published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Quantitative multielemental analysis using Particle Induced X-ray Emission (PIXE) using 1 and 2 MeV proton bombardment on thin targets has been achieved. The method is based on the calculation of atomic ratios from experimentally determined relative x-ray efficiency curves. Sample preparation techniques involving digestion and homogenous deposition of samples and standards with a minimum of contamination have been investigated. The accuracy of the method has been evaluated using five standard reference materials obtained from the National Bureau of Standards. The elimination of bremsstrahlung associated with the charging effect of non-conducting samples in PIXE analysis has been accomplished using thin carbon foils in the beam path. Applications of the PIXE technique to studies on deep-sea ferromanganese nodules were performed. The utility of PIXE in the analysis of noduoles and in the following of the distribution of a large number of elements through the various stages of a processing scheme were demonstrated.

No description available.

Annual application of N at rates of 118 (118N), 236 (236N), and 354 (354N) kg•ha⁻¹ on 35 year old 'Western Schley' pecan trees during four years had little effect on mineral composition and foliar N. No differences in yield, nut quality, and reproductive characteristics were found. Alternate bearing intensity in four consecutive years was 37, 33 and 28% in 118N, 236N, and 354N, respectively, with a significant linear response. Rates from 118 to 236 kg N•ha⁻¹ satisfy N needs for pecan in irrigated pecan orchard of the southwest of United States. The effect of one-time banding of zinc sulfate (74 kg Zn•ha⁻¹) and zinc-EDTA (19 kg Zn•ha⁻¹) was evaluated over a period of four years on ‘Wichita’ pecans growing in alkaline soil. Significant differences in foliar Zn levels were found one month after application of Zinc-EDTA. Differences also were noted during the next three years on approximately 25% of the sampling dates. Yield, leaflet area, and trunk cross sectional area were not affected. Zinc-EDTA increased Zn uptake by 'Wichita' pecan trees in alkaline conditions during three years. A field study indicated that manure or manure plus Zn increased foliar Zn levels in pecans after two years of annual applications. Manure (24 ton ha⁻¹) plus zinc sulfate (258 kg Zn•ha⁻¹ as zinc sulfate) treatment had the highest foliar Zn levels. No differences were observed in trunk growth, leaf area, leaf weight, nut filling, and yield. Manganese toxicity symptoms are exhibited when leaf Mn levels are higher than 1700 μg•g⁻¹ during the standard date sampling of July and affected reproductive characteristics and leaf and shoot growth. More severe visible symptoms include delayed budbreak and die-back of young shoots. In potted pecan trees, zinc EDTA treated trees had a foliar Zn of 244 μg•g⁻¹, in foliar sprayed trees (eight foliar sprays of a combination of zinc sulfate and UAN32) had 140 μg•g⁻¹, and in control trees had 33 μg•g⁻¹. Soil adsorption isotherms showed that of the three fertilizers evaluated Zn sulfate was adsorbed most strongly by the soil (1.5 mg Zn•g⁻¹ of soil). Soil adsorption from Zn EDTA solutions was insignificant.

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No description available.

No description available.

This thesis provides a detailed evaluation of different environmentally friendly dispersants in invert-emulsion drilling fluids that can be used to drill wells under difficult conditions such as HPHT. The drilling fluid is weighted by manganese tetraoxide (Mn3O4) particles, which have a specific gravity of 4.8 and a mean particle diameter of ca1 micrometers. Manganese tetraoxide has different wetting properties and surface chemistry than other weighting agents. Hence, there is a need to find dispersants for manganese tetraoxide that give reduced sag, reduced rheology, and low fluid-loss at HPHT conditions. This is particularly important for deep wells with narrow operating windows between pore-pressure and fracture pressure gradients. The stricter global environmental regulations mandated the dispersants to be environmentally friendly, e.g. within OCNS group D or E. First, oil compatibility tests and particle settling time experiments were conducted on 31 dispersants. From the experiments, we identified 3 oil-compatible dispersants that gave the longest settling time in base oil and belonged to OCNS group D. We investigated the effectiveness of selected chemicals in dispersing manganese tetraoxide at HPHT conditions. 1.95 and 2.4 S.G. drilling fluid samples were first prepared and tested without any contaminant and then in the presence of rev dust and cement as contaminants. Drilling fluid samples were statically aged at 400 degrees F and 500 psi for 16 hours. Sag and rheological measurements were taken before and after aging to determine the effect of HPHT conditions on fluid properties. Then, HPHT dynamic filtration tests were done at 500 psi differential pressure and 300 degrees F to determine HPHT dynamic fluid-loss. We have found that one of the dispersants (nonionic) gives low rheology and reduced sag before and after static aging. It also gives the lowest fluid-loss of the selected dispersants. For 2.4 S.G. fluid without contaminants, 10-minute gel strength was reduced from 50 to 32 lb/100 ft^2, plastic viscosity from 37 to 25 cp, sag from 0.249 to 0.135 lbm/gal, and fluid-loss was reduced from 44.4 to 39.6 cm^3 with the addition of dispersant. This dispersant prevents agglomeration of particles, thereby reducing fluid rheology, sag, and fluid-loss.

