Cette thèse s’intègre dans l’axe 3 du programme « ETIAGE » qui a associé pendant quatre ans (2010-2014) la Lyonnaise des Eaux, la Communauté Urbaine de Bordeaux (CUB), l’AEAG, et le FEDER, région Aquitaine avec l’université de Bordeaux, le CNRS et IRSTEA. L’objectif de l’axe 3 était de documenter les apports métalliques du bassin versant de la CUB aux eaux de la section garonnaise de l’estuaire de la Gironde. Ce vaste estuaire européen est l’un des plus turbides au monde, avec en période d’étiage la présence devant Bordeaux d’une zone de turbidité maximum (ZTM, >1 g.L-1 de MES en surface) qui transporte des particules estuariennes et des éléments traces potentiellement toxiques. Les travaux de cette thèse se sont focalisés sur les apports métalliques via le fonctionnement des deux principales stations d’épuration (STEP) de la CUB. De ce fait, l’objectif de cette recherche est d’analyser en détail les concentrations, les flux et la réactivité de huit contaminants métalliques définis comme prioritaires par l’Union Européenne Cr, Cu, Cr, Hg, Ni, Pb, Zn, As, et le contaminant émergent Ag, des STEP de la CUB. Les taux d’abattement calculés sont importants, de l’ordre de 80 % pour la majorité des métaux, essentiellement lors de l’étape de décantation. Malgré cette efficacité, les apports en éléments traces métalliques (ETM) urbains via les STEP pendant les épisodes orageux et dans des situations de faible débit peuvent augmenter les concentrations et les flux dans l’estuaire fluvial de la Gironde et ainsi avoir des conséquences sur la qualité des eaux estuariennes. Les concentrations en Ag sont supérieures aux concentrations normales de bruit de fond dans l’estuaire fluvial de la Gironde, faisant de Ag un excellent traceur urbain. Le traitement dans les STEP concentre les ETM dans les boues extraites dont les concentrations métalliques restent en-deçà des normes d’épandage. Toutefois, les concentrations en éléments traces peuvent être de 15 (Ag) à 30 (Cu) fois supérieures aux concentrations naturelles du bruit de fond en raison du fort enrichissement des boues en Hg, Ag, Cr, Cu et Zn. De plus, environ 70 % des éléments traces Cd, Ag, Pb, Cu, et Zn contenus dans ces boues sont potentiellement biodisponibles et peuvent avoir un impact néfaste à court et long terme sur les environnements récepteurs. En raison de l’augmentation prévisible de la démographie des villes côtières, les résultats de cette étude participent à l’élaboration de nouveaux concepts et outils (récupération, recyclage, valorisation) pour améliorer quantitativement et qualitativement les rejets urbains solides et liquides. / This study is a part of the third axis of the « ETIAGE » project, a four year collaboration (2010-2014) between the Lyonnaise des Eaux, the Communauté Urbaine de Bordeaux (CUB), AEAG, and FEDER, Aquitaine region with the University of Bordeaux, CNRS and IRSTEA. The axis 3 objectives were to document the trace metal inputs from the CUB watershed into the waters of the Garonne section of the Gironde estuary. The Gironde Estuary is one of the largest macrotidal and highly turbid estuaries in Western Europe characterized by the presence of a strong maximum turbidity zone (MTZ) with high suspended particulate matter (SPM) concentrations (>1 g.L-1 in surface water) transporting estuarine particles and potentially hazardous trace elements. This study has focused on the trace metal inputs from the two main wastewater treatment plants (WWTP) of the CUB. The objective of this research was therefore to study in detail the daily concentrations, fluxes, and dynamics of 8 EU priority contaminants Cr, Cu, Cr, Hg, Ni, Pb Zn, As, and the emerging contaminant Ag from the WWTPs in the CUB. The calculated removal rates are significant, around 80 % for the majority of metals, mainly as a result of the decantation phase. Despite this high removal efficiency, during periods of heavy rainstorms and low river discharges, the urban metal inputs via the WWTPs may still significantly increase metal concentrations and fluxes in the fluvial Gironde Estuary impacting water quality. In addition, the WWTP fluxes and concentrations of Ag exceeded common background concentrations in the Gironde fluvial estuary, making it an interesting urban tracer. The treatment within the WWTPs concentrates the trace metals in the sludge, yet, metal concentrations remained below legal norms for agricultural use. However, the analysis of WWTP sludge revealed that trace element concentrations are 15 (Ag) and 30 (Cu) times higher than natural background concentrations with high enrichment of Hg, Ag, Cr, Cu and Zn with over 70 % of Cd, Ag, Pb, Cu, and Zn being potentially bioavailable. Therefore, with increasing urban pressure on environmental quality, these results support the need for the development of efficient water quality monitoring tools.

No description available.

No description available.

