to describe the first stage of the photocatalytic reaction in the concentration range 0.078-0.521 mM. At pH 5 the rate constant was 2.09×10⁻⁶ ± 4.32×10⁻⁷ M.s⁻¹. Complete degradation of all the three EDCs was achieved with UV/H₂O₂ in 60 minutes at catalyst concentration of (2.94×10⁻² M). On the other hand complete degradation of the EDCs was achieved in just 2 minutes with ozonation. For high concentration EDCs, TiO₂/UV gave low efficiency of degradation as compared with ozone and H2O2/UV. First-order kinetics was found to describe the photocatalytic reaction of the EDCs.

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O entendimento de como ocorre o transporte de solutos em Ãguas subterrÃneas à fundamental para o correto gerenciamento deste recurso cada vez mais sujeito a pressÃes antrÃpicas. Para a modelagem deste processo, um parÃmetro fundamental à o coeficiente de dispersÃo hidrodinÃmica, cujo componente mais importante, em meio poroso, à a dispersividade longitudinal (αL). A determinaÃÃo de αL ocorre normalmente atravÃs de experimentos com aplicaÃÃo restrita Ãs Ãreas de interesse e resultados normalmente imprecisos. O presente trabalho teve como objetivo principal calibrar αL em aquÃferos atravÃs do MÃtodo Iterativo do Gradiente de ConcentraÃÃo (MIGC) elaborado a partir de uma adaptaÃÃo da metodologia proposta para o MÃtodo Iterativo do Gradiente HidrÃulico (MIGH). O processo se inicia a partir da simulaÃÃo hidrodinÃmica, posteriormente sÃo inseridas concentraÃÃes obtidas em campo ou hipotÃticas no modelo de simulaÃÃo de transporte de solutos. Em seguida à gerada uma matriz de concentraÃÃes que servirà de base para o processo iterativo do MIGC. Foram estruturados dois modelos, um denominado modelo observado ou fixo, no qual as concentraÃÃes de campo sÃo fixadas e outro modelo denominado de calculado ou nÃo fixo. Ao longo do processo de calibraÃÃo sÃo geradas matrizes de concentraÃÃes que permitem calcular os gradientes espaciais de concentraÃÃo nos modelos fixo e nÃo fixo. A mÃdia dos Ãngulos entre os gradientes de concentraÃÃes observados e calculados e o erro mÃdio quadrÃtico sÃo os critÃrios de convergÃncia para aferir o processo de calibraÃÃo. Nas cinco modelagens apresentadas, os resultados para estes dois critÃrios indicam a eficiÃncia do mÃtodo de calibraÃÃo. Seguindo a metodologia clÃssica de calibraÃÃo de parÃmetros, no MIGC as iteraÃÃes continuam enquanto os valores mÃnimos para os referidos critÃrios nÃo forem atingidos e ocorre, por conseguinte, a alteraÃÃo dos valores da dispersividade longitudinal entre as iteraÃÃes. Este mecanismo à baseado na razÃo entre os gradientes de concentraÃÃes observados e calculados em cada uma das cÃlulas do modelo. Os resultados foram obtidos a partir do uso de concentraÃÃes de nitrato em dois exemplos hipotÃticos com graus de complexidade diferenciados e um caso real aplicado na regiÃo do municÃpio do Crato, inserido na Bacia Sedimentar do Araripe, situada no sul do estado do CearÃ, Brasil. Para os casos estudados houve uma convergÃncia expressiva das mÃdias dos Ãngulos formados entre os gradientes de concentraÃÃo observados e calculados e do erro mÃdio quadrÃtico das concentraÃÃes, obtendo-se, como resultado final, uma matriz com a maioria dos valores de αL prÃximos aos determinados inicialmente. O MIGC se apresenta como um mÃtodo prÃtico e rÃpido para a calibraÃÃo da dispersividade longitudinal. Sugere-se o desenvolvimento de um programa computacional que automatize o MIGC para que o mesmo seja otimizado em situaÃÃes mais complexas.
The understanding of how the transport of solutes in ground water occurs is critical to the proper management of this resource increasingly subjected to thropogenic pressures. In order to model this process, a key parameter is the coefficient of hydrodynamic dispersion, whose most important component in porous environments is the longitudinal dispersivity (αL). The determination of αL usually takes place through experiments restricted to areas of interest and with often inaccurate results. Numerical methods are also used in order to attain parameter estimation. This study aimed mainly at calibrating αL in aquifers through the Iterative Method of the Gradient of Concentration (IMGC) derived from an adaptation of the methodology proposed for the Iterative Method of Hydraulic Gradient (IMHG). The process starts from the hydrodynamic simulation. Later, concentrations obtained from fields or in a hypothetic way are inserted using the model of simulation of solute transportation. Then, a matrix of concentrations is generated, which will work as the basis for the iterative process of IMGC. Two models were structured: one called observed or fixed model in which the concentration field is fixed and another model named calculated or not fixed. Throughout the calibration process arrays of concentrations are generated and used for calculating the spatial concentration of gradients in fixed and not fixed models. The average angle between the gradients of observed and calculated concentrations and the mean squared error are the convergence criteria to assess the calibration process. In the five models presented in this research, the results for these two criteria indicate the efficiency of the calibration method. Following the classical methodology of parameter calibration in the IMGC iterations continue as the minimum values for these criteria are not attained, therefore, the change of the longitudinal dispersivity varies among iterations. This mechanism is based on the ratio between the observed and calculated gradients of concentrations at each model cells. The results were obtained from the use of nitrate concentrations at two hypothetical samples with different degrees of complexity and also with a real case applied int he municipality of Crato, inserted in the Sedimentary Basin region of Araripe. For the cases analyzed in this study, there was a significant decay of the average angle formed between the gradients of observed and calculated concentration and the mean squared error of concentrations, obtaining as a result, a matrix with αL values close to those initially stipulated. IMGC presents itself as a practical method. It is suggested the development of a computer program that automates IMGC so that it is better used in more complex situation.

Increases in reactive nitrogen from human actions have led to negative impacts on surface water (SW) and groundwater (GW) quality, and it is important to better understand denitrification processes in aquatic systems. The hyporheic zone has unique biogeochemical conditions, and is known to attenuate contaminants originating from SW and traveling through the hyporheic zone, together with necessary reactants. However, the ability of the hyporheic zone to attenuate contaminants from deeper upwelling GW plumes as they exit to SW is less understood. I used MODFLOW and SEAM3D to simulate hyporheic flow cells induced by riverbed dunes and upwelling GW together with mixing dependent denitrification of an upwelling nitrate (NO3-) plume. My basecase model scenario entailed dissolved organic carbon (DOC) and dissolved oxygen (DO) advecting from SW and DO and NO3- advecting from GW, which is typical of water in agricultural land uses. I conducted a sensitivity analysis to determine controls on mixing dependent denitrification. Mixing dependent denitrification increased with increasing hydraulic conductivity, decreasing lower bottom flux, as well as increasing DOC in SW and NO3- in GW. Non-mixing dependent denitrification also occurred when there was SW NO3-, and I found its magnitude was much greater than mixing dependent denitrification. Nevertheless, potential for hyporheic zones to attenuate upwelling NO3- plumes seems to be substantial, though highly variable depending on biogeochemical reaction rates as well as geomorphic, hydraulic and biogeochemical conditions. Stream and river restoration efforts may be able to increase both mixing and non-mixing dependent reactions by increasing hyporheic zone residence times.
Master of Science