Characterization, bioavailability and health risk assessment of mercury in dust impacted by gold mining

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)

Ion exchange resins an functional fibres: a comparative study for the treatment of brine waste water

Magister Scientiae - MScTo improve the adsorption capacity of polyacrylonitrile (PAN) fibres, hydrophilic amidoxime fibres were prepared by subsequent conversion of the cyano groups to an amidoxime group by reacting with hydroxylamine at 80°C at an optimum amidoximation time of 2 hrs. The amidoxime fibre was hydrolyzed/alkali treated in a solution of sodium hydroxide to enhance or improve the adsorption properties. This was followed by characterization of the amidoxime and hydrolyzed fibres using Scanning electron microscopy (SEM); Fourier transform Infrared Spectroscopy (FTIR) and exchange capacity (cationic and anionic). SEM showed that the hydrolysis process made the surface of Amidoxime fibre rougher than that of Polyacrylonitrile fibre. FTIR revealed that the hydrolyzed Amidoxime fibres contained conjugated imine (-C=N-) sequences. Functionalization enhanced the sorption of amidoxime fibres by an increase of 20 % in the cationic exchange capacity. This was achieved by the part conversion of the cyano groups into the carboxylic acid groups. The fibres showed faster kinetics largely due the available exchange sites on the surface of the fibres hence the equilibration was achieved much quicker.South Afric

A scoping study of component-specific toxicity of mercury in urban road dusts from three international locations

This scoping study presents an investigation of the total and bioaccessible mercury concentrations in road dust (RD) from three international urban sites, where a one-off sampling campaign was conducted at each. This was done to address the hypothesis that the matrix in which mercury is found influences its ability to become accessible to the body once inhaled. For that purpose, the samples were analysed for total and pulmonary bioaccessible mercury and the data compared to the chemical structure of individual particles by SEM. The results obtained from this study suggest that a high mercury content does not necessarily equate to high bioaccessibility, a phenomenon which could be ascribed to the chemical character of the individual particles. It was found that the Manchester samples contained more pulmonary soluble mercury species (as determined by elemental associations of Hg and Cl) in comparison to the other two samples, Curitiba, Brazil, and Johannesburg, South Africa. This finding ultimately underlines the necessity to conduct a site-specific in-depth analysis of RD, to determine the concentration, chemical structure and molecular speciation of the materials within the complex matrix of RD. Therefore, rather than simply assuming that higher bulk concentrations equate to more significant potential human health concerns, the leaching potential of the metal/element in its specific form (for example as a mineral) should be ascertained. The importance of individual particle behaviour in the determination of human health risk is therefore highlighted

Adsorptive removal of mercury from acid mine drainage: a comparison of silica and maghemite nanoparticles

<div><p>Mercury adsorption by silica and maghemite nanoparticles (NPs) was studied with the aim of comparing their performance in the remediation of acid mine drainage (AMD) contaminated water. Calculated distribution coefficients (<i>K</i>_d) showed that both NPs are exceptional adsorbents. However, adsorbate coverage per unit area was 30 times higher for maghemite than for silica NPs, despite the latter having a surface area ∼15 times greater. Maghemite adsorbed 75% of available Hg compared to 56% by silica, making it a more efficient sorbent than silica under AMD conditions. Kinetics and isotherm data for both adsorbents were fitted by the pseudo-second-order (<i>R</i>² = 1) and the Freundlich (<i>R</i>² ≥ 0.98) models, implying that adsorption to both NP types was by chemisorption. Adsorption increased with NP concentrations and pH and was enhanced in the presence of manganese and sulfate ions although adsorption to silica was inhibited in 1:2 Hg-to-Mn systems. Importantly, trends in simulated wastewater were replicated in actual AMD-contaminated water samples. This study highlights the fact that properties besides surface area and charge of adsorbents determine adsorbent performance, and superior attributes may not always lead to higher adsorption efficiencies.</p></div