In the light of increasing demand and diminishing supplies a sustainable urban water management for Melbourne and other cities will need to include water recycling and reuse of reclaimed water and stormwater. One key issue in stormwater reuse is the need for storage between times of collection until times of demand. Aquifer storage and recovery (ASR) would be a valuable option as it has limited space requirements and restricts loss from evaporation. However, stormwater commonly contains elevated levels of heavy metals, of which Zn and Cu are the most mobile. Stormwater also contains suspended solids, organic carbon, oxygen and nutrients, which influence the behaviour of injected metals and induce geochemical changes in the aquifer. While stormwater ASR has been practiced in limestone aquifers in South Australia, field data for sandy aquifers, which are more prevalent around Melbourne, are very limited. Risk assessment regarding the potential impact of stormwater ASR on the quality of the aquifer and groundwater resources in sandy aquifer is therefore necessary. After a characterisation of stormwater from different Melbourne catchments confirmed comparatively high concentrations of Zn and Cu in stormwater, three siliceous aquifer sediments were used in a series of batch sorption experiments as well as column experiments imitating one ASR cycle to assess the impact of different parameters on Zn and Cu behaviour. The reactive geochemical transport model PHT3D was then modified to simulate experimental results with the outlook that it could be used as a predictive tool for long term evaluation. The study showed that Zn adsorption was limited and desorption of large fractions occurred, indicating that injected amounts of Zn are mobile and would mainly be recovered. In contrast, Cu adsorption was higher and desorption was limited, indicating that injected amounts of Cu would mainly accumulate in the aquifer. The release of metals was triggered by reduction in pH, increase in ionic strength and particle mobilisation. Metal concentrations were also increased after storage phases, while minor sediment constituents, especially organic matter, significantly reduce metal mobility. The different role of dissolved and solid organic carbon is critical in understanding Cu behaviour during stormwater ASR. Pretreatment of stormwater to reduce the injection of colloids, organic carbon and metals are recommended to limit metal accumulation in the subsurface. Monitoring of water quality throughout the ASR cycle would be encouraged to validate the current findings with field data. Special attention should be paid to backflushed water quality to ensure correct disposal.

Tetrachloroethylene and its daughter-products represent a group of contaminations which are frequently found at sites with industrial activities, such as metal processing, electrotechnical and pharmaceutical industries as well as dry cleaning of clothing and the production of colours, paints and laquers. Due to their toxicity and persistence under natural conditions "denser-than-water" non aqueous phase liquids are substantial threats to the subsurface environment as well as the surface ecosystems including human beings. During the last two decades a number of technical solutions has been presented to enhance the situation of contaminated areas. One of the more recently established concepts are permeable reactive barriers. Permeable reactive barriers are passive in situ treatment zones containing a reactive material suitable to remove the contamination from the groundwater. They are installed downgradient from the pollution source perpendicular to the groundwater flow direction to immobilise or degrade the dissolved pollutants in the groundwater as it flows through. This project was organised in two main parts. The first part assessed seven different iron powders in batch experiments to determine the most efficient powder in terms of degradation velocity. The second part of the study employed this powder in a column experiment using different mixing ratios with sand to evaluate its performance under simulated subsurface conditions in a permeable reactive barrier. The aim of this experiment was to obtain a more detailed description of the behaviour and performance of the selected material. In the batch experiment the most promissing iron powder produced a half-life of tetrachloroethylene of 2.36 h. The column study demonstrated that cis-dichloroethylene has the longest half-life compared to tetrachlorethylene and trichloroethylene with 1.65 h. Having the longest half-life of all chloroethylenes included in this investigation the cis-dichloroethylene concentration will determine the dimensioning of a permeable barrier for remediation purposes.

