<p>This study evaluated SO4 2- removal from circumneutral mine water (CMW) collected from Middleburg coal mine using coal FA collected from Hendrina power station. The following parameters were investigated: the effect of the amount of FA, the effect of the final pH achieved during treatment, the effect of the initial pH of the mine water and the effect of Fe and Al on SO4 2- removal from mine water. The precipitation of ettringite at alkaline pH was evaluated to further reduce the SO4 2- concentration to below the DWAF limit for potable water. Removal of SO4 2- from mine water was found to be dependent on: the final pH achieved during treatment, the amount of FA used to treat the mine water and the presence of Fe and Al in the mine water. Treatment of CMW using different CMW:FA ratios / 5:1, 4:1, 3:1, and 2:1 resulted in 55, 60, 70 and 71 % SO4 2- removal respectively. Treatment of CMW to pH 8.98, 9.88, 10.21, 10.96, 11.77 and 12.35 resulted in 6, 19, 37, 45, 63 and 71 % SO4 2- removal respectively. When the CMW was modified by adding Fe and Al by mixing with Navigation coal mine AMD and treated to pH 10, 93 % SO4 2- removal was observed. Further studies were done to evaluate the effects of Fe and Al separately. Treatment of simulated Fe containing AMD (Fe-AMD) to pH 9.54, 10.2, 11.8, and 12.1 resulted in 47, 52, 65, and 68 % SO4 2- removal respectively. When Al containing AMD was treated to pH 9.46, 10.3, 11.5 and 12 percentage SO4 2- removal of 39, 51, 55 and 67 % was observed respectively.</p>

<p>This study evaluated SO4 2- removal from circumneutral mine water (CMW) collected from Middleburg coal mine using coal FA collected from Hendrina power station. The following parameters were investigated: the effect of the amount of FA, the effect of the final pH achieved during treatment, the effect of the initial pH of the mine water and the effect of Fe and Al on SO4 2- removal from mine water. The precipitation of ettringite at alkaline pH was evaluated to further reduce the SO4 2- concentration to below the DWAF limit for potable water. Removal of SO4 2- from mine water was found to be dependent on: the final pH achieved during treatment, the amount of FA used to treat the mine water and the presence of Fe and Al in the mine water. Treatment of CMW using different CMW:FA ratios / 5:1, 4:1, 3:1, and 2:1 resulted in 55, 60, 70 and 71 % SO4 2- removal respectively. Treatment of CMW to pH 8.98, 9.88, 10.21, 10.96, 11.77 and 12.35 resulted in 6, 19, 37, 45, 63 and 71 % SO4 2- removal respectively. When the CMW was modified by adding Fe and Al by mixing with Navigation coal mine AMD and treated to pH 10, 93 % SO4 2- removal was observed. Further studies were done to evaluate the effects of Fe and Al separately. Treatment of simulated Fe containing AMD (Fe-AMD) to pH 9.54, 10.2, 11.8, and 12.1 resulted in 47, 52, 65, and 68 % SO4 2- removal respectively. When Al containing AMD was treated to pH 9.46, 10.3, 11.5 and 12 percentage SO4 2- removal of 39, 51, 55 and 67 % was observed respectively.</p>

Magister Scientiae - MSc / This study evaluated SO4 2- removal from circumneutral mine water (CMW) collected from Middleburg coal mine using coal FA collected from Hendrina power station. The following parameters were investigated: the effect of the amount of FA, the effect of the final pH achieved during treatment, the effect of the initial pH of the mine water and the effect of Fe and Al on SO4 2- removal from mine water. The precipitation of ettringite at alkaline pH was evaluated to further reduce the SO4 2- concentration to below the DWAF limit for potable water. Removal of SO4 2- from mine water was found to be dependent on: the final pH achieved during treatment, the amount of FA used to treat the mine water and the presence of Fe and Al in the mine water. Treatment of CMW using different CMW:FA ratios; 5:1, 4:1, 3:1, and 2:1 resulted in 55, 60, 70 and 71 % SO4 2- removal respectively. Treatment of CMW to pH 8.98, 9.88, 10.21, 10.96, 11.77 and 12.35 resulted in 6, 19, 37, 45, 63 and 71 % SO4 2- removal respectively. When the CMW was modified by adding Fe and Al by mixing with Navigation coal mine AMD and treated to pH 10, 93 % SO4 2- removal was observed. Further studies were done to evaluate the effects of Fe and Al separately. Treatment of simulated Fe containing AMD (Fe-AMD) to pH 9.54, 10.2, 11.8, and 12.1 resulted in 47, 52, 65, and 68 % SO4 2- removal respectively. When Al containing AMD was treated to pH 9.46, 10.3, 11.5 and 12 percentage SO4 2- removal of 39, 51, 55 and 67 % was observed respectively. / South Africa