1. ŽODYNAS, SIMBOLIAI IR SANTRUMPOS Alopecia – alopecija, plaukų iškritimas, jų netekimas, slinkimas, plikimas, plikumas, plikis Alopecia areata – lizdinis, židininis plaukuotosios galvos dalies ar kitų kūno vietų (blakstienų, antakių, gaktos, pažastų ir kt.) plaukų iškritimas, plikimas Alopecia barbae – vyrų barzdos ir ūsų plikimas Alopecia diffusa – difuzinis, išsklaidytas plikimas Alopecia totalis – visų galvos plaukų netekimas, plikumas, plikis Alopecia universalis – visiškas ar dalinis galvos plaukų netekimas, lydimas dalinio ar visiško kitų kūno vietų plaukų iškritimo; plikumas, plikis Anti–TPO – antitiroidiniai mikrosominiai antikūniai Ca – kalcis Ca2+ – dvivalentis kalcis Cd – kadmis Cr – chromas Cu – varis ENG – eritrocitų nusėdimo greitis FT4 – laisvas tiroksinas Hg – gyvsidabris KMU – Kauno medicinos universitetas Me – mikroelementas Mg – magnis Mn – manganas P – fosforas Pb – švinas PSO – Pasaulinė sveikatos apsaugos organizacija PTH – parathormonas SD – standartinė paklaida TSH – tirostimuliuojantis hormonas Zn – cinkas 2. ĮŽANGA Alopecija yra nepiktybinis, uždegiminis, autoimuninis ir labai neprognozuojamas žmonių ir gyvūnų plaukų slinkimas ir plikimas. Manoma, kad iki 2 proc. visos žmonijos populiacijos gali bent kartą gyvenime nuplikti ar slinkti plaukai (Barahamani ir kt. 2002, Sahn 1995). Galimas galvos, antakių, blakstienų, barzdos ar kitų plaukuotų kūno vietų plaukų slinkimas ar plikimas. Šia liga gali sirgti įvairaus amžiaus abiejų lyčių visų... [to full text]

The methods of analysis with a focused ion beam, commonly termed as nuclear microscopy, include quantitative physical processes like PIXE and RBS. The element concentrations in a sample can be quantitatively mapped with a sub-micron spatial resolution and a sub-ppm sensitivity. Its fully quantitative and non-destructive nature makes it particularly suitable for analysing biological samples. The applications in biomedical research are manifold. The iron overload hypothesis in Parkinson\\\'s disease is investigated by a differential analysis of human substantia nigra. The trace element content is quantified in neuromelanin, in microglia cells, and in extraneuronal environment. A comparison of six Parkinsonian cases with six control cases revealed no significant elevation in iron level bound to neuromelanin. In fact, a decrease in the Fe/S ratio of Parkinsonian neuromelanin was measured, suggesting a modification in its iron binding properties. Drosophila melanogaster, or the fruit fly, is a widely used model organism in neurobiological experiments. The electrolyte elements are quantified in various organs associated with the olfactory signalling, namely the brain, the antenna and its sensilla hairs, the mouth parts, and the compound eye. The determination of spatially resolved element concentrations is useful in preparing the organ specific Ringer\\\'s solution, an artificial lymph that is used in disruptive neurobiological experiments. The role of trace elements in the progression of atherosclerosis is examined in a pilot study. A differential quantification of the element content in an induced murine atherosclerotic lesion reveals elevated S and Ca levels in the artery wall adjacent to the lesion and an increase in iron in the lesion. The 3D quantitative distribution of elements is reconstructed by means of stacking the 2D quantitative maps of consecutive sections of an artery. The feasibility of generating a quantitative elemental rodent brain atlas by Large Area Mapping is investigated by measuring at high beam currents. A whole coronal section of the rat brain was measured in segments in 14 h. Individual quantitative maps of the segments are pieced together to reconstruct a high-definition element distribution map of the whole section with a subcellular spatial resolution. The use of immunohistochemical staining enhanced with single elements helps in determining the cell specific element content. Its concurrent use with Large Area Mapping can give cellular element distribution maps.

Plants are able to take up and accumulate certain environmental contaminants such as heavy metals. When the plants are ingested by man, these contaminants are transferred along the food chain. Due to the poorly regulated medicinal plant trade in South Africa, many opportunities exist for heavy metal contamination of medicinal plants namely contaminated harvest sites as well as poor drying, processing, storage, transport and manufacturing conditions. The concentrations of five heavy metals (As, Cd, Co, Ni, Pb) and six microelements (B, Cu, Fe, Mn, Mo, Zn) were determined in some commonly used South African medicinal plants obtained from street markets. Elemental content was determined using inductively coupled plasma optical emission spectrophotometry (ICP-OES). Some of the medicinal plant samples investigated contained As and Cd at levels exceeding the World Health Organization limits of 1 and 0.3 mg kg-1 respectively. Lead and Ni were detected in all the samples. Elevated Fe and Mn levels were recorded in certain plant species. The results revealed multiple metal contamination in some medicinal plant parts sold in local markets and is thus grounds for concern. The effects of Cd application on growth parameters of some medicinal plant species belonging to the Hyacinthaceae (Albuca setosa, Eucomis autumnalis, Eucomis humilis, Merwilla plumbea) gave insight into heavy metal accumulation and distribution in these species. Application of Cd at 5 mg l-1 over a 12 week period reduced growth in A. setosa. The medicinally used A. setosa bulbs accumulated 37 mg kg-1 Cd after 12 weeks. Cadmium application at 2 mg l-1 over a six week period had no effect on growth parameters of E. autumnalis or E. humilis. However, a substantial