The distribution of platinum group elements and increase of thein emissions in the environment are mostly related to the use of automobile catalyst. The antropogenic emissions of these noble metals accumulate aloung the roads. The methods such as ICP-OES and XRD were used for determinativ of phase and elemental composition of these samples. The matrix of the gasoline catalyst is composed of Al, Ce oxides with Pt-Pd-Rh coatings. Matrix of diesel catalyst is composed of cordierite with Pt coatings. ICP-MS was used for determination Pt, Pd and Rh. Before the analysis was performed such as pre-concetration fire assay fusion into a NiS button. The leaching characterization of Pt, Pd and Rh was examined during kinetic batch experiments in sodium chloride (1g/l, NaCl), 20 mM Na2P4O7 (NaPyr), fulvic acid (FK, DOC 50 mg/L) and 20 mM citric acid . The results show, that the dissolution of Pt and Pd is the fastest in citric acid and sodium pyrophosphate. Sodium chloride in the concentrations employed, which could be derived from melt waters formed during winter road treatment, does not have a substantiv impal on the speciation and mobilization of Pt and Pd. Organic acid does not have significantly impct on the release of Pt and Pd to the solution. The calculated normalized bulk released NRi values in the range 0,16...

<p>Highly polluted urban storm water from e.g. highways can contain large amounts of heavy metals that may cause harm if they are discharged into recipients. To remove the heavy metals a possible low-cost method that does not require much maintenance, could be the use of reactive filters with filter materials consisting of industrial residues or other cheap mineral based materials. Dissolved metal ions are removed by reactive filters through the processes of ions binding to active sites on the surface of the filter materials, or by formation of insoluble precipitates.</p><p>The ability of CaO-treated granulated blast-furnace slag, iron oxide coated sand, olivine and nepheline to remove seven heavy metals (Cr, Cd, Cu, Ni, Zn, Pb and Hg) from urban storm water was studied. Initially batch experiments were performed where the effect of pH, dissolved organic carbon (DOC) and dissolved ions on the adsorption efficiency was studied. The experiments were conducted with urban storm water and with a reference solution (10 mM NaNO3), both containing the same concentration of heavy metals (approx. 1 μM). The two materials with the best results were further investigated in a column study, where the capacity of the filter was tested. Chemical equilibrium calculations using the program Visual MINTEQ were performed in order to assess the role of precipitation as a mechanism for removal.</p><p>The results show that the blast-furnace slag was the most effective filter material and that it has great potential to be used as a heavy metal remover. Also the iron oxide coated sand worked satisfactory. The highest degree of removal was obtained for lead, cadmium and nickel, for which the removal efficiency exceeded 90% after a load of 300 times the water volume in the columns. For some metals, mainly copper, chromium and mercury the dissolved organic matter affected the removal negatively. The chemical mechanisms causing the removal are specific adsorption to the surfaces of the materials, and for the blast-furnace slag probably precipitation of insoluble metal sulfides.</p> / <p>Starkt förorenat dagvatten som rinner av från exempelvis motorvägar, kan innehålla betydliga mängder tungmetaller som kan orsaka skada om de kommer ut i omgivande vattendrag. En billig metod för tungmetallavskiljning, som inte kräver så mycket underhåll, skulle kunna vara att använda reaktiva filtermaterial bestående av restprodukter eller andra mineraliska lågkostnadsmaterial. Reaktiva filter fungerar som metallavskiljare genom att de lösta metalljonerna binder till ytgrupper på filtermaterialen eller att svårlösliga utfällningar bildas.</p><p>Förmågan att avskilja sju tungmetaller (Cr, Cd, Cu, Ni, Zn, Pb och Hg) ur dagvatten har undersökts för fyra mineraliska filtermaterial, kalciumoxiddopad masugnsslagg, järnoxidsand, olivin och nefelin. Studien inleddes med skakförsök där adsorptionens pH-beroende undersöktes. Försöken gjordes dels med dagvatten, dels med en referenslösning (10 mM NaNO3) med samma tungmetallkoncentration (ca 1μM). Detta gjordes för att studera effekter av löst organiskt material och andra ligander på adsorptionen. Därefter testades de material som uppvisat bäst resultat i skakförsöket i kolonnförsök, ett försök som mer efterliknar en praktisk tillämpning och där filtrets kapacitet kan studeras. Genom kemiska jämviktsberäkningar med programmet Visual MINTEQ var det möjligt att undersöka om bildningen av svårlösliga metallutfällningar bidrog till metallavskiljningen.</p><p>Resultaten visar att slaggen var det effektivaste filtermaterialet och att detta har stor potential att användas för avskiljning av tungmetaller. Även järnoxidsanden fungerade tillfredsställande. De metaller som avskiljdes bäst var bly, kadmium och nickel, för vilka avskiljningen var > 90 % i kolonnförsöket efter en belastning motsvarande 300 gånger vattenmängden i kolonnerna. För vissa metaller, främst koppar, krom och kvicksilver, försämrades avskiljningen betydligt när löst organiskt material fanns närvarande. Mekanismerna som står för avskiljningen är till störst del adsorption till grupper på filtermaterialens ytor, men bildning av svårlösliga metallsulfider är också tänkbar för slaggen.</p>