>Magister Scientiae - MSc / South African power stations generate large amounts of highly alkaline fly ash (FA). This waste product has a serious impact on the environment. Acid mine drainage (AMD) is another environmental problem associated with mining. AMD has high heavy metal content in addition to high SO/- concentrations. Several studies have shown that 80-90 % of SO/- can be removed when FA is codisposed with AMD rich in Fe and AI. In South Africa, many sources of contaminated mine waters have circumneutral pH and much lower concentrations of Fe and Al (unlike AMD), but are rich in Ca, Mg and SO2-4. This study evaluated sol removal from circumneutral mme water (CMW) collected from Middleburg coal mine using coal FA collected from Hendrina power station. The following parameters were investigated: the effect of the amount of FA, the effect of the final pH achieved during treatment, the effect of the initial pH of the mine water and the effect of Fe and Al on SO/- removal from mine water. The precipitation of ettringite at alkaline pH was evaluated to further reduce the SO/- concentration to below the DWAF limit for potable water. Removal of sol from mine water was found to be dependent on: the final pH achieved during treatment, the amount of FA used to treat the mine water and the presence of Fe and Al in the mine water. Treatment of CMW using different CMW:FA ratios; 5:1, 4:1, 3:1, and 2:1 resulted in 55, 60, 70 and 71 % SO/- removal respectively. Treatment of CMW to pH 8.98, 9.88, 10.21, 10.96, 11.77 and 12.35 resulted in 6, 19, 37, 45, 63 and 71 % SO/- removal respectively. When the CMW was modified by adding Fe and Al by mixing with Navigation coal mine AMD and treated to pH 10, 93 % SO/- removal was observed. Further studies were done to evaluate the effects of Fe and Al separately. Treatment of simulated Fe containing AMD (Fe-AMD) to pH 9.54, 10.2, 11.8, and 12.1 resulted in 47, 52,65, and 68 % SO/- removal respectively. When Al containing AMD was treated to pH 9.46, 10.3, 11.5 and 12 percentage SO/- removal of 39, 51,55 and 67 % was observed respectively. Ion chromatography (IC), inductively coupled plasma-mass spectrometry (ICPMS) and inductively coupled plasma-atomic emission (ICP-AES) analysis of the product water, x-ray diffraction (XRD) and x-ray fluorescence (XRF) spectrometry analysis of FA and solid residues collected after treatment of mine water complemented with PHREEQC thermodynamic modelling have shown that the mechanism of S042 - removal from mine water depends on the composition of the mine water. The sol- removal mechanism from CMW was observed to depend on gypsum precipitation. On the other hand sol- removal from mine water containing Fe and Al was dependent on the precipitation of gypsum and Fe and Al oxyhydroxysulphates. The oxyhydroxysulphates predicted by PHREEQC as likely to precipitate were alunite, basaluminite, ettringite, jarosites and jurbanite. Treatment of CMW with FA to pH 12.35 removed sol- from 4655 ppm to approximately 1500 ppm. Addition of amorphous AI(OH)3 to CMW that was treated to pH greater than 12 with FA was found to further reduce the sol concentration to 500 ppm which was slightly above the threshold for potable water of 400 ppm. The further decrease of sol concentration from 1500 to 500 ppm was due to ettringite precipitation. Mine water treatment using FA was found to successfully remove all the major elements such as Fe, AI, Mn and Mg to below the DWAF limit for drinking water. The removal of the major elements was found to be pH dependent. Fe and Al were removed at pH 4-7, while Mn and Mg were removed at pH 9 and 11 respectively. The process water from FA treatment followed by gypsum seeding and addition of AI(OH)3 had high concentration of Ca, Cr, Mo and B and a pH of greater than 12. The pH of the process water from FA treatment followed by gypsum seeding and addition of AI(OH)3 was reduced by reacting the process water with CO2 to 7.06. The process water from the carbonation process contained trace elements such as Cr, Mo and B above the DWAF effluent limit for domestic use. Carbonation of the process water reduced the water hardness from 5553 ppm to 317 ppm due to CaC03 precipitation, thereby reducing the Ca concentration from 2224 ppm to 126 ppm.

