A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Master of Science, 2017 / Six different plant species that grow in a natural wetland impacted by old gold mining and other industrial activities were randomly selected with surface sediments. These included: Cyperus eragrostis (Nutgrass), Datura stramonium (Jimson weed), Melilotus alba (White sweetclover), Panicum coloratum (Blue panicgrass), Persicaria lapathifolia (Pale smartweed) and Phragmites australis (Common reed). These were used to investigate the levels of mercury in the wet and dry seasons, as well as to evaluate which of the species could be utilized for the remediation of mercury contaminated areas. The results obtained indicated that metal contamination could be determined from sediments and plant tissues. The pH values of the sediment samples were mostly neutral to slightly acidic and the redox potential was high in the wet season. On the other hand the dry season was characterised by very acidic and moderately oxidizing conditions. In summer all six plant species had higher concentration of HgT in sediments, whereas in winter the levels of HgT were elevated in the aerial tissues of the plants. The mercury accumulation patterns differed according to individual plant species and seasonality. Seasonal differences were significant but generally the MeHg concentrations in the wet season were higher in both surface sediments and plant tissues. Mercury methylation differed between species but concentration of MeHg was in general higher in plants with high concentration of mercury in sediments. The conversion of bioavailable HgT seemed more pronounced in tissues of the plants sampled in the wet season unlike those sampled in the dry season. Generally bioaccumulation factors were less than 1 in both the wet and dry seasons for all the plant species indicating that Hg was mainly retained in sediments. The translocation factor values were greater than 1 meaning metals were accumulated fundamentally in aboveground tissues for the plants D. stramonium, P. lapathifolia, P. coloratum and C. eragrostis in both the wet and dry seasons. The small bioaccumulation factors combined with translocation factor values greater than 1 were an indication that mercury present in the sediments was not the only source of mercury for the plant species growing in a contaminated environment. For P. australis the translocation of mercury was heavily influenced by seasonality, however this was not the case with M. alba. All the selected plant species demonstrated the capacity to grow in a heavily contaminated area, where P. australis and M. alba seemed to have developed an exclusion strategy to deal with toxic heavy metals therefore suitable for phytostabilisation. D. stramonium, P. lapathifolia, P. coloratum and C. eragrostis on the other hand exhibited characteristics of plants that can be successfully used for phytoextraction and phytovolatilization. / XL2018

A Thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Doctor of Philosophy 2015. / Gold mining in South Africa has been the backbone of the economy for many years. With it came economic well-being, the growth and development of satellite towns, cities and metropolitan cities, e.g. Johannesburg-a place of gold. Unfortunately, it also came with adverse effects, most of which are now evident, after a century of mining, with little or no regard for pollution prevention or any form of remediation. Of interest, in this study, is the presence of tailings storage facilities (TSFs) found within the residential areas, in close proximity to commercial district and industry, having been built around them. Currently, some 270 TSFs lie dormant, pregnant with vast number of toxic heavy metals from the initially low efficient but selective gold processing techniques. This led to the deposition of the sand dumps, with high sulphur, iron, chromium, cadmium, arsenic, and mercury amongst other toxic metals. Exposure to oxygen, and water, the pyrites were oxidized and formed acid mine drainage (AMD), which resulted in the leaching out all toxic heavy metals into ground water and surface water causing serious water pollution and environmental degradation. Due to the low efficient gold processing technique, some gold amount was discarded together with the tailings materials. The reprocessing of these dumps led to the generation of dust, which is easily distributed over large areas of land. The unrehabilitated, semi-rehabilitated, and the abandoned TSFs contributed to all forms of pollution, majorly, windblown dust from unprotected tops and sides, AMD leaching toxic heavy metals. In this study, mercury, one of the most toxic elements found within the vast TSFs was determined. This was carried out as part of a larger environmental impact assessment on the effects and scale of pollution from the gold mining in the Witwatersrand. The study area consisted of the greater Johannesburg area, covering commercial business district (CBD), the industrial areas (Aeroton, City Deep, Germiston, Selby, Springs), and the residential areas (Alberton, Boksburg, Centurion, Germiston, Greenside, Sandton, Springs). Dust samples were collected from paved surfaces in the streets, and accessible buildings, were sieved into three sieved into three fractions (PM100, PM50, PM25), and most of the work focused on the smallest size fraction (PM25) in order to study impact of inhalable and respirable dust. Three sequential extraction procedures (modified BCR-the European Community Bureau of Reference, selective sequential procedure (SSE), and novel sequential extraction procedure (n-SEP)) were applied for partitioning and evaluating the mobility, availability and persistence of mercury in urban dusts. Bioavailability of mercury was assessed by leaching dust with artificial gastric and lung fluids which mimicked body conditions. Contamination levels were assessed based on the enrichment factor (EF), contamination factor (Cf) and geoaccumulation index (Igeo) were calculated to further assess the environmental risk and provide a preliminary estimate of the main sources of mercury in street dust. Non-carcinogenic effects and carcinogenic effects due to exposure to urban street dusts were assessed for both children and adults. The total mercury (HgTOT) ranged from 269 to 1350 μg kg-1. In the PM25 size fraction, mercury exhibited the following decreasing order of HgTOT: industrial area > CBD > residential area. This order shows that the HgTOT concentration in the street dust decreased with increased distance from the TSFs. The highlight was that the highest HgTOT was reported in industrial areas next to the TSFs, tailings reprocessing areas, and tailings footprints. Furthermore, in residential areas grossly affected by TSFs and tailings reprocessing, reported high HgTOT values similar to those reported for industrial samples. These results indicated that the presence of TSFs were largely responsible for the mercury found in the dust. The results from the characterization of the dust showed a large concentration of fine particulate matter, with the characteristically high quartz (74 – 98 wt. %), and minor minerals phases such as chloritoid, chlorite, K-feldspar, jarosite, mica, muscovite, pyrite, and pyrophyllite, all below 10 wt. %. These have been known to enrich trace metals, hence a high concentration of mercury. The close proximity of the tailings to the communities led to the determination of bioavailability of mercury from dust. The bioaccessible Hg extracted by lung fluid (up to 3% of HgTOT) was higher than that of gastric fluid (up to 1% of HgTOT) and was related to the mobile pool of Hg in dust. This suggests that human exposure to Hg in dust via inhalation is greater than that via the gastric tract. These values were very similar to the values obtained from water soluble phase in the sequential extraction procedure (average 1.4% of HgTOT). This indicated that these fluids were able to extract the most bioavailable fraction of Hg, which is responsible for most of the transformation reactions involving mercury. Contamination assessment factor was carried out to classify the pollution levels and indicate whether they are from natural or anthropogenic sources. Based on the EF, Cf, and Igeo, 70, 82, and 84% of the street dust samples were classified as heavily enriched, very highly contaminated, and strongly polluted by mercury, respectively, indicating that they are of anthropogenic origin. The human health risk model was useful in identifying the areas of health risks from exposure to mercury pollution. It showed that children were more vulnerable than adults when exposed to mercury in dust via ingestion. The cancer risk for exposure to As, Cd, and Cr by both children and adults was significantly high for oral ingestion of dust. Cr (VI) was the highest contributor followed by As and lastly Cd. For inhalation pathway, the possibility of developing cancer after a lifetime exposure was low and below the acceptable limits (10-6).

[pt] Foi estudada a determinação de mercúrio em gasolina pela técnica do vapor frio, com redução em meio orgânico e de solução de três componentes (microemulsão). Foram utilizadas várias metodologias empregando a técnica de geração de vapor frio e detecção em espectrômetro de absorção atômica, a saber: determinação direta em gasolina; determinação direta em gasolina estabilizada na forma de microemulsão, com e sem pré-concentração em rede de ouro; e determinação direta em gasolina estabilizada na forma de microemulsão utilizando uma armadilha para vapores de gasolina antes da pré-concentração em rede de ouro. Analisando os resultados, foi verificado que a determinação de mercúrio em gasolina estabilizada na forma de microemulsão fornece medidas mais repetitivas do que em gasolina in natura; além disso, foi observada a necessidade de utilizar pré-concentração em rede de ouro, devido aos baixos níveis de mercúrio em gasolina; entretanto, foi detectado que os vapores de gasolina envenenam o ouro. Dentre as armadilhas estudadas para evitar o envenenamento do ouro, foi escolhida a armadilha com solução de K2Cr2O7/H2SO4, na qual, os vapores rovenientes do frasco de reação foram borbulhados e o Hg0, oxidado; posteriormente, a solução foi reduzida com SnCl2/ H2SO4 e os vapores enviados para a rede de ouro. Assim, os resultados indicaram que o método para determinação de mercúrio total em gasolina, no qual o mercúrio é reduzido diretamente da gasolina como microemulsão, utilizando armadilha de K2Cr2O7/H2SO4 antes da pré-concentração em ouro, com detecção por CV-AAS, é recomendado. Após uma otimização multivariada, curvas analíticas apresentaram coeficientes de correlação de até 0,9999 com uma massa característica correspondente de 2ng de mercúrio. O limite de detecção obtido por este método foi de 0,10 ng/mL (0,14 ng/g). / [en] The mercury determination in gasoline by cold vapor and AAS, with reduction in organic liquids and in solution of three components (microemulsion)was studied. Some methodologies were used, with cold vapor generation and atomic absorption spectrometer, to know: direct determination in gasoline; direct determination in gasoline stabilized as microemulsion, with and without preconcentration in gold; and direct determination in gasoline stabilized as microemulsion using a trap for gasoline vapors before the preconcentration in gold. Analyzing the results, it was verified that the measurements from the gasoline stabilized as microemulsion supplies more repetitive readings than the gasoline in nature; moreover, it was observed that is necessary to use preconcentration in gold, due to the lower mercury levels in gasoline; however, it was detected that the gasoline vapors poison the gold. Amongst the studied traps to prevent the poisoning of the gold, the trap with solution of K2Cr2O7/ H2SO4 was chosen, in which, the vapors proceeding from the reaction bottle had been bubbled and the Hg0, oxidated; later, the solution was reduced with SnCl2/ H2SO4 and vapors sent to the gold. Thus, the results had indicated that the method for total mercury determination in gasoline, in which the mercury is reduced directly from the gasoline as microemulsion, using the K2Cr2O7/H2SO4 trap before the preconcentration in gold, with CV-AAS detection, is recommended. After multivariate optimization analytical curves showed coefficients of correlation as good as 0.9999 with a corresponding characteristic mass of 2ng of mercury. The limit of detection obtained for this method was 0.10 ng/mL (0.14 ng/g).

