The aim of this thesis is the elaboration of a detailed literature review on the use of ion exchangers for the preconcentration of platinum group metals. This work contains an actual literature review on this issue. In this work you will find information about the current occurrence of platinum metals in the environment, their impact on health, properties, resources and the use. There are also described ways of decomposition, extraction and use of ion exchangers. In the experimental part this thesis deals with optimization of ion exchangers and following application of real samples from the city of Brno.

Background: Platinum group metal (PGM) mining and refining is a large constituent of the mining sector of South Africa and contributes significantly to the gross domestic product. The PGMs include the rare metals platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir) and osmium (Os). During the refining process workers are potentially exposed to various chemical forms of the PGMs via the respiratory and dermal exposure routes. Historically, emphasis has been on respiratory exposure while the extent of skin exposure is still unknown. Among the different forms of PGMs, the salts are potential sensitisers, with platinum being a known respiratory sensitiser. Workers occupationally exposed to platinum and rhodium have reported respiratory as well as skin symptoms. However, it is unknown if these metals in the salt form are permeable through human skin, and whether dermal exposure could contribute to sensitisation. Evidence regarding differences between African and Caucasian skin anatomy and structure, as well as permeation through skin is contradictory, and no information is available on metal permeation through African skin. The in vitro diffusion method has been utilised successfully in occupational toxicology to demonstrate that metals such as chromium, cobalt and nickel, to name a few, permeate through human skin. The permeability of platinum and rhodium has not been investigated previously. Aims and objectives: The research aim was to obtain insight into the permeability of platinum and rhodium through intact human skin and to provide information needed to determine the potential health risk following dermal exposure to these metals. The specific objectives included: (i) to critically review the in vitro diffusion method that is used to determine the permeability of metals through human skin, (ii) to investigate the permeation of potassium tetrachloroplatinate (K2PtCl4) and rhodium chloride (RhCl3) as representative PGM salts through intact human skin over a 24-hour period, (iii) to evaluate the difference in permeability of platinum and rhodium through intact human skin, (iv) to evaluate the difference in permeability of platinum through intact African and Caucasian human skin. Methods: Abdominal skin obtained after cosmetic procedures was obtained from five female Caucasian and three female African donors between the ages of 28 and 52 with ethical approval from the North-West University. Full thickness skin tissue was mounted in a vertical Franz diffusion cell. Skin integrity was tested by measuring the electrical resistance across the skin before and after conclusion of the experiments, using a Tinsley LCR Data bridge Model 6401. The donor solution of 32.46 mg K2PtCl4 in 50 ml of synthetic sweat (pH 6.5), and 43.15 mg RhCl3 in 50 ml of synthetic sweat (pH 6.5) was prepared. The donor solution was applied to the stratum corneum side of the skin and physiological receptor solution (pH 7.35) was added to the receptor compartment. The concentration of the metals in the receptor solution was determined by high resolution inductively coupled plasma-mass spectrometry after extraction at various intervals during the 24 hours of the study. After completion of the study, the skin was rinsed four times to remove any platinum or rhodium remaining on the skin surface. The skin was digested using hydrogen peroxide, nitric acid and hydrochloric acid during different steps to determine the mass of the metals remaining in the skin by inductively coupled plasma-optical emission spectrometry. Results: The comparison of published in vitro skin permeation studies involving metals is impeded by the variations in the experimental design and dissimilarity in the reporting of results. Differences in experimental design included, most noticeably, the use of various donor and receptor solutions, different temperatures wherein the receptor compartment was placed, differences in skin thickness and variations in exposed skin surface areas. The metals considered in the review, namely chromium, cobalt, gold, lead, mercury, nickel, platinum, rhodium and silver, permeate through intact human skin under physiological conditions. Large variations in the permeability results were observed, with the notable differences in methodology as the probable reason. Results obtained from the in vitro experiments indicate that platinum and rhodium permeated through intact Caucasian skin with flux values of 0.12 and 0.05 ng/cm2/h, respectively. The cumulative mass of platinum (2.57 ng/cm2) that permeated after 24 hours of exposure was statistically significantly (p = 0.016) higher than rhodium permeation (1.11 ng/cm2). The mass of platinum (1 459.47 ng/cm2) retained in the skin after 24 hours of exposure was statistically significantly (p < 0.001) higher than rhodium retention (757.04 ng/cm2). The comparison of permeability between two different racial groups indicates that platinum permeated through the skin of both racial groups with the flux through African skin found as 1.93 ng/cm2/h and 0.27 ng/cm2/h through Caucasian skin. The cumulative mass of platinum permeated after 24 hours of exposure was statistically significantly (p = 0.044) higher through African skin (37.52 ng/cm2) than Caucasian skin (5.05 ng/cm2). The retention of platinum in African skin (3 064.13 ng/cm2) was more than twice the mass retained in Caucasian skin (1 486.32 ng/cm2). Conclusions: The in vitro diffusion method is an applicable method to determine skin permeability of metals. However, the experimental design and format of data reporting should be standardised to enable comparison of results from different studies. Platinum and rhodium permeated through intact human skin, with platinum permeation significantly higher. African skin was significantly more permeable by platinum than Caucasian skin. Both platinum and rhodium were retained inside the skin after 24 hours of exposure, possibly forming a reservoir which could contribute to continued permeation through the skin even after removal thereof from the skin. Platinum and rhodium permeated through full thickness skin and thereby could possibly contribute to local skin symptoms such as dermatitis and urticaria found in occupationally exposed workers. By permeating through the upper layers of the skin, these metals could potentially reach the viable epidermis and contribute to sensitisation. / PhD (Occupational Hygiene), North-West University, Potchefstroom Campus, 2015