Increased groundwater usage, rainfall decline and activities such as mining have resulted in the acidification of certain wetlands in the south-west of Western Australia. This study investigated the influence of pH, the factor most commonly associated with acidification, on the invertebrate and diatom community structure of 20 wetlands in the south-west region of Western Australia. Few studies in Western Australia have investigated both biotic groups, particularly in relation to pH. Consequently, this study examined the comparative sensitivity of the two biotic groups to pH in order to identify the most effective biotic tool for assessing the ecological impacts of pH decrease. The wetlands included in this study displayed a wide range of pH from acidic (pH < 6.5) to alkaline (pH > 7.5). Other environmental parameters were also variable. Separation of the wetlands into three pH groups; Group 1 – acidic, Group 2 – circumneutral and Group 3 – alkaline, demonstrated that the acidic Group 1 wetlands generally had higher electrical conductivity than the remaining groups. This was probably due to the association of many Group 1 sites with mining and acid sulphate soils. Seasonal trends in environmental variables across the three pH groups were mostly unclear although some trends were evident within the individual pH groups. The study showed that invertebrate community structure differed in response to pH. However, the results also demonstrated that invertebrate distribution patterns were influenced by other factors. / Potential indicator species identified from the study included Macrothrix indistincta and Tanytarsus fuscithorax/semibarbitarsus which were abundant in acidic waters and Alona quadrangularis which was common in circumneutral sites. Taxa such as Calamoecia tasmanica subattenuata were common over a wider range of pH (acidic to circumneutral) but may still have potential to act as indicators of pH decline. Diatom community structure was also shown to be influenced by pH, with the variable identified as a major determinant of diatom distribution patterns. Nitzschia paleaeformis and Navicula aff. cari were generally recorded from acidic wetlands and are potentially useful as indicators of low pH conditions. Brachysira brebissonii and Frustulia magaliesmontana were also identified as species with the potential to indicate pH decline. In contrast, taxa including Gomphonema parvulum, Staurosira construens var. venter and Nitzschia palea were generally associated with moderate to high pH levels. A comparative study of the two biotic groups using multivariate analyses revealed that diatoms were more sensitive to pH than invertebrates. Further investigation with a larger number of environmental variables would be necessary to ascertain the other factors primarily influencing invertebrate community structure. Nonetheless, the findings imply that diatoms and invertebrates differ in their responsiveness to various environmental factors and may provide complementary information on the integrity of a system. Multivariate analyses on an expanded data-set of 40 sites found that pH accounted for the greatest amount of variation in the data and was conducive to the development of a diatom-based pH inference model. / The strongest model was produced using weighted averaging (WA) with classical deshrinking. While the model displayed a high correlation coefficient, the prediction error was also relatively high, probably as a result of the comparatively small and heterogeneous data-set. Incorporation of the data into a larger training set would be likely to improve the predictive ability. Applications for the model include pH reconstructions or use in monitoring programs. The current study has shown that pH is an important variable influencing both invertebrate and diatom community structure in wetlands in the south-west of Western Australia. However, the greater sensitivity of diatoms to pH suggests that they would be the most effective tool for the biological monitoring of pH in wetlands threatened or impacted by acidification. An integrated monitoring program including both diatoms and invertebrates may provide additional information on the impacts of pH decline and the overall integrity of the systems and should be investigated further.

