The oxidation of sulfidic mine tailings and subsequent acid and salt accumulation results in acid drainage and poses a severe reclamation problem. The objectives of this study were to quantify the processes leading to these problems and propose feasible solutions. Characterization of 120 sulfidic surface samples, collected from the Sullivan mine tailings ponds, was carried out for dominant physiological groups of microorganisms, sulfur forms, water and acid extractable cations qualitative physical characteristics, pH, conductivity, organic matter and moisture content. Acid tolerant fungi and iron, sulfur and acid tolerant heterotrophic bacteria were enumerated by the most-probable-number technique. Iron bacteria (Thiobacillus ferrooxidans) occurred often and can be implicated as the cause of Fe⁺² oxidation in samples not buffered at near neutral pH values by bases. Sulfur bacteria (thiobacillus species were commonly found and classified as T. thioparus, T. neapolitanus, or T. thiooxidans. A pH-dependent succession of these thiobacilli occurs in the tailings. Acid tolerant heterotrophic bacteria populations were highly correlated with those of the thiobacilli suggesting a symbiotic relationship, particularly in samples with pH >2.5. The numbers of acid tolerant fungi tended to increase proportionally with oxidation, suggesting increased colonization with time. Chemical analysis for major sulfur forms indicates that iron mono- sulfide oxidation is rapid resulting in the formation and persistence of Fe⁺³ (as amorphous Fe oxyhydroxides in mineralogical analysis) and elemental sulfur. Some accumulation of other oxidizable sulfur forms is indicated by the high levels of total oxidizable sulfur. A portion of this sulfur not accounted for by CS₂ extractable elemental sulfur may be present as amorphous elemental sulfur. The oxidation of elemental sulfur and other sulfur intermediates to sulfate is pronounced in the surface 0-2 cm based on the laboratory oxidation of a bulk tailings sample. Mineralogical analysis shows that gypsum is the predominant sulfate containing mineral at basic to slightly acid pH values. Under moderately to strongly acid conditions, jarosite type minerals occurred in high amounts. Mineralogical analysis also showed that the decomposition of basic minerals and chlorite occurred initially, with the dissolution of micas and K-feldspars being less rapid. The absence of detectable kaolinite or other Al silicate residues indicates that alumino-silicate dissolution may be congruent. Mineralogical results showing dissolution of minerals is supported by general increases in water extractable cations (including Fe, Al, Ca, Mg, K and Na) and decreases in these same acid extractable cations as weathering proceeds. These processes ultimately result in a highly oxidized surface in which acid production is slow. It is suggested that erosional processes be inhibited where an oxidized surface exists to prevent the exposure of reduced tailings beneath the surface. Furthermore, steps should be taken to minimize the addition of fresh tailings over oxidized surfaces. The use of correlations between the qualitative physical characteristics texture, structure and color, obtained in this study, can serve as guides to estimating the degree of tailings oxidation in the field. If more precision is required, the colorimetric determination of CS₂ extractable elemental sulfur is suggested, particularly on the more oxidized samples. Proper management of the tailings to maintain present oxidized surfaces should reduce the acid drainage considerably until reclamation is undertaken. The quantification of the changes in tailings properties with increases in weathering can be useful in evaluating reclamation strategies. / Land and Food Systems, Faculty of / Graduate

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This item was digitized as part of the Million Books Project led by Carnegie Mellon University and supported by grants from the National Science Foundation (NSF). Cornell University coordinated the participation of land-grant and agricultural libraries in providing historical agricultural information for the digitization project; the University of Arizona Libraries, the College of Agriculture and Life Sciences, and the Office of Arid Lands Studies collaborated in the selection and provision of material for the digitization project.