difference in total Cd accumulation was detected in the plants (40.2 and 15.3 mg kg-1 respectively). Cadmium application at 2 mg l-1 significantly reduced the fresh weight of leaves, bulbs and roots of M. plumbea. Although most of the Cd was stored in the roots, the medicinally used bulbs accumulated up to 11.6 mg kg-1 when applied at 10 mg l-1. The antagonistic effect between Cd and Zn treatments and their effect on micronutrient distribution in M. plumbea were investigated. Five treatments were evaluated: (1) Hoagland’s nutrient solution (HS) (control) (2) HS + Cd 2 mg l-1 (single) (3) HS + Cd 2 mg l-1 + Zn 50 mg l-1 (combination) (4) HS + Cd 2 mg l-1 + Zn 100 mg l-1 (combination) (5) HS + Cd 2 mg l-1 + Zn 150 mg l-1 (combination). Cadmium readily accumulated in leaves, bulbs and roots of M. plumbea when supplied at 2 mg l-1. Zinc at 50 mg l-1 led to increased Cd accumulation. However, further increases in Zn concentration showed an antagonistic effect of Zn on Cd uptake and accumulation. Thus, increasing Zn levels in soils may be favourable for reducing toxic Cd accumulation in M. plumbea plants. Boron was not significantly affected by the addition of Cd to the media. However, with an increase in Zn, leaf B content increased while the B content in the bulbs and roots decreased. Copper and Mo levels were not significantly affected by treatments with Cd or Cd/Zn combinations. Compared to the control, Cd and Cd/Zn applications caused an increase in Mn content in leaves, bulbs and roots. Iron levels of M. plumbea were not significantly affected by Cd in the media. However, with an increase of Zn in the Cd-containing media, Fe content in the leaves, bulbs and roots increased. Tulbaghia violacea is one of the few medicinal plants that is also frequently used as a leafy vegetable. Application of Cd at 2 and 5 mg l-1 to T. violacea of varying sizes (small 8 - 10 g, medium 16 - 20 g, large 80 – 95 g) elicited a difference in growth response, Cd accumulation and micronutrient distribution. Leaf length and fresh weight of leaves of the medium-size plants decreased with application of Cd at 2 mg l-1 whilst 5 mg l-1 Cd significantly decreased the number of leaves in small-sized plants. Small plants accumulated more Cd in the leaves than medium- or large-sized plants. Application of Cd at 2 mg l-1 and 5 mg l-1 lowered the leaf Cu, Fe, Mo and Zn contents in small- and medium-size plants. This study indicated that T. violacea has the ability to accumulate Cd. In addition, plant size plays an important role with regards to Cd accumulation and elemental distribution. The effect of various nutrient applications (10%, 50% and 100% Hoagland’s nutrient solutions (HS); and HS deficient in N, P or K) on growth parameters and micronutrient distribution in Dioscorea dregeana were investigated. Irrigating plants with 50% HS resulted in better growth performance, whereas a deficiency of either N, P or K negatively affected seedling growth. Plants grown in 10% HS contained higher total B, Fe and Mo levels compared to seedlings grown in 50% and 100% HS. Compared to the control, P deficiency resulted in a Fe increase in the leaves, tuber and roots while a lack of P and K significantly increased total Mn content in D. dregeana. The effect of excess Zn (100, 200 and 300 mg l-1) on growth performance, chlorophyll content and microelemental distribution on Dioscorea sylvatica was investigated. Growth parameters showed a significant decrease when supplied with Zn at 100 mg l-1. Zinc phytotoxicity was evident by the reduction in chlorophyll content. Highest Zn concentrations were detected in the roots. Certain micronutrients appear to be redistributed due to Zn toxicity. The effect of microelements (Cu, Zn) and heavy metals (Cd, Pb, Hg) on germination and seedling development of Bowiea volubilis, Eucomis autumnalis and Merwilla plumbea was investigated. Copper and Zn applied at 1 mg l.1 significantly reduced the percentage germination of E. autumnalis. Low concentrations (. 1 mg l.1) of Cu and Zn negatively affected the root growth of all three species. Mercury concentrations of 0.5 and 1 mg l.1 significantly decreased the percentage germination of B. volubilis and E. autumnalis respectively. Cadmium and Hg at 2 mg l.1 showed a negative effect on the root growth of B. volubilis. Concentrations of 0.5 mg l.1 of all heavy metals tested significantly decreased shoot length of M. plumbea. The effect of Cd on biological activity (anti-inflammatory, antibacterial and antifungal) of medicinal plants with previously confirmed activity was evaluated. When supplied with Cd at 2 mg l-1, Eucomis humilis bulbous extracts showed lower anti-inflammatory activity than the control for both COX-1 and COX-2 activity. Eucomis autumnalis bulbous extracts had greater COX-1 activity compared to the control. However, Cd suppressed the activity of COX-2. Compared with non-Cd-treated Merwilla plumbea plants (control), those supplied with Cd at 10 mg l-1 showed increased antibacterial activity against Bacillus subtilis, Klebsiella pneumoniae and Staphylococcus aureus. However, no change in activity against Escherichia coli was observed. Cadmium accumulation in the bulbs had no effect on antifungal activity of Tulbaghia violacea. Thus, optimized agricultural practices are essential for quality control of cultivated medicinal plants. The studies presented in this thesis collectively answer several questions related to heavy metal involvement in South African medicinal plants. The findings substantiate the need to regulate and monitor the South African medicinal plant trade against heavy metal contamination which will in turn provide a product of safety and quality to the consumer. / Thesis (Ph.D.)-University of KwaZulu-Natal, Pietermaritzburg, 2008.

