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Thesis (M.Sc.)(Soil Science)--University of Pretoria, 2008. / Includes summary. Includes bibliographical references. Available on the Internet via the World Wide Web.

No description available.

Mining areas produce large amounts of waste that are important sources of potentially toxic elements (PTE), such as heavy metals. These PTEs can contaminate the environment and cause serious threats to the ecosystem and human health. The in-situ remediation by the addition of amendments is an efficient alternative for the immobilization of contaminants and for reduction of the risks associated with these pollutants. Phosphate, lime, and organic compounds are the most used amendments for in-situ remediation. We evaluated the effect of rates of amendments in desorption kinetics and speciation of Zn, Cd, and Pb in a soil contaminated by mining activities. The soil was collected in a disabled Zn mining area in the city of Vazante, state of Minas Gerais, Brazil. The contaminated soil was incubated with either phosphate, or calcium carbonate, or biochar, or biosolid. Desorption kinetics was evaluated by the \"stirred-flow\" method that consists of a constant flow with a Mehlich-3 solution. The speciation was performed by X-ray absorption spectroscopy (XAS) and sequential extraction. The analysis with synchrotron radiation X-ray absorption near the edge (XANES) was performed for Pb and Zn. We also performed a mapping by μ-XRF (micro X-ray fluorescence) and in some spots on the map we performed the speciation by μ-XANES for Zn in the soil amended with phosphate. An experiment with columns was carried out with samples from the soil amended with phosphate to evaluate leaching of Zn, Pb, and Cd. The treatment with phosphate affected the species of Zn. However, some Zn species that were formed and can be mobilized most easily. Zn was more easily mobilized in the highest rate of phosphate probably because of the decrease of the pH. The treatments with biosolid, biochar and calcite did not change Zn species. However, in some rates, Zn desorption decreased while Zn contents increased in the recalcitrant fraction. The main species in the unamended soil was Pb-bentonite and anglesite. The soil amended with calcite and pyromorphite decreased the desorption kinetics of Pb and increased the Pb extracted in the residual fraction, and this could be due to formation of pyromorphite. The soil amended with biosolid and biochar increased the Pb extracted in the organic fraction and decreased in the residual fraction. In these treatments part of the species of Pb present on this soil was transformed in Pb-citrate. The addition of biochar and biosolid increased the desorption kinetics of Pb in all rates applied. The treatment with either biochar or biosolid was effective to decrease the Cd desorption. In these organic amendments, the content of Cd associated to organic matter (OM)increased. The treatments with phosphate and calcite also increased the Cd associated to OM extracted in the F3. These inorganic amendments were effective to decrease the desorption kinetics of Cd. / Áreas de mineração produzem grandes quantidades de resíduos que são importantes fontes de elementos potencialmente tóxicos (EPT), tais como os metais pesados. Esses EPTs podem contaminar o meio ambiente e causar sérias ameaças ao ecossistema e à saúde humana. A remediação in-situ pela adição de condicionadores é alternativa eficiente para a imobilização de contaminantes e para redução dos riscos associados a esses poluentes. Fosfato, calcita e compostos orgânicos são os condicionadores mais utilizadas para remediação in-situ. Neste estudo foi avaliado o efeito da aplicação de condicionadores na cinética de dessorção e especiação de Zn, Cd e Pb em um solo contaminado por atividades de mineração. O solo foi coletado em uma área desativada de mineração de Zn, localizada na cidade de Vazante, MG. A solo contaminado foi incubado com fosfato, carbonato de cálcio, biocarvão ou biossólido. A cinética de dessorção foi avaliada pelo método fluxo constante com a solução de Mehlich-3. A especiação foi realizada por espectroscopia de absorção de raios-x (XAS) e extração sequencial, enquanto a análise absorção de raios-x próxima da borda (XANES) foi realizada para Pb e Zn. Também realizamos o mapeamento por μ-XRF (microfluorescência de raios-x) e em alguns pontos no mapa realizamos a especiação por μ-XANES do Zn no solo tratado com fosfato. Foi também conduzido um experimento com colunas para avaliar a lixiviação de Zn, Pb e Cd no solo tratado com fosfato. A adição de fosfato afetou as espécies de Zn. No entanto, algumas espécies de Zn que foram formadas e assim podem ser mobilizadas com mais facilidade. O Zn foi mais facilmente mobilizado na maior taxa de fosfato, provavelmente devido à diminuição do pH. Os tratamentos com biossólido, biocarvão e calcita não alteraram as espécies de Zn. No entanto, em algumas doses, a dessorção de Zn diminuiu, enquanto o teor de Zn aumentou na fração recalcitrante. As principais espécies no solo sem alterações foram a bentonita Pb e a anglesita. O solo corrigido com calcita diminuiu a cinética de dessorção do Pb e aumentou o Pb extraído na fração residual, o que pode ser devido à formação de piromorfita. Os solos tratados com biossólido e com biocarvão aumentaram o teor de Pb associado à matéria orgânica e diminuíram na fração residual. Nestes tratamentos parte das espécies de Pb presentes neste solo foi transformada em Pb ligado a citrato. Essas alterações orgânicas aumentaram substancialmente a cinética de dessorção do Pb em todas as doses adicionadas. Os tratamentos com biocarvão e com biossólido foram efetivos para diminuir a dessorção de Cd. Nestas alterações orgânicas o Cd associado à matéria orgânica aumentou. Os tratamentos com fosfato e calcita também aumentaram o teor de Cd na fração orgânica. Essas alterações inorgânicas também foram eficazes para diminuir a cinética de dessorção do Cd.