One of the environmental concerns associated with mining waste is the contamination of soil. This study addresses the decontamination of soil, particularly of Co and Ni using Berkheya coddii (B. coddii). B. coddii is a hyperaccumulater plant that is able to decontaminate Co and Ni from the contaminated land. The use of B. coddii to decontaminate soil or waste must be based on a cognizance of the complicated, integrated effects of pollutant sources and soil-plant variables. Phytoextraction pot trials using B. coddii were carried out under green house condition, with controlled watering. A contaminated metallurgical waste residue known as Rustenburg Base Mine Refineries waste (RBMR waste soil) collected from Rustenburg while a serpentine (native) soil (N soil) where B. coddii grows naturally was collected from Mpumalanga. The experiment involved the addition of sulfur doses to both soils in order to test whether acidification and higher sulfur availability could enhance the uptake of both Co and Ni by B. coddii. The results indicate that the addition of sulfur from 2.0 to 8.0 g per kilogram decreased pH in both substrates. RBMR waste soil pH was found to have decreased from 7.8 to 7.4 while the N soil pH was found to have decreased from 6.4 to 4.7. The reduction oxidation potential (redox potential) in both substrates was observed to have decreased along with the increase in sulfur dosage. The mean redox potential for RBMR waste soil was found to be 350 mV and 506 mV for the N soil after the addition of sulfur. Conductivity increased along with the increase in sulfur dosage in both substrates. The mean conductivity for the N soil was found to be 961 μS/cm while that of the RBMR waste soil was found to be 1453 μS/cm after the addition of sulfur. The decrease in soil pH was significant (p = 0.00115) in the N soil than RBMR waste soil. Despite the increase in sulfur dosage and decrease in soil pH in both substrates, B. coddii observed growing. Although it was evident that B. coddii is able to grow in the RBMR waste soil, it was observed that the RBMR waste soil limits the root depth of the B. coddii, reducing chances for the roots to penetrate into the ground especially when dry. The RBMR waste soil becomes more compacted than the N soil when dry. It is therefore crucial to ensure that there is enough moisture to allow for the B. coddii being able to survive effectively in the RBMR waste soil. B. coddii plant height in the RBMR waste soil after four months was observed to be in the range of 190 to 200 mm tall. This was found to be less than the height observed for the B. coddii planted in the N soil, which was in the range of 350 to 400 mm. Nonetheless, plants grown in both substrates were able to absorb Ni and Co into their tissues. More Co and Ni were found to have accumulated into the leaf tissues than in other parts of the plant. This could be an advantage since one would harvest only the leaf part or the canopy (shoots) and allow B. coddii to resprout in order to continue taking up more Co and Ni from the same waste substrate to remediation levels that could be stipulated by Government as desirable for the ecosystem and the protection of human health. Although the accumulated Ni and Co can be recovered from biomass, this alone might not provide sufficient economic justification for phytoextraction due to the low concentrations that could be recovered. B. coddii was found to absorb higher concentrations of Co and Ni from the N soil than from the RBMR waste soil. However, the results found in this study may not be conclusive. This could be due to many variables that could control metal uptake which were not investigated. These include mycorrhizal fungi and metal forms in the soil. Moreover, this study was performed in a green house and not in the outdoor environment. Ni is generally toxic to most plants, hyperaccumulators (i.e. B.coddii) contain elements that nullify the toxic effect of nickel, and in this case the accumulated nickel is bound to malate to form a harmless nickel complex which could be absorbed by the plants as nutrients.

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This study consisted of laboratory and greenhouse experiments designed to determine the effect of sulfur waste materials on acidulation and other properties of calcareous soils. The laboratory experiment was conducted in the Soils, Water and Engineering Department, University of Arizona, for a period of nine weeks. Laveen soil (containing 6% CaCO₃) was treated with two levels of Morocco rock phosphate (0, 500 ppm P), and two different waste materials of sulfur, Cake S and Foam S, each with three levels (0, 5000, 10000 ppm). Treated soils were incubated for two periods (three and nine weeks) at 27°C and 66% water holding capacity. The design of the experiment was a complete randomized block with 24 treatments and two replications. Data were evaluated by analysis of variance and multiple means comparison tests for soil pH, soluble phosphorus, and sulfate, and regression analysis for the isotherm. Results showed that Foam sulfur had a greater effect as compared with Cake sulfur on soil pH, soluble phosphorus and sulfate and significantly shifted the isotherm to the right. Rock phosphate had no effect on soil pH and sulfate, but tended to decrease soluble phosphorus and shifted the isotherm to the left as compared with the control. The second experiment was conducted in the greenhouse near the Agricultural Sciences Building, University of Arizona, for a period of 32 weeks starting on August 20, 1979. Two calcareous soils, Pima and Laveen, (2% and 6% CaCO₃, respectively) were investigated with three levels of rock phosphate (0, 250, 500 ppm P), and three sources of sulfur (Cake, Foam and pure sulfur) each at two levels (0, 8000 ppm S). Two levels of super phosphate were used as a standard treatment. The chemical treatments were mixed with the soil and transferred to plastic pots and moistened to 70% water holding capacity, then covered with plastic sheets and incubated for eight weeks. Following the incubation, tomatoes were planted and grown for a six week period. Dry weights were measured only in the Pima soil but were eliminated due to poor stand in the Laveen soil. Barley was planted after the tomato harvest. Tomato and barley plants were irrigated with distilled water until the first harvest, after which barley was irrigated with tap water and CaSO₄ saturated to eliminate sulfur deficiency detected prior to the first harvest. The experiment was a complete randomized block design with 36 treatments and three replications. Data for soils and plants were evaluated by analysis of variance, multiple means comparison test, and regression analysis. From the results of this study the conclusions were as follows: (1) Foam sulfur tended to increase soluble P and Zn, lowered soil pH, and shifted the P isotherm to the right in the soil. Plant P and dry weight were increased more by the Foam S than Cake S and pure sulfur. However, Foam S tended to increase soluble salts more than Cake S and pure S. (2) Cake S also caused an increase in soluble P in the soil, reduced soil pH, and increased plant P and dry weight as well, although the effects were less than with Foam S. (3) Rock phosphate plus sulfur resulted in an increase in soluble P after 32 weeks of application. (4) Soils with low CaCO₃ content, higher organic matter content, and higher cation exchange capacity favored increased oxidation of sulfur to sulfate resulting in increased soluble P and lower soil pH. (5) Linear regression analysis of the P sorption isotherm was carried out by plotting the P remaining in the solution (ppm) on the X-axis versis P sorbed by the soil (ppm); a linear power function resulted. By this relationship, any regression equation can be used to evaluate the P status of a soil and the statistical differences between treatments.

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