Le thème principal de cette recherche est la remédiation des sols contaminés par des hydrocarbures en utilisant des traitements d'oxydation chimique à pH neutre. Les minéraux à base de fer sont susceptibles de catalyser cette réaction d'oxydation. L'étude concerne donc dans un premier temps la synthèse des minéraux réactifs contenant des espèces FeII et FeIII (la magnétite et la rouille verte) et, dans un second temps, leur utilisation pour catalyser l'oxydation chimique. Les procédés d'oxydation testés incluent l'oxydation de type « Fenton-like (FL) » et de type persulfate activé (AP). La formation de la magnétite et de la rouille verte a été étudiée par des transformations abiotiques de différents oxydes ferriques (ferrihydrite, goethite, hématite et lépidocrocite) mis en présence de cations FeII. La magnétite a été utilisée pour catalyser les oxydations (FL et AP) dans la dégradation des hydrocarbures aliphatiques et aromatiques polycycliques (HAP) à pH neutre. Une dégradation importante des hydrocarbures aliphatiques a été obtenue par ces deux oxydants, aussi bien pour des pétroles dégradés naturellement que pour un pétrole brut. L'oxydation catalysée par la magnétite a également été efficace pour la remédiation de deux sols contaminés par HAP provenant d'anciens sites de cokerie. Aucun sous-produit n'a été observé dans nos expériences d'oxydation. En revanche, une très faible dégradation des hydrocarbures a été observée lorsque les espèces FeII solubles ont été utilisées comme catalyseur. Des expériences d'oxydation ont également été réalisées en colonne. Ces études d'oxydation ont révélé l'importance du type de catalyseur utilisé pour l'oxydation, la disponibilité des HAP dans les sols et l'effet de la matrice du sol. Les résultats suggèrent que la magnétite peut être utilisée comme source de fer pour activer les deux oxydations par Fenton-like et persulfate à pH neutre. Ce travail a de fortes implications sur la remédiation par oxydation chimique in situ des sols pollués par des hydrocarbures / The main theme of this research is the use of reactive iron minerals in the remediation of hydrocarbon contaminated soils via chemical oxidation treatments at circumneutral pH. The contribution of this thesis is two-fold including the abiotic synthesis of mixed FeII-FeIII oxides considered as reactive iron minerals (magnetite and green rust) and their use to catalyze chemical oxidation. Oxidation methods tested in this study include Fenton-like (FL) and activated persulfate oxidation (AP). The formation of magnetite and green rust was studied by abiotic FeII-induced transformations of various ferric oxides like ferrihydrite, goethite, hematite and lepidocrocite. Then, the ability of magnetite was tested to catalyze chemical oxidation (FL and AP) for the degradation of aliphatic and polycyclic aromatic hydrocarbons (PAHs) at circumneutral pH. Significant degradation of oil hydrocarbons occurring in weathered as well as in crude oil was obtained by both oxidants. Magnetite catalyzed oxidation was also effective for remediation of two PAHs contaminated soils from ancient coking plant sites. No by-products were observed in all batch slurry oxidation systems. Very low hydrocarbon degradation was observed when soluble FeII was used as catalyst under the same experimental conditions. Magnetite also exhibited high reactivity to catalyze chemical oxidation in column experiments under flow through conditions. Oxidation studies revealed the importance of catalyst type for oxidation, PAHs availability in soils and the soil matrix effect. Results of this study suggest that magnetite can be used as iron source to activate both Fenton-like and persulfate oxidation at circumneutral pH. This study has important implications in the remediation of hydrocarbon polluted soils through in-situ chemical oxidation