Abstract Food sustainability depends significantly on packaging since it helps maintainfood safe and fresh throughout its shelf life, resulting in the least amount ofwaste and the least negative environmental impact. The main objective of thisstudy is to determine the adsorbed and released amount of antimicrobial agents(benzoic acid and thymol) on modified calcium carbonate (MCC) by investigating adsorption isotherm at 25°C and desorption kinetics at both 22°C and5°C of anti-microbial to identify potential solutions to enhance the long-termsustainability of fresh products such as meat. These agents were incorporatedinto specialized food pads to mitigate bacterial growth in food packaging instead of being directly added to the food. Additionally, the study aimed to determine the amount of carbon dioxide generated when MCC, used as an adsorbent in combination with citric acid, comes into contact with the meat liquid,as this has an impact on the growth of aerobic microorganisms.The findings revealed that MCC adsorbed 44% and 55% of the initial quantities of benzoic acid (BA) and thymol, respectively. Furthermore, after 12 seconds from an initial adsorption amount of 19 mg/g, the maximum amount ofthymol released from MCC was measured at 0.120 mg/ml (approximately0.126%). Similarly, for an initial adsorption amount of 15 mg/g, the quantityof BA released was found to be 0.080 mg/ml (approximately 0.106%). TheUV-spectrophotometer was utilized to determine the amounts of adsorbed anddesorbed anti-microbial agents, while Checkmate 3 was used to assess the release of carbon dioxide.Significantly, the utilization of food pads demonstrated a significant enhancement in the release of carbon dioxide. Interestingly, the presence of anti-microbial agents did not have any influence on the generation of carbon dioxide.This research provides valuable insights into the potential application of foodpads and MCC as effective strategies for preserving fresh meat products bycontrolling microbial activity and promoting sustainability. / Sammanfattning Livsmedelshållbarhet beror i hög grad på förpackningar eftersom det hjälpertill att hålla maten säker och fräsch under hela dess hållbarhetstid, vilket resulterar i minskad mängd avfall och mindre negativ miljöpåverkan. Huvudsyftetmed denna studie var att bestämma den adsorberade och frigjorda mängdenantimikrobiella medel (bensoesyra och tymol) på modifierat kalciumkarbonat(MCC) genom att undersöka adsorptionsisoterm vid 25°C och desorptionskinetiken vid både 22°C och 5 °C av antimikrobiellt medel för att identifierapotentiella lösningar för att förbättra den långsiktiga hållbarheten för färskaprodukter som kött. Dessa medel inkorporerades i specialiserade food pad föratt mildra bakterietillväxt i livsmedelsförpackningar istället för att läggas direkt till maten. Dessutom syftade studien till att fastställa mängden koldioxidsom genereras när MCC, som används som adsorbent i kombination med citronsyra, kommer i kontakt med köttvätskan, eftersom detta har en inverkan påtillväxten av aeroba mikroorganismer.Resultaten visade att MCC adsorberade 44 % och 55 % av de initiala mängderna bensoesyra (BA) respektive tymol. Vidare, efter 12 sekunder från eninitial adsorptionsmängd på 19 mg/g, mättes den maximala mängden tymolsom frigjordes från MCC till 0,120 mg/ml (ungefär 0,126%). På liknande sätt,för en initial adsorptionsmängd på 15 mg/g, visade sig mängden frisatt BA vara0,080 mg/ml (ungefär 0,106%). UV-spektrofotometern användes för att bestämma mängderna av adsorberade och desorberade antimikrobiella medel,medan Checkmate 3 användes för att bedöma frisättningen av koldioxid.Betecknande nog visade användningen av food pad betydande förbättring avutsläppet av koldioxid. Intressant nog har närvaron av antimikrobiella medelinte haft någon inverkan på genereringen av koldioxid. Denna forskning gervärdefulla insikter om den potentiella tillämpningen av food pad och MCC someffektiva strategier för att bevara färska köttprodukter genom att kontrolleramikrobiell aktivitet och främja hållbarhet.