Aims and objectives: The general aim of this study was to determine the personal respiratory exposure and biological monitoring of manganese (Mn) present in welding fumes as well as its neurological influence on welders. The objectives of this study were: (i) to assess the respiratory exposure of welders to Mn present in welding fumes; (ii) to assess the biological Mn load of welders via the use of nail clippings; (iii) to establish possible correlations between respiratory exposure to Mn and its presence in nail clippings, and (iv) to determine the possible difference in finger dexterity and coordination between Mn exposed welders and a control group. Methods: A gravimetrical method was used to determine the respiratory exposure of welders. A cassette containing a 0.8-μm, cellulose ester membrane filter, attached to the side of a welding helmet provided, was connected via a stainless steel fitting to the inside (respiratory zone) of the helmet. Chemical analysis (metal content) of the welding fumes was done according to the NIOSH 7300 method, using Inductively Coupled Argon Plasma, Atomic Emission Spectroscopy (ICP-AES). Nail clippings were collected at the beginning and end of the study to determine the Mn level in the nails in both welders as well as paired controls. The nails were deposited into small, plastic vials and also analysed according to the NIOSH 7300 method. A Perdue pegboard and mirror drawing test was also conducted to determine the influence of Mn exposure on finger dexterity and hand-eye coordination of welders. Results: Mn exposure in the welding fumes did not exceed the occupational exposure limit – recommended limit (OEL-RL) (1 mg/m3) of the Regulations for Hazardous Chemical Substances (RHCS), although two of these exposures exceeded the action level (0.5 mg/m3). No statistical significant correlations were found between the Mn respiratory exposure and the Mn found in the nails of the welders. Mn in the nails of exposed welders was statistical significantly higher (p = 0.003) than that of controls. The only statistical significant differences found in the motor function tests between the controls and welders were the test which was done by using their non-dominant hand in the beginning of the study (p = 0.016) and when the non-dominant hand values were pooled (p = 0.012). The usage of both hands simultaneously showed results that leaned toward statistical significant decrease of the welders compared to the control subjects (p = 0.090). In all these cases the controls inserted more pins than the welders. Only one moderately positive correlation (r = 0.612; p = 0.02) was found between Mn in the welding fumes and the number of errors made in the mirror drawing coordination test done by the welders. Discussion and Conclusions: The Mn in the nails of the control group was significantly lower than the Mn in the nails of the welders. This indicates that Mn respiratory exposure may influence Mn body burden although no correlation between Mn in welding fumes and Mn in nails were found. Nail Mn may serve as a biomarker to determine Mn body burden. Only the use of the non-dominant hand of the control subjects compared to the welders showed a significant decrease in finger dexterity of the welders. The moderately positive association between the Mn in the welding fumes and the number of errors made in the mirror drawing coordination test done by the welders indicates that with an increase in Mn in welding fumes, a decrease in hand-eye coordination will occur. It can be concluded that welders’ finger dexterity and hand-eye coordination may be influenced by the exposure to Mn in the welding fumes. / Thesis (MSc (Occupational Hygiene))--North-West University, Potchefstroom Campus, 2013