Highly polluted urban storm water from e.g. highways can contain large amounts of heavy metals that may cause harm if they are discharged into recipients. To remove the heavy metals a possible low-cost method that does not require much maintenance, could be the use of reactive filters with filter materials consisting of industrial residues or other cheap mineral based materials. Dissolved metal ions are removed by reactive filters through the processes of ions binding to active sites on the surface of the filter materials, or by formation of insoluble precipitates. The ability of CaO-treated granulated blast-furnace slag, iron oxide coated sand, olivine and nepheline to remove seven heavy metals (Cr, Cd, Cu, Ni, Zn, Pb and Hg) from urban storm water was studied. Initially batch experiments were performed where the effect of pH, dissolved organic carbon (DOC) and dissolved ions on the adsorption efficiency was studied. The experiments were conducted with urban storm water and with a reference solution (10 mM NaNO3), both containing the same concentration of heavy metals (approx. 1 μM). The two materials with the best results were further investigated in a column study, where the capacity of the filter was tested. Chemical equilibrium calculations using the program Visual MINTEQ were performed in order to assess the role of precipitation as a mechanism for removal. The results show that the blast-furnace slag was the most effective filter material and that it has great potential to be used as a heavy metal remover. Also the iron oxide coated sand worked satisfactory. The highest degree of removal was obtained for lead, cadmium and nickel, for which the removal efficiency exceeded 90% after a load of 300 times the water volume in the columns. For some metals, mainly copper, chromium and mercury the dissolved organic matter affected the removal negatively. The chemical mechanisms causing the removal are specific adsorption to the surfaces of the materials, and for the blast-furnace slag probably precipitation of insoluble metal sulfides. / Starkt förorenat dagvatten som rinner av från exempelvis motorvägar, kan innehålla betydliga mängder tungmetaller som kan orsaka skada om de kommer ut i omgivande vattendrag. En billig metod för tungmetallavskiljning, som inte kräver så mycket underhåll, skulle kunna vara att använda reaktiva filtermaterial bestående av restprodukter eller andra mineraliska lågkostnadsmaterial. Reaktiva filter fungerar som metallavskiljare genom att de lösta metalljonerna binder till ytgrupper på filtermaterialen eller att svårlösliga utfällningar bildas. Förmågan att avskilja sju tungmetaller (Cr, Cd, Cu, Ni, Zn, Pb och Hg) ur dagvatten har undersökts för fyra mineraliska filtermaterial, kalciumoxiddopad masugnsslagg, järnoxidsand, olivin och nefelin. Studien inleddes med skakförsök där adsorptionens pH-beroende undersöktes. Försöken gjordes dels med dagvatten, dels med en referenslösning (10 mM NaNO3) med samma tungmetallkoncentration (ca 1μM). Detta gjordes för att studera effekter av löst organiskt material och andra ligander på adsorptionen. Därefter testades de material som uppvisat bäst resultat i skakförsöket i kolonnförsök, ett försök som mer efterliknar en praktisk tillämpning och där filtrets kapacitet kan studeras. Genom kemiska jämviktsberäkningar med programmet Visual MINTEQ var det möjligt att undersöka om bildningen av svårlösliga metallutfällningar bidrog till metallavskiljningen. Resultaten visar att slaggen var det effektivaste filtermaterialet och att detta har stor potential att användas för avskiljning av tungmetaller. Även järnoxidsanden fungerade tillfredsställande. De metaller som avskiljdes bäst var bly, kadmium och nickel, för vilka avskiljningen var &gt; 90 % i kolonnförsöket efter en belastning motsvarande 300 gånger vattenmängden i kolonnerna. För vissa metaller, främst koppar, krom och kvicksilver, försämrades avskiljningen betydligt när löst organiskt material fanns närvarande. Mekanismerna som står för avskiljningen är till störst del adsorption till grupper på filtermaterialens ytor, men bildning av svårlösliga metallsulfider är också tänkbar för slaggen.