Background: Platinum group metal (PGM) mining and refining is a large constituent of the mining sector of South Africa and contributes significantly to the gross domestic product. The PGMs include the rare metals platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir) and osmium (Os). During the refining process workers are potentially exposed to various chemical forms of the PGMs via the respiratory and dermal exposure routes. Historically, emphasis has been on respiratory exposure while the extent of skin exposure is still unknown. Among the different forms of PGMs, the salts are potential sensitisers, with platinum being a known respiratory sensitiser. Workers occupationally exposed to platinum and rhodium have reported respiratory as well as skin symptoms. However, it is unknown if these metals in the salt form are permeable through human skin, and whether dermal exposure could contribute to sensitisation. Evidence regarding differences between African and Caucasian skin anatomy and structure, as well as permeation through skin is contradictory, and no information is available on metal permeation through African skin. The in vitro diffusion method has been utilised successfully in occupational toxicology to demonstrate that metals such as chromium, cobalt and nickel, to name a few, permeate through human skin. The permeability of platinum and rhodium has not been investigated previously. Aims and objectives: The research aim was to obtain insight into the permeability of platinum and rhodium through intact human skin and to provide information needed to determine the potential health risk following dermal exposure to these metals. The specific objectives included: (i) to critically review the in vitro diffusion method that is used to determine the permeability of metals through human skin, (ii) to investigate the permeation of potassium tetrachloroplatinate (K2PtCl4) and rhodium chloride (RhCl3) as representative PGM salts through intact human skin over a 24-hour period, (iii) to evaluate the difference in permeability of platinum and rhodium through intact human skin, (iv) to evaluate the difference in permeability of platinum through intact African and Caucasian human skin. Methods: Abdominal skin obtained after cosmetic procedures was obtained from five female Caucasian and three female African donors between the ages of 28 and 52 with ethical approval from the North-West University. Full thickness skin tissue was mounted in a vertical Franz diffusion cell. Skin integrity was tested by measuring the electrical resistance across the skin before and after conclusion of the experiments, using a Tinsley LCR Data bridge Model 6401. The donor solution of 32.46 mg K2PtCl4 in 50 ml of synthetic sweat (pH 6.5), and 43.15 mg RhCl3 in 50 ml of synthetic sweat (pH 6.5) was prepared. The donor solution was applied to the stratum corneum side of the skin and physiological receptor solution (pH 7.35) was added to the receptor compartment. The concentration of the metals in the receptor solution was determined by high resolution inductively coupled plasma-mass spectrometry after extraction at various intervals during the 24 hours of the study. After completion of the study, the skin was rinsed four times to remove any platinum or rhodium remaining on the skin surface. The skin was digested using hydrogen peroxide, nitric acid and hydrochloric acid during different steps to determine the mass of the metals remaining in the skin by inductively coupled plasma-optical emission spectrometry. Results: The comparison of published in vitro skin permeation studies involving metals is impeded by the variations in the experimental design and dissimilarity in the reporting of results. Differences in experimental design included, most noticeably, the use of various donor and receptor solutions, different temperatures wherein the receptor compartment was placed, differences in skin thickness and variations in exposed skin surface areas. The metals considered in the review, namely chromium, cobalt, gold, lead, mercury, nickel, platinum, rhodium and silver, permeate through intact human skin under physiological conditions. Large variations in the permeability results were observed, with the notable differences in methodology as the probable reason. Results obtained from the in vitro experiments indicate that platinum and rhodium permeated through intact Caucasian skin with flux values of 0.12 and 0.05 ng/cm2/h, respectively. The cumulative mass of platinum (2.57 ng/cm2) that permeated after 24 hours of exposure was statistically significantly (p = 0.016) higher than rhodium permeation (1.11 ng/cm2). The mass of platinum (1 459.47 ng/cm2) retained in the skin after 24 hours of exposure was statistically significantly (p < 0.001) higher than rhodium retention (757.04 ng/cm2). The comparison of permeability between two different racial groups indicates that platinum permeated through the skin of both racial groups with the flux through African skin found as 1.93 ng/cm2/h and 0.27 ng/cm2/h through Caucasian skin. The cumulative mass of platinum permeated after 24 hours of exposure was statistically significantly (p = 0.044) higher through African skin (37.52 ng/cm2) than Caucasian skin (5.05 ng/cm2). The retention of platinum in African skin (3 064.13 ng/cm2) was more than twice the mass retained in Caucasian skin (1 486.32 ng/cm2). Conclusions: The in vitro diffusion method is an applicable method to determine skin permeability of metals. However, the experimental design and format of data reporting should be standardised to enable comparison of results from different studies. Platinum and rhodium permeated through intact human skin, with platinum permeation significantly higher. African skin was significantly more permeable by platinum than Caucasian skin. Both platinum and rhodium were retained inside the skin after 24 hours of exposure, possibly forming a reservoir which could contribute to continued permeation through the skin even after removal thereof from the skin. Platinum and rhodium permeated through full thickness skin and thereby could possibly contribute to local skin symptoms such as dermatitis and urticaria found in occupationally exposed workers. By permeating through the upper layers of the skin, these metals could potentially reach the viable epidermis and contribute to sensitisation. / PhD (Occupational Hygiene), North-West University, Potchefstroom Campus, 2015