The fate of the carbon and nitrogen in dairy farm effluent (DFE) applied onto soil was investigated through laboratory experiments and field lysimeter studies. They resulted in the development and testing of a complex carbon (C) and nitrogen (N) simulation model (CaNS-Eff) of the soil-plant-microbial system. To minimise the risk of contamination of surface waters, regulatory authorities in New Zealand promote irrigation onto land as the preferred treatment method for DFE. The allowable annual loading rates for DFE, as defined in statutory regional plans are based on annual N balance calculations, comparing N inputs to outputs from the farming system. Little information is available, however, to assess the effects that these loading rates have on the receiving environment. It is this need, to understand the fate of land-applied DFE and develop a tool to describe the process, that is addressed in this research. The microbially mediated net N mineralisation from DFE takes a central role in the turnover of DFE, as the total N in DFE is dominated by organic N. In a laboratory experiment, where DFE was applied at the standard farm loading rate of 68 kg N ha⁻¹, the net C mineralisation from the DFE was finished 13 days after application and represented 30% of the applied C, with no net N mineralisation being measured by Day 113. The soluble fraction of DFE appeared to have a microbial availability similar to that of glucose. The low and gradually changing respiration rate measured from DFE indicated a semi-continuous substrate supply to the microbial biomass, reflecting the complex nature and broad range of C compounds in DFE. The repeated application of DFE will gradually enhance the mineralisable fraction of the total soil organic N and in the long term increase net N mineralisation. To address the lack of data on the fate of faecal-N in DFE, a ¹⁵N-labelled faecal component of DFE was applied under two different water treatments onto intact soil cores with pasture growing on them. At the end of 255 days, approximately 2% of the applied faecal ¹⁵N had been leached, 11 % was in plant material, 11 % was still as effluent on the surface, and 40% remained in the soil (39% as organic N). Unmeasured gaseous losses and physical losses from the soil surface of the cores supposedly account for the remaining ¹⁵N (approximately 36%). Separate analysis of the total and ammonium nitrogen contents and ¹⁵N enrichments of the DFE and filtered sub-samples (0.5 mm, 0.2µm) showed that the faecal-N fraction was not labelled homogeneously. Due to this heterogeneity, which was exacerbated by the filtration of DFE on the soil surface, it was difficult to calculate the turnover of the total faecal-N fraction based on ¹⁵N results. By making a simplifying assumption about the enrichment of the ¹⁵N in the DFE that infiltrated the soil, the contribution from DFE-N to all plant available N fractions including soil inorganic N was estimated to have been approximately 11 % of the applied DFE-N. An initial two-year study investigating the feasibility of manipulating soil water conditions through controlled drainage to enhance denitrification from irrigated DFE was extended a further two years for this thesis project. The resulting four-year data set provided the opportunity to evaluate the sustainability of DFE application onto land, an extended data set against which to test the adequacy of CaNS-Eff, and to identify the key processes in the fate of DFE irrigated onto soil under field conditions. In the final year of DFE irrigation, 1554 kg N ha⁻¹ of DFE-N was applied onto the lysimeters, with the main removal mechanism being pasture uptake (700 kg N ha⁻¹ yr⁻¹ removed). An average of 193 kg N ha⁻¹ yr⁻¹ was leached, with 80% of this being organic N. The nitrate leaching decreased with increasing soil moisture conditions through controlled drainage. At the high DFE loading rate used, the total soil C and N, pH and the microbial biomass increased at different rates over the four years. The long-term sustainability of the application of DFE can only be maintained when the supply of inorganic N is matched by the demand of the pasture. The complex simulation model (CaNS-Eff) of the soil-plant-microbial system was developed to describe the transport and transformations of C and N components in effluents applied onto the soil. The model addresses the shortcomings in existing models and simulates the transport, adsorption and filtration of both dissolved and particulate components of an effluent. The soil matrix is divided into mobile and immobile flow domains with convective flow of solutes occurring in the mobile fraction only. Diffusion is considered to occur between the micropore and mesopore domains both between and within a soil layer, allowing dissolved material to move into the immobile zone. To select an appropriate sub-model to simulate the water fluxes within CaNS-Eff, the measured drainage volumes and water table heights from the lysimeters were compared to simulated values over four years. Two different modelling approaches were compared, a simpler water balance model, DRAINMOD, and a solution to Richards' equation, SWIM. Both models provided excellent estimation of the total amount of drainage and water table height. The greatest errors in drainage volume were associated with rain events over the summer and autumn, when antecedent soil conditions were driest. When soil water and interlayer fluxes are required at small time steps such as during infiltration under DFE-irrigation, SWIM's more mechanistic approach offered more flexibility and consequently was the sub-model selected to use within CaNS-Eff. Measured bromide leaching from the lysimeters showed that on average 18% of the bromide from an irrigation event bypassed the soil matrix and was leached in the initial drainage event. This bypass mechanism