Em muitos países e principalmente no Brasil, compostos oxigenados tais como etanol e metil terta-butil-éter (MTBE) têm sido adicionados à gasolina em cerca de 26% do seu volume para aumentar a octanagem do motor e diminuir a emissão de monóxido de carbono e os níveis de ozônio na atmosfera. O derramamento de tais gasolinas, referidas como gasolina oxigenada tem um efeito cosolvente, provocando um aumento da concentração dos hidrocarbonetos na água subterrânea. A taxa de dissolução em água da gasolina oxigenada, que é dependente das propriedades químicas dos compostos orgânicos, determinam o grau e a severidade de contaminação da água subterrânea nas vizinhanças do derramamento. O objetivo do trabalho foi analisar e quantificar o potencial de contaminação da água subterrânea e de solos arenosos residuais dos arenitos da Formação Botucatu por derramamento de gasolina oxigenada. As análises realizadas buscam fornecer dados para a modelagem numérica em casos envolvendo derramamento de gasolina. Ensaios de equilíbrio em lote e de dissolução em colunas foram realizados objetivando a determinação da concentração aquosa de hidrocarbonetos da gasolina em equilíbrio de fases e a avaliação do tempo estimado para total dissolução em água dos hidrocarbonetos da gasolina pura. Ambos os ensaios analisaram também o efeito cosolvente do etanol na mistura. Verificou-se a validade da lei de Raoult e do modelo log-linear na determinação da concentração aquosa da gasolina pura e oxigenada. Em colunas de solos não saturados avaliou-se a difusão na fase vapor dos compostos orgânicos da gasolina em função do tempo. Finalizando as análises, fez-se uma simulação numérica do transporte da gasolina em zonas não saturadas fazendo-se uso do programa R-UNSAT. / In many countries and mainly in Brazil oxygenated compounds such as ethanol and MTBE have been added to gasoline up to 26% to increase the octane level and to reduce carbon monoxide and ozone levels in the air. The spill of such gasolines, referred as oxygenated gasoline has a potential cosolvent effect, resulting in an increased groundwater concentration of hydrocarbons. The rate of oxygenated gasoline dissolution, which is dependent of the chemical properties of the compounds, determines the degree and severity of groundwater contamination in the vicinity of the spill. The goal of this research was to analyze and to quantify the potential of contamination of the groundwater and of the residual sandy soils from Botucatu sandstone due to the spill of oxigenated gasoline. The performed analysis supply data to the numerical model in case of gasoline spills. Laboratory batch and column leaching tests were carried out in order to determine the equilibrium aqueous concentration of the hydrocarbons compounds of gasoline and to evaluate the time scale for aqueous dissolution of the hydrocarbons compounds. Both tests have analyzed the cosolvent effect of ethanol in the mixture. It was verified the validity of the Raoult's law and the log-linear cosolvency model to estimate the solubility of the hydrocarbons compounds from unamended gasoline and from oxygenated gasoline. Column tests with unsaturated undisturbed soil samples were carried out to investigate the vapor-phase diffusion of aromatic hydrocarbons compounds with time. Finally the transport of gasoline in unsaturated zones was simulated with the R-UNSAT model.