Peats and organic-rich soils are a key part of the global carbon (C) cycle due to their sequestration and storage of atmospheric C as organic matter. Atmospheric deposition as a result of human activities has led to increased inventories of lead (Pb) and mercury (Hg) in UK peats and organic-rich soils. Ombrotrophic peat bogs, which receive all their nutrients and pollutants from the atmosphere, provide a historic record of Pb and Hg deposition within their solid phase. Organic-rich forest soil systems can also act as sinks for anthropogenic Pb but vertical transport of Pb can distort these temporal records. The long-term outlook may, however, be affected by processes which lead to decomposition of organic matter e.g. drying out of peatlands and soils due to climatic change, since these may release Pb into the aqueous phase and volatile Hg to the atmosphere. The associations and speciation of Pb and Hg within peats and organic-rich soils are not well understood but are key to understanding both the potential for release of these pollutants into other environmental compartments and the risks to ecosystems and human health posed by such a release. Investigation of 4 sites in central Scotland showed that, depending on vertical depth, ~40-99% of Pb in ombrotrophic peat was in association with large (0.22 μm – 100 kDa) humic molecules. Near-surface regions where intact plant material had not yet undergone complete humification showed the lowest proportion of Pb-humic association. Historical Pb deposition was retained to similar degrees across each site with recorded inventories to 1986 of 0.340-0.561 g m-2. However, perturbation of the 206Pb/207Pb isotope ratio profile at Glentress forest indicated that limited migration of petrol-sourced Pb may be occurring. Similarly, perturbation of the 210Pb profile at Auchencorth Moss, in addition to discrepancies in the apparent time period in which peak Pb deposition occurred, indicated that Pb may also be subject to migration within this ombrotrophic system. With respect to Hg, between-site differences in speciation were observed. For example, Hg2+ represented < 25% of the total Hg species in the top 10 cm of solid phase ombrotrophic peat but > 50% of the total in forest soil. In contrast, aqueous phase Hg was entirely in the inorganic form across all sites. The occurrence of a solid phase [Hg] peak in layers corresponding to the ~1955 height of coal burning, in addition to the narrow range of peatland Hg inventories to 1950 (2.20-3.23 g m-2) provide evidence that Hg deposition records may be maintained in organic-rich systems to a greater degree than previously assumed. Differences observed in the associations of Pb and the speciation of Hg between the surface vegetation of ombrotrophic bogs and the underlying peat suggests that plants play an integral role in the biogeochemical behavior and sequestration of Pb and Hg in these terrestrial systems.

Mercury (Hg) has always been a serious risk to the environment and human health. It is a very common contamination in petroleum industry, which may lower product quality, threaten operation safety and worker’s health even at a very low concentration. Consequently the detection of mercury is very necessary. Gold is widely used as sensing material of mercury because it has a specific affinity with mercury and the adsorption of mercury changes characteristics of gold such as resistivity and effective mass density. In this thesis, common methods for sensing mercury vapor concentration were summarized and a surface acoustic wave (SAW) sensor utilizing the adsorption of mercury on gold electrodes was proposed for 1 μg/m3 level low concentration mercury vapor detection. The working principle of SAW sensor was studied and finite element method models were built to optimize the sensor design. The influence of several physical structure parameters such as electrode width and pitch on the sensor sensitivity and response time were studied using the simulation model. According to the simulation results a prototype of SAW sensor was designed and fabricated. The sensor was then analyzed with network analyzer and tested with mercury vapor. Preliminary results were presented and analyzed in this work. Finally potential future work was proposed and discussed.