accounted for the high amount of organic N leached under DFE-irrigation onto these soils and a description of this bypass process needed to be included in CaNS-Eff. Between 80 and 90% of the N and C leached from the lysimeters was particulate (> 0.2 µm in size), demonstrating the need to describe transport of particulate material in CaNS-Eff. The filtration behaviour of four soil horizons was measured by characterising the size of C material in a DFE, applying this DFE onto intact soil cores, and collecting and analyzing the resulting leachate using the same size characterisation. After two water flushes, an average of 34% of the applied DFE-C was leached through the top 0-50 mm soil cores, with a corresponding amount of 27% being leached from the 50-150 mm soil cores. Most of the C leaching occurred during the initial DFE application onto the soil. To simulate the transport and leaching of particulate C, a sub-model was developed and parameterised that describes the movement of the effluent in terms of filtering and trapping the C within a soil horizon and then washing it out with subsequent flow events. The microbial availability of the various organic fractions within the soil system are described in CaNS-Eff by availability spectra of multiple first-order decay functions. The simulation of microbial dynamics is based on actual consumption of available C for three microbial biomass populations: heterotrophs, nitrifiers and denitrifiers. The respiration level of a population is controlled by the amount of C that is available to that population. This respiration rate can vary between low level maintenance requirements, when very little substrate is available, and higher levels when excess substrate is available to an actively growing population. The plant component is described as both above and below-ground fractions of a rye grass-clover pasture. The parameter set used in CaNS-Eff to simulate the fate of DFE irrigated onto the conventionally drained lysimeter treatments over three years with a subsequent 10 months non-irrigation period was derived from own laboratory studies, field measurements, experimental literature data and published model studies. As no systematic calibration exercise was undertaken to optimise these parameters, the parameter set should be considered as "initial best estimates" and not as a calibrated data set on which a full validation of CaNS-Eff could be based. Over the 42 months of simulation, the cumulative drainage from CaNS-Eff for the conventionally drained DFE lysimeter was always within the 95% CI of the measured value. On the basis of individual drainage bulking periods, CaNS-Eff was able to explain 92% of the variation in the measured drainage volumes. On an event basis the accuracy of the simulated water filled pore space (WFPS) was better than that of the drainage volume, with an average of 70% of the simulated WFPS values being within the 95% CI for the soil layers investigated, compared to 44% for the drainage volumes. Overall the hydrological component of CaNS-Eff, which is based on the SWIM model, could be considered as satisfactory for the purposes of predicting the soil water status and drainage volume from the conventionally drained lysimeter treatment for this study. The simulated cumulative nitrate leaching of 4.7 g NO₃-N m⁻² over the 42 months of lysimeter operation was in good agreement to the measured amount of 3.0 (± 2.7) g NO₃-N m⁻². Similarly, the total simulated ammonium leaching of 2.7g NH₄- N m⁻² was very close to the measured amount of 2.5 (± 1.35) g NH₄- N m⁻² , however the dynamics were not as close to the measured values as with the nitrate leaching. The simulated amount of organic N leached was approximately double that measured, and most of the difference originated from the simulated de-adsorption of the dissolved fraction of organic N during the l0-month period after the final DFE irrigation. The 305 g C m⁻² of simulated particulate C leached was close to the measured amount of 224 g C m⁻² over the 31 months of simulation. The dissolved C fraction was substantially over-predicted. There was good agreement in the non-adsorbed and particulate fractions of the leached C and N in DFE. However, the isothermic behaviour of the adsorbed pools indicated that a non-reversible component needed to be introduced or that the dynamics of the de-adsorption needed to be improved. Taking into account that the parameters were not calibrated but only "initial best estimates", the agreement in the dynamics and the absolute amounts between the measured and simulated values of leached C and N demonstrated that CaNS-Eff contains an adequate description of the leaching processes following DFE irrigation onto the soil. The simulated pasture N production was in reasonable agreement with the measured data. The simulated dynamics and amounts of microbial biomass in the topsoil layers were in good agreement with the measured data. This is an important result as the soil microbial biomass is the key transformation station for organic materials. Excepting the topsoil layer, the simulated total C and N dynamics were close to the measured values. The model predicted an accumulation of C and N in the topsoil layer as expected, but not measured. Although no measurements were available to compare the dynamics and amounts of the soil NO₃-N and NH₄-N, the simulated values appear realistic for an effluent treatment site and are consistent with measured pasture data. Considering the large amount of total N and C applied onto the lysimeters over the 42 months of operation (4 t ha⁻¹ of N and 42 t ha⁻¹0f C), the various forms of C and N in dissolved and particulate DFE as well as in returned pasture, and that the parameters used in the test have not been calibrated, the simulated values from CaNS-Eff compared satisfactorily to the measured data.