Em muitos países e principalmente no Brasil, compostos oxigenados tais como etanol e metil terta-butil-éter (MTBE) têm sido adicionados à gasolina em cerca de 26% do seu volume para aumentar a octanagem do motor e diminuir a emissão de monóxido de carbono e os níveis de ozônio na atmosfera. O derramamento de tais gasolinas, referidas como gasolina oxigenada tem um efeito cosolvente, provocando um aumento da concentração dos hidrocarbonetos na água subterrânea. A taxa de dissolução em água da gasolina oxigenada, que é dependente das propriedades químicas dos compostos orgânicos, determinam o grau e a severidade de contaminação da água subterrânea nas vizinhanças do derramamento. O objetivo do trabalho foi analisar e quantificar o potencial de contaminação da água subterrânea e de solos arenosos residuais dos arenitos da Formação Botucatu por derramamento de gasolina oxigenada. As análises realizadas buscam fornecer dados para a modelagem numérica em casos envolvendo derramamento de gasolina. Ensaios de equilíbrio em lote e de dissolução em colunas foram realizados objetivando a determinação da concentração aquosa de hidrocarbonetos da gasolina em equilíbrio de fases e a avaliação do tempo estimado para total dissolução em água dos hidrocarbonetos da gasolina pura. Ambos os ensaios analisaram também o efeito cosolvente do etanol na mistura. Verificou-se a validade da lei de Raoult e do modelo log-linear na determinação da concentração aquosa da gasolina pura e oxigenada. Em colunas de solos não saturados avaliou-se a difusão na fase vapor dos compostos orgânicos da gasolina em função do tempo. Finalizando as análises, fez-se uma simulação numérica do transporte da gasolina em zonas não saturadas fazendo-se uso do programa R-UNSAT. / In many countries and mainly in Brazil oxygenated compounds such as ethanol and MTBE have been added to gasoline up to 26% to increase the octane level and to reduce carbon monoxide and ozone levels in the air. The spill of such gasolines, referred as oxygenated gasoline has a potential cosolvent effect, resulting in an increased groundwater concentration of hydrocarbons. The rate of oxygenated gasoline dissolution, which is dependent of the chemical properties of the compounds, determines the degree and severity of groundwater contamination in the vicinity of the spill. The goal of this research was to analyze and to quantify the potential of contamination of the groundwater and of the residual sandy soils from Botucatu sandstone due to the spill of oxigenated gasoline. The performed analysis supply data to the numerical model in case of gasoline spills. Laboratory batch and column leaching tests were carried out in order to determine the equilibrium aqueous concentration of the hydrocarbons compounds of gasoline and to evaluate the time scale for aqueous dissolution of the hydrocarbons compounds. Both tests have analyzed the cosolvent effect of ethanol in the mixture. It was verified the validity of the Raoult's law and the log-linear cosolvency model to estimate the solubility of the hydrocarbons compounds from unamended gasoline and from oxygenated gasoline. Column tests with unsaturated undisturbed soil samples were carried out to investigate the vapor-phase diffusion of aromatic hydrocarbons compounds with time. Finally the transport of gasoline in unsaturated zones was simulated with the R-UNSAT model.

Phytoplankton blooms compromise the quality of freshwater ecosystems and the efficient processing of water by treatment works worldwide. This research aims to determine whether in-situ filamentous biofiltration processes mediated by living roots and synthetic filters as media can reduce or remove the phytoplankton loading (micro-algae and cyanobacteria) prior to a potable water treatment works intake. The underlying biofiltration mechanisms were investigated using field and laboratory studies. A novel macroscale biofilter with three plant species, named the "Living-Filter", installed in Farmoor II reservoir, UK, was surveyed weekly for physicochemical and biological variables under continuous flow conditions during 17 weeks. The efficiency of a mesoscale biofilter using the aquatic plant Phalaris arundinacea and synthetic filters, was tested with Microcystis aeruginosa under continuous flow conditions and in batch experiments. The 'simultaneous allelochemical method' was developed for quantifying allelochemicals from Phalaris in aqueous samples. Microscale studies were used to investigate biofilter allelochemical release in response to environmental stressors and Microcystis growth inhibition in filtered and unfiltered aqueous root exudate. Results demonstrate that the removal of phytoplankton biomass by physical mechanisms has a removal efficiency of &le;45% in the "Living-Filter" (filamentous biofilter plus synthetic fabric) and that the removal of Microcystis biomass using only biofilters was 25%. Chemical mechanisms that reduce Microcystis cell numbers are mediated by allelochemicals released from biofilter roots. Root exudate treatments on Microcystis revealed that Microcystis growth is inhibited by allelochemicals, not by nutrient competition, and that protists and invertebrates play a role in removing Microcystis. Filamentous biofilters can remove phytoplankton biomass by physical, chemical and biological mechanisms. Biofilters and synthetic filters in combination improve removal efficiency. Application of macroscale biofilters prior to potable water treatment works benefits the ecosystem. Plant properties, biofilter size to surface water ratio, and retention time must be considered to maximise the benefits of biofiltration processes.

PhDENV / Department of Ecology and Resource Management / See the attached abstract below