Dans un bassin versant, la connectivité hydrologique constitue un état hydrologique qui lie le versant à la zone riveraine. Ses impacts sur la production du débit et le transfert des éléments dissous vers le cours d’eau sont présumés substantiels. L’étude vise à 1) détecter les hydrotopes et les connexions hydrologiques à l’aide d’un réseau de puits qui permet la mesure des fluctuations de la nappe phréatique (NP); 2) identifier la variabilité spatio-temporelle et la signature géochimique des sources potentielles en eau à l’aide des éléments majeurs et traces et 3) examiner la contribution spatio-temporelle respective des sources en eau du bassin lors d’un événement de précipitation. L’étude s’effectue dans un bassin versant forestier du Bouclier canadien (l’Hermine). Nous démontrons l’existence de quatre hydrotopes représentant un gradient de convergence de l’eau, soulignant la diversité de comportement de NP. Les connexions hydrologiques se caractérisent par des coefficients de Spearman élevés des relations entre la profondeur de la NP et le débit, dans leur partie en aval, et s’enclenchent par le fill and spill. Le comportement de NP est influencé par la distance aux limites du bassin, l’horizonation du sol et la topographie souterraine. En somme, trois sources en eau se connectent à partir du versant vers la zone riveraine durant l’événement pluvial de manière chronologique: 1) les horizons B et la NP de l’ensemble du bassin (Sr); 2) les horizons LFH des zones de convergence (Ba et Zn) et 3) une dépression de sol humide sur le versant nord (Co et Mn). / In watersheds, hydrologic connectivity consists of a hydrologic state that links the upper part of a hillslope to the riparian zone. Its impacts on streamflow generation and transfer of dissolved elements towards the stream are considered substantial. This study aims to 1) detect hydrotops and hydrologic connections with a network of wells that allow measurements of water table (WT) fluctuations; 2) identify spatial and temporal variability and the geochemical signature of potential sources of water with major and trace elements and 3) examine the spatial and temporal contribution of sources of water within the watershed during a storm event. The study takes place in a small forested watershed of the Canadian Shield (the Hermine). We demonstrate the existence of four hydrotops representing a water convergence gradient, highlighting diversity of behavior of the WT. Hydrological connections are characterized by high Spearman coefficients of the relationship between WT depth and streamflow in their downstream portion. Some hydrological connections are engaged by the fill and spill mechanism. WT behavior is influenced by the distance limits of the basin, soil horizonation and subsurface topography. In sum, three water sources connect the hillslope to the riparian zone during the storm event in chronological order: 1) WT and B horizons of the entire basin (Sr), 2) LFH horizons of convergence zones (Ba and Zn) and 3) a depression of wet soil on north hillslope (Co and Mn).

The Wonderfonteinspruit (WFS) flows through the richest gold mining region in the world and has subsequently been exposed to the related pollution for more than a century. In order to determine the extent of mining related pollution in the WFS, sediment, water, soil, grass and cattle tissue samples were collected, analysed and compared from an experimental group and a control group. This study identified cobalt, nickel, zinc, selenium, cadmium, gold, lead and uranium as elements of interest by comparing sediment samples from the WFS and the Mooi River (MR) (which served as a control or background site). The cobalt concentration was found to be 16.37 times higher, the nickel concentration was 30.4 times higher, the copper concentration was 3.59 times higher, the zinc concentration was 103.49 times higher, the selenium concentration was 7.14 times higher, the cadmium concentration was 17.88 times higher, the gold concentration was 4.78 times higher, the lead concentration was 1.32 times higher and the uranium concentration was 375.78 times higher in the initial comparison with sediments from the MR. These results were all found to be significant. All these elements are by products of non-ferrous mining activities as was described in the literature review. The elevated concentrations of these elements, which were found in the streambed sediment of a site in the Lower-Wonderfonteinspruit, suggest that they could have resulted due to upstream gold mining activities. These gold mining activities were initiated more than a century ago and continue to this day. Analysis of the different particle size fractions (sand, silt and clay fractions) revealed that the highest elemental concentrations were found in the clay sized fractions. The clay sized fraction usually contains secondary soil minerals which have the ability to adsorb dissolved cations onto their surface areas. Further analysis revealed that the sand fraction of the WFS sediment contained a substantial concentration of cobalt, nickel, copper, zinc, lead and uranium which, upon initial inspection could not be explained. X-Ray Diffraction (XRD) analysis revealed that more than 90 % of the WFS sand, silt and clay fractions consisted of quartz, which was much higher than that of the MR. Due to the particle size of quartz, it generally dominates the sand and silt fractions, and finding it at levels above 90 % in the clay sized fraction is thought to be highly irregular. This could be explained by the extraction and processing of gold reefs from the goldfields in the catchment. The gold reefs consisted of quartz veins that were milled to a fine dust and pumped onto slime and sand dumps after the gold was extracted. The most abundant ore minerals found within these dumps were uraninite(UO2), brannerite (UO3Ti2O4), arsenopyrite (FeAsS), cobaltite (CoAsS), galena (PbS), pyrrhotite (FeS), gersdofite (NiAsS) and chromite (FeCr2O4), which contain some of the elements of interest. These dumps are either located in close proximity to the WFS or connected to the WFs via canals or pipelines. Erosion of these dumps would then introduce this finely milled quartz into the stream system. Therefore, the elements found in the sediment of the WFS were not only introduced to the system in the dissolved form, but also in the particulate form. The water samples that were collected from the experimental site (WFS) were found to exceed the cobalt, nickel, copper, zinc, selenium and cadmium concentrations ranges which are normally found in natural waters. In addition to this, the cadmium, lead and nickel concentration in the WFS water samples were found to occasionally exceed the target water quality ranges for livestock water as set by DWAF (1996). Water samples that were collected from the control group were found to exceed only the selenium concentration found in natural water sources as found by Crittenden et al., (2005). Cattle in the experimental group drink directly from the WFS and may stir up the sediment and thereby increasing the elemental concentrations within the water prior to ingestion. The target water quality ranges (TWQR) for livestock watering, as set by DWAF 1996, were exceeded by the average nickel and lead concentrations found in the disturbed WFS water samples. Although the elemental concentrations in the respective water samples were fairly low there was a definite practical significant difference between the WFS water and the MR water samples, as well as the disturbed WFS water and the MR water samples. The WFS water quality seemed to have a very large standard deviation which could serve as an indication that the elemental concentrations are highly variable over time. The elemental concentrations that were found in soil samples from the respective sites were compared to elemental concentrations found in normal agricultural soil as presented by Bergman (1992), which revealed the following results. The cobalt concentrations in the soil samples from the soil along WFS site, soil along MR site and irrigation MR site exceeded the agricultural threshold value. The nickel concentrations in the soil samples from the soil along WFS site, soil along MR site, wetland WFS and irrigation MR site exceeded the agricultural threshold value. The zinc concentrations in the soil samples from the soil along WFS site exceeded the agricultural threshold value. Copper, selenium, cadmium and lead concentrations did not exceed the agricultural threshold values in any of the respective sites. The agricultural threshold value for uranium concentrations was exceeded in the soil samples from the soil along the WFS site and the wetland WFS site. The comparison between the elemental concentrations that were found in the soil samples from the irrigated soil WFS site and the irrigated soil MR site revealed a practically significant difference for the copper, zinc and uranium concentrations. The comparison between the elemental concentrations found in soil samples from the soil along the WFS site and the soil along the MR site revealed a practically significant difference for all elements of interest. The analysis of the elemental concentration in the different particle size fractions of soil samples from all the sites (excluding the irrigated pastures) displayed highest elemental concentrations in the clay sized fraction. The elemental concentrations that were found in this fraction are generally considered to be available for plant uptake, as most of them are usually bound to the surface of secondary soil minerals. The sites with the highest concentration of plant available elements were found to be the soil along WFS site and the wetland WFS site. The elemental concentrations found in the grass samples from the respective sampling sites were compared to elemental concentrations that are normally found in grass pastures (Underwood & Suttle, 2001). The cobalt, nickel, copper and concentrations that were found in the grass samples from most of the sites in both the control and experimental groups were all found to exceed the concentration ranges found in natural pastures. The cadmium and zinc concentrations in the grass samples from the soil along WFS site were found to exceed the respective concentration ranges found in natural pastures. The normal uranium concentration found in irrigated or natural grasses could not be found in an extensive search. Dreesen et al. (1982) reported 0.16 mg/kg uranium in grasses and 1.8 mg/kg uranium in shrubs that grew on soil-covered tailings material. All the sites in the experimental group, including the control WFS site, drastically exceeded these concentrations, which may suggest that the grasses in the experimental sites have been exposed to elevated uranium concentrations. The grass samples with the highest average elemental concentrations were found in the soil along WFS site and irrigated soil WFS site. Lead was to be the only element of interest to have the highest concentration in grass samples from the irrigated soil WFS site. The irrigated soil WFS site portrayed significant transfer factors for nickel, copper, zinc, lead and uranium. This could serve as an indication that the grasses under irrigation in the WFS site absorb and accumulate the highest concentration of elements in respect to the soil concentrations found in the various sites. Therefore, the irrigation from the WFS has a profound effect on the nickel, copper, zinc, lead and uranium concentration in the grass samples under irrigation. The results obtained from the comparative analysis of the elemental concentration in grass samples from the irrigation WFS and irrigation MR sites revealed that all elemental concentrations except for that of zinc had a difference that was practically significant, with the uranium concentration having the