This study examined biological mercury removal from soil using mercury-resistant bacteria in soil microcosms. Mercuric chloride was used to artificially contaminate Kidman soil to mercury concentrations of 5 ppm and 10 ppm. Soil moisture content was maintained at three levels, 20%, 30% and 50%. Mercury resistant-bacteria were added to soil samples and the mercury removal rate was compared to control samples without added bacteria. Mercury removal rate was initially enhanced by the addition of bacteria. After 30 days, no difference was observed between samples and controls with initial mercury concentration of 5 ppm when soil moisture content was 20%. At an initial mercury concentration of 10 ppm, soil samples had less mercury remaining than controls after 30 days. Autoclaved soil had a decreased mercury removal rate compared to soil not autoclaved. Addition of nutrient (sucrose) did not increase the mercury removal rate. A slurry-type bioreactor was found to be more efficient than a non-stir type. After 30 days of continuous stirring, 85-90% of the added mercury (10 ppm) was removed, while under the same conditions except no stirring, only around 60% of the mercury was removed. Overall, biological detoxification of mercury from contaminated soil can be achieved by using a slurry-type bioreactor with additon of mercury-resistant bacteria.

This thesis carefully investigates some of the limitations of existing methods for atomic spectroscopic determination of mercury, selenium and arsenic in biological and environmental materials. In particular the need for adequate sample preparation to ensure reliable atomic spectroscopic determination of these metalloids was demonstrated extensively. The thesis evaluates four most commonly used wet digestion methods for the accurate determination of mercury in biological and environmental materials by cold vapour atomic absorption spectroscopy. Excellent recovery efficiencies were obtained with this digestion mixture in fish homogenate, horse kidney, soil, canned fish and hair samples for inorganic and organic mercury. The suitability of the digestion method for the reliable determination of mercury in soil, hair and canned fish samples was also demonstrated. Mercury levels in these samples were found within normal acceptable range. The thesis outlines a new simple procedure for overcoming the loss of mercury due to sample charring. It also described a new sample ultrasound low temperature wet digestion method for biological and environmental materials. The main advantage of this approach over other conventional methods is its ability to release all mercury in inorganic form from biological and environmental samples at much lower temperatures than reported earlier / Doctor of Philosophy (PhD)

<p>Mercury is the only metal that is in liquid form at room temperature and it has over the years been used in various combinations to extract gold, in measuring devices, medicaments, paper industry, batteries and fluorescent lights as well as in dentistry as dental amalgam. Dental amalgam is a mixture of 50 % mercury and 50% of an alloy consisting of silver, tin, copper and zink particles and has been used in dentistry for many years. The environmental effect of mercury release into the sewer from dental practices and clinics, and the inability of the wastewater treatment plants to remove it from the sludge lead to the introduction of amalgam separators in Sweden in 1980. The ISO standard 11143 regulates the efficacy of the amalgam separators, which should be at a 95% level, but is based on a laboratory test rather than a clinical evaluation.</p><p>This study looks at the available amalgam separators in use in four areas of Sweden, Uppsala, Stockholm, Östergötland and Skåne and compares their clinical efficiency. The clinical efficiency ranged between 75 to 95%, with most units below the 90% mark. In Östergötland a new improved separator is being tried, the Capere unit, which is based on finely ground pine bark treated with a chelator sensitive to all metals and used in conjunction with a cotton filter and a regular amalgam separator. This was shown to be superior to the other separators, with a 99, 9% removal of even the smallest amalgam particles and ionic mercury from the wastewater before leaving the clinic. Otherwise, combining more than one amalgam separator of the brands available on the Swedish market did not improve the efficiency of them.</p>

Henry R. Hirsch. / "October 15, 1961." "...presented to the Department of Physics, Massachusetts Institute of Technology, in partial fulfillment of the requirements for the degree of Doctor of Philosophy." "Reprinted from Journal of the Optical Society of America, vol. 51, no. 11, 1192-1202, November, 1961." / Army Signal Corps Contract DA36-039-sc-78108, Department of the Army Task 3-99-20-001 and Project 3-99-00-000.

Adrian C. Melissinos, Sumner P. Davis. / "November 10, 1958." "Reprinted from The physical review, v.115, no.1, July 1, 1959" / Includes bibliographical references. / Army Signal Corps Contract DA36-039-sc-78108. Dept. of the Army Task 3-99-20-001 and Project 3-99-00-000.