In this study, a reversed-phase high performance liquid chromatography (RP-HPLC) method has been developed to separate and determine Pt and Pd after formation of their chelates with N,N-diethyl-N&#039 / -benzoylthiourea (DEBT). With the aim of reducing the number of steps in treating the samples, the method developed does not require the elimination of excess chelating reagent before the analysis of metal chelates. The different physical and chemical parameters affecting separation were examined in details. The whole analysis was completed on a C18 column in 16 min at 280 nm, with the mobile phase of acetonitrile-methanol-water (80:10:10, v:v:v) containing 0.20 mol l-1 pH 5.0 acetate buffer at a flow rate of 0.8 ml min-1. Detection limits of the method, based on 3s, were found as 14.2 ug l-1 for Pd and 0.77 mg l-1 for Pt using a 20-ul sample loop. Reproducibility of the method for ten repeated measurements was found as 2.36 % for 0.60 mg l-1 Pd and 2.58 % for 10.0 mg l-1 Pt as % RSD. The proposed method is a rapid, simple and highly selective method for the simultaneous determination of Pt and Pd by HPLC without the need for any interference elimination process.

В работе рассмотрены теоретические аспекты международной конкурентоспособности промышленного предприятия; проанализирована деятельность ПАО «ГМК «Норильский никель» в контексте его международной конкурентоспособности; разработаны предложения по повышению международной конкурентоспособности ПАО «ГМК «Норильский никель». / The paper considers the theoretical aspects of the international competitiveness of an industrial enterprise; analyzed the activities of PJSC MMC Norilsk Nickel in the context of its international competitiveness; proposals were developed to improve the international competitiveness of PJSC MMC Norilsk Nickel.

Thesis (M. Sc.(Geography)) -- University of Limpopo, 2019 / Global production of Platinum Group Metals (PGMs) is dominated by South Africa due to its large economic resources base in the Bushveld Igneous Complex (BIC). PGMs are used in a wide range of high technology applications worldwide including medicinal, industrial and commercial purposes, and its contribution to the Gross Domestic Product (GDP) and creating jobs for many. In an area where mining activities dominate, there are likely to be problems that need effective environmental management approaches, which can be facilitated through legislations. Marula Platinum Mine (MPM) is located in Limpopo province BIC which has the second largest number of mining productivity in South Africa. Environmental legislations have been put in place by the South African government in order to avoid or minimise the footprints caused by PGM mining. This study looked at environmental compliance with solid waste management practices by Marula Platinum Mine (MPM) as guided by Mineral and Petroleum and Resource Development Act (MPRDA) and National Environmental Management Act (NEMA) as well as the environmental impacts of MPM in the surrounding communities. Both primary (questionnaires, field observations and key informant interviews) and secondary (NEMA, MPRDA, journals, reports, pamphlets, internet and books) data was used to address the objectives of the study. Descriptive method and Statistical Package for Social Sciences (SPSS) version 25 were used for the analysis of data. The key research results revealed that MPM was compliant with 65% and 21% partially compliant with solid waste management practices. Only 14% of information on solid waste management practices could not be accessed because MPM is still operational. MPM had also had negative footprints on the surrounding villages such as dust generation and cracks on walls and floors on houses of community members, strikes and increase in the usage of substance abuse. Recommendations of the study are that MPM should address challenges that hinder environmental compliance so as to be 100% compliant with MPRDA and NEMA regulations. MPM should also provide other mitigation measures for blasting of explosives to reduce dust generation and problems of cracks on houses of surrounding village members.

Text in English / The purpose of this study was to establish the vulnerabilities of the security control measures that are being used at Impala Platinum mines and refinery to prevent the theft of Platinum Group Metals (PGMs). It is important to ensure that the security control measures in place are effective and efficient in preventing the occurrence of such theft. The research examined the security risk management approach to the prevention of theft of PGMs and the causes of theft of PGMs by organised crime syndicates operating in South Africa and abroad. The study found that Impala Platinum employees, in collusion with contractors and members of mine security services, are involved in the theft of PGMs. To achieve the goals and objective of the research study, effective security control measures were identified that will help Impala Platinum mines and refinery to overcome the risks and challenges related to the theft of PGMs. / Security Risk Management / M. Tech. (Security Management)