largest effect size. The results obtained from the comparative analysis of the elemental concentration in grass samples from the soil along WFS and soil along MR sites revealed that all elemental concentrations had a difference that was practically significant uranium, nickel and zinc concentrations having the largest effect sizes. Considering that a large effect size is achieved at a value equal to or greater than 0.8, the uranium concentration therefore had a massive difference in both comparisons. The results obtained from the comparative analysis of the elemental concentration in grass samples from the wetland WFS and control WFS sites revealed that only the cobalt, nickel and uranium concentrations had differences that were practically significant, with the cobalt concentration having the largest effect size. The results obtained from the comparative analysis of the elemental concentration in the grass samples from the soil along WFS and control WFS sites revealed that all the elemental concentrations except for the lead concentration had a difference that was practically significant. The cobalt, nickel and zinc had the largest effect sizes. The elemental concentrations that were found in cattle liver, kidney and muscle tissue samples from both the experimental and control groups were compared to elemental concentrations normally found in cattle samples as found in Pulse (1994), ATSDR (2004), and ATSDR (2011). This comparison revealed the following results: The nickel, cadmium and lead concentration that were found in the cattle liver, kidney and muscle tissue samples from both the experimental and control groups were found to be within the ranges normally found in cattle. Cobalt concentrations found in the liver and muscle tissue samples of cattle from both the experimental and control groups exceeded the normal ranges, and the cobalt concentrations found in the kidney samples from the experimental group exceeded the normal range. The copper concentration found in the kidney samples from the cattle in the experimental group exceeded that of the normal concentration range. The zinc concentration found in the liver and kidney samples in the cattle from the experimental group, and the kidney samples from the cattle in the control group exceeded the normal range. The selenium concentration found in the liver, kidney and muscle tissue samples in the cattle from the experimental group, and the kidney samples from the cattle in the control group exceeded the normal range. The uranium concentration found in the liver, kidney and muscle tissue samples in the cattle from the experimental group exceeded the normal range. The comparison between cattle tissue samples from the experimental and control group revealed that nickel, zinc, selenium, lead and uranium concentrations all reveal a practically significant difference. Uranium, nickel and lead portrayed the largest differences between the two groups. The uranium concentration in the cattle samples from the experimental group was 126.75 times higher in the liver, 4350 times higher in the kidney, 47.75 times higher in the spleen, 31.6 times higher in the muscle tissue, 60 times higher in the bone and 129 times higher in the hair than that of the cattle samples from the control group. In addition to this, the uranium did not only accumulate in the predicted tissue samples (bone, liver and kidney), but also in the muscle tissue samples. The nickel concentrations in the cattle samples were all found to be higher in the experimental group, with liver 1.4 times higher, kidney 387.5 times higher, spleen 2.1 times higher, muscle tissue 2.8 times higher, bone 167.5 times higher and hair 76.5 times higher than that of the cattle samples from the control group. The lead concentrations found in the cattle samples from the experimental group were found to be 3.8 times higher in the liver, 17.3 times higher in the kidney, 3.3 times higher in the spleen, 3.2 times higher in the muscle tissue, 9 times higher in the bone and 12.2 times higher in the hair than the cattle samples from the control group. Furthermore, the study revealed that the major route of ingestion for all the elements of interest, excluding nickel and cobalt was via the ingestion of grass. The major route for nickel and cobalt ingestion was via soil ingestion. The elemental concentrations from water ingestion were found to be a less significant. It was shown that a predictive cattle consumption model was developed and calibrated from data gathered from a control and experimental group. Animal matter analysed for both groups were related to the cattle age of six years. Although good correlation between observed and simulated values was achieved, the exiting model fit is non-unique. To obtain a more precise model fit a similar dataset is required for both groups, but at a different age. The predictive model also showed that if only grass were to be used as input, there were no significant changes in the correlation between observed and simulated values. This has a huge advantage in terms of costs associated with laboratory analyses as the analysis of grass will be sufficient for using the model. A human health risk assessment was performed based on the results of the cattle consumption model. It was shown that no toxic risk exits for both the control and experimental groups if an intake rate of 0.13 kg of meat per day was assumed. Furthermore, Figure 6-11 clearly indicates that an intake rate of up to 0.38 kg of meat per day also has no toxic risk for both groups, which strongly suggests that there is no risk to the human food chain. The cattle grazing in the WFS appear to be in a good physical condition and according to the farmer; the reproduction rate is at desirable levels. Good farming practices would have also played a significant role to achieve this. / Thesis (MSc (Environmental Sciences))--North-West University, Potchefstroom Campus, 2012.

The Wonderfonteinspruit (WFS) flows through the richest gold mining region in the world and has subsequently been exposed to the related pollution for more than a century. In order to determine the extent of mining related pollution in the WFS, sediment, water, soil, grass and cattle tissue samples were collected, analysed and compared from an experimental group and a control group. This study identified cobalt, nickel, zinc, selenium, cadmium, gold, lead and uranium as elements of interest by comparing sediment samples from the WFS and the Mooi River (MR) (which served as a control or background site). The cobalt concentration was found to be 16.37 times higher, the nickel concentration was 30.4 times higher, the copper concentration was 3.59 times higher, the zinc concentration was 103.49 times higher, the selenium concentration was 7.14 times higher, the cadmium concentration was 17.88 times higher, the gold concentration was 4.78 times higher, the lead concentration was 1.32 times higher and the uranium concentration was 375.78 times higher in the initial comparison with sediments from the MR. These results were all found to be significant. All these elements are by products of non-ferrous mining activities as was described in the literature review. The elevated concentrations of these elements, which were found in the streambed sediment of a site in the Lower-Wonderfonteinspruit, suggest that they could have resulted due to upstream gold mining activities. These gold mining activities were initiated more than a century ago and continue to this day. Analysis of the different particle size fractions (sand, silt and clay fractions) revealed that the highest elemental concentrations were found in the clay sized fractions. The clay sized fraction usually contains secondary soil minerals which have the ability to adsorb dissolved cations onto their surface areas. Further analysis revealed that the sand fraction of the WFS sediment contained a substantial concentration of cobalt, nickel, copper, zinc, lead and uranium which, upon initial inspection could not be explained. X-Ray Diffraction (XRD) analysis revealed that more than 90 % of the WFS sand, silt and clay fractions consisted of quartz, which was much higher than that of the MR. Due to the particle size of quartz, it generally dominates the sand and silt fractions, and finding it at levels above 90 % in the clay sized fraction is thought to be highly irregular. This could be explained by the extraction and processing of gold reefs from the goldfields in the catchment. The gold reefs consisted of quartz veins that were milled to a fine dust and pumped onto slime and sand dumps after the gold was extracted. The most abundant ore minerals found within these dumps were uraninite(UO2), brannerite (UO3Ti2O4), arsenopyrite (FeAsS), cobaltite (CoAsS), galena (PbS), pyrrhotite (FeS), gersdofite (NiAsS) and chromite (FeCr2O4), which contain some of the elements of interest. These dumps are either located in close proximity to the WFS or connected to the WFs via canals or pipelines. Erosion of these dumps would then introduce this finely milled quartz into the stream system. Therefore, the elements found in the sediment of the WFS were not only introduced to the system in the dissolved form, but also in the particulate form. The water samples that were collected from the experimental site (WFS) were found to exceed the cobalt, nickel, copper, zinc, selenium and cadmium concentrations ranges which are normally found in natural waters. In addition to this, the cadmium, lead and nickel concentration in the WFS water samples were found to occasionally exceed the target water quality ranges for livestock water as set by DWAF (1996). Water samples that were collected from the control group were found to exceed only the selenium concentration found in natural water sources as found by Crittenden et al., (2005). Cattle in the experimental group drink directly from the WFS and may stir up the sediment and thereby increasing the elemental concentrations within the water prior to ingestion. The target water quality ranges (TWQR) for livestock watering, as set by DWAF 1996, were exceeded by the average nickel and lead concentrations found in the disturbed WFS water samples. Although the elemental concentrations in the respective water samples were fairly low there was a definite practical significant difference between the WFS water and the MR water samples, as well as the disturbed WFS water and the MR water samples. The WFS water quality seemed to have a very large standard deviation which could serve as an indication that the elemental concentrations are highly variable over time. The elemental concentrations that were found in soil samples from the respective sites were compared to elemental concentrations found in normal agricultural soil as presented by Bergman (1992), which revealed the following results. The cobalt concentrations in the soil samples from the soil along WFS site, soil along MR site and irrigation MR site exceeded the agricultural threshold value. The nickel concentrations in the soil samples from the soil along WFS site, soil along MR site, wetland WFS and irrigation MR site exceeded the agricultural threshold value. The zinc concentrations in the soil samples from the soil along WFS site exceeded the agricultural threshold value. Copper, selenium, cadmium and lead concentrations did not exceed the agricultural threshold values in any of the respective sites. The agricultural threshold value for uranium concentrations was exceeded in the soil samples from the soil along the WFS site and the wetland WFS site. The comparison between the elemental concentrations that were found in the soil samples from the irrigated soil WFS site and the irrigated soil MR site revealed a practically significant difference for the copper, zinc and uranium concentrations. The comparison between the elemental concentrations found in soil samples from the soil along the WFS site and the soil along the MR site revealed a practically significant difference for all elements of interest. The analysis of the elemental concentration in the different particle size fractions of soil samples from all the sites (excluding the irrigated pastures) displayed highest elemental concentrations in the clay sized fraction. The elemental concentrations that were found in this fraction are generally considered to be available for plant uptake, as most of them are usually bound to the surface of secondary soil minerals. The sites with the highest concentration of plant available elements were found to be the soil along WFS site and the wetland WFS site. The elemental concentrations found in the grass samples from the respective sampling sites were compared to elemental concentrations that are normally found in grass pastures (Underwood & Suttle, 2001). The cobalt, nickel, copper and concentrations that were found in the grass samples from most of the sites in both the control and experimental groups were all found to exceed the concentration ranges found in natural pastures. The cadmium and zinc concentrations in the grass samples from the soil along WFS site were found to exceed the respective concentration ranges found in natural pastures. The normal uranium concentration found in irrigated or natural grasses could not be found in an extensive search. Dreesen et al. (1982) reported 0.16 mg/kg uranium in grasses and 1.8 mg/kg uranium in shrubs that grew on soil-covered tailings material. All the sites in the experimental group, including the control WFS site, drastically exceeded these concentrations, which may suggest that the grasses in the experimental sites have been exposed to elevated uranium concentrations. The grass samples with the highest average elemental concentrations were found in the soil along WFS site and irrigated soil WFS site. Lead was to be the only element of interest to have the highest concentration in grass samples from the irrigated soil WFS site. The irrigated soil WFS site portrayed significant transfer factors for nickel, copper, zinc, lead and uranium. This could serve as an indication that the grasses under irrigation in the WFS site absorb and accumulate the highest concentration of elements in respect to the soil concentrations found in the various sites. Therefore, the irrigation from the WFS has a profound effect on the nickel, copper, zinc, lead and uranium concentration in the grass samples under irrigation. The results obtained from the comparative analysis of the elemental concentration in grass samples from the irrigation WFS and irrigation MR sites revealed that all elemental concentrations except for that of zinc had a difference that was practically significant, with the uranium concentration having the largest effect size. The results obtained from the comparative analysis of the elemental concentration in grass samples from the soil along WFS and soil along MR sites revealed that all elemental concentrations had a difference that was practically significant uranium, nickel and zinc concentrations having the largest effect sizes. Considering that a large effect size is achieved at a value equal to or greater than 0.8, the uranium concentration therefore had a massive difference in both comparisons. The results obtained from the comparative analysis of the elemental concentration in grass samples from the wetland WFS and control WFS sites revealed that only the cobalt, nickel and uranium concentrations had differences that were practically significant, with the cobalt concentration having the largest effect size. The results obtained from the comparative analysis of the elemental concentration in the grass samples from the soil along WFS and control WFS sites revealed that all the elemental concentrations except for the lead concentration had a difference that was practically significant. The cobalt, nickel and zinc had the largest effect sizes. The elemental concentrations that were found in cattle liver, kidney and muscle tissue samples from both the experimental and control groups were compared to elemental concentrations normally found in cattle samples as found in Pulse (1994), ATSDR (2004), and ATSDR (2011). This comparison revealed the following results: The nickel, cadmium and lead concentration that were found in the cattle liver, kidney and muscle tissue samples from both the experimental and control groups were found to be within the ranges normally found in cattle. Cobalt concentrations found in the liver and muscle tissue samples of cattle from both the experimental and control groups exceeded the normal ranges, and the cobalt concentrations found in the kidney samples from the experimental group exceeded the normal range. The copper concentration found in the kidney samples from the cattle in the experimental group exceeded that of the normal concentration range. The zinc concentration found in the liver and kidney samples in the cattle from the experimental group, and the kidney samples from the cattle in the control group exceeded the normal range. The selenium concentration found in the liver, kidney and muscle tissue samples in the cattle from the experimental group, and the kidney samples from the cattle in the control group exceeded the normal range. The uranium concentration found in the liver, kidney and muscle tissue samples in the cattle from the experimental group exceeded the normal range. The comparison between cattle tissue samples from the experimental and control group revealed that nickel, zinc, selenium, lead and uranium concentrations all reveal a practically significant difference. Uranium, nickel and lead portrayed the largest differences between the two groups. The uranium concentration in the cattle samples from the experimental group was 126.75 times higher in the liver, 4350 times higher in the kidney, 47.75 times higher in the spleen, 31.6 times higher in the muscle tissue, 60 times higher in the bone and 129 times higher in the hair than that of the cattle samples from the control group. In addition to this, the uranium did not only accumulate in the predicted tissue samples (bone, liver and kidney), but also in the muscle tissue samples. The nickel concentrations in the cattle samples were all found to be higher in the experimental group, with liver 1.4 times higher, kidney 387.5 times higher, spleen 2.1 times higher, muscle tissue 2.8 times higher, bone 167.5 times higher and hair 76.5 times higher than that of the cattle samples from the control group. The lead concentrations found in the cattle samples from the experimental group were found to be 3.8 times higher in the liver, 17.3 times higher in the kidney, 3.3 times higher in the spleen, 3.2 times higher in the muscle tissue, 9 times higher in the bone and 12.2 times higher in the hair than the cattle samples from the control group. Furthermore, the study revealed that the major route of ingestion for all the elements of interest, excluding nickel and cobalt was via the ingestion of grass. The major route for nickel and cobalt ingestion was via soil ingestion. The elemental concentrations from water ingestion were found to be a less significant. It was shown that a predictive cattle consumption model was developed and calibrated from data gathered from a control and experimental group. Animal matter analysed for both groups were related to the cattle age of six years. Although good correlation between observed and simulated values was achieved, the exiting model fit is non-unique. To obtain a more precise model fit a similar dataset is required for both groups, but at a different age. The predictive model also showed that if only grass were to be used as input, there were no significant changes in the correlation between observed and simulated values. This has a huge advantage in terms of costs associated with laboratory analyses as the analysis of grass will be sufficient for using the model. A human health risk assessment was performed based on the results of the cattle consumption model. It was shown that no toxic risk exits for both the control and experimental groups if an intake rate of 0.13 kg of meat per day was assumed. Furthermore, Figure 6-11 clearly indicates that an intake rate of up to 0.38 kg of meat per day also has no toxic risk for both groups, which strongly suggests that there is no risk to the human food chain. The cattle grazing in the WFS appear to be in a good physical condition and according to the farmer; the reproduction rate is at desirable levels. Good farming practices would have also played a significant role to achieve this. / Thesis (MSc (Environmental Sciences))--North-West University, Potchefstroom Campus, 2012.

The combination of analytical sensitivity and selectivity provided by time-of-flight secondary ion mass spectrometry (ToF-SIMS), with advanced statistical interrogation by principal component analysis (PCA), has allowed a significant advancement in the forensic discrimination of pen, pencil and glass materials based on trace characterisation.