No description available.

No description available.

The research used dendro-chemical analysis of ash tree rings and current year leaf litter to track Cd, Pb, Zn, Cu, Mn, Cr, and Sn spread and cycling from a closed garbage dump-toxic waste site. This technique allowed for determination of areal extent, contaminant levels and time period of initial contaminant contact. Only Zn, Sn, and Cu were found in elevated quantities in the xylem wood and Pb in the leaf litter. Elemental concentrations of Pb, Sn and Cd in xylem wood and leaves of ash were positively correlated. Tin was the only element to demonstrate a clear initial contact period and elemental accumulation with age. Significant levels of Cu accumulated in the heartwood while Zn revealed significant but inconsistent accumulated patterns. Expected attenuation zones associated with municipal solid waste landfill leachate dispersion were not found; thus the pathway for contaminant dispersion was likely through groundwater flow. / An elemental index was developed to facilitate the use of dendro-chemical analysis in periods of suppressed tree growth resulting from environmental pollution.

Innovative means and methods were tested to develop an economical, pragmatic and environmentally sustainable soil remediation process for heavy metal contaminated soils. An unsaturated-flow soil washing procedure was devised to dissolve the soil-bound toxic heavy metals; the latter were extracted by a chemical washing solution that percolated through the soil matrix. Subsequently, the leached toxic heavy metals were selectively concentrated, by a chemical precipitation process, into a solid waste. Thereby, a fraction of the spent ethylenediaminetetraacetic acid (EDTA), within the washing and rinsing leachate, was theoretically regenerated and recycle-ready. / The unsaturated-flow washing procedure was perfected by applying different treatments to a soil from a secure landfill. This soil was contaminated with Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, S and Zn. The major contaminants were Fe, Pb, Zn, S, Cu and Mn, making up 25, 1.9, 1.0, 0.4, 0.4 and 0.2%wt of the soil. The extraction responses of the contaminants and those of Al, Ca, Mg and P were established for citric acid (0.5 M) and different molarities of diammonium EDTA ((NH4)2EDTA). The DOW Chemical Company supplied the (NH4)2EDTA (i.e. VERSENE), a 1.37M industrial cleaner, which roughly costs $1.85kg-1 in bulk. The affordability of VERSENE was a pre-condition for hoping to satisfy the economical feasibility of remediating trace metal contaminated soils. / Ultimately, the developed unsaturated-flow washing procedure was tested in a pilot-scale experiment, for its ability to remediate a soil from an abandoned car battery recycling facility. The latter soil was severely contaminated with Pb (3.9%wt). Drip irrigation was used to apply (NH4) 2EDTA and water-rinsing solutions to the surface of soil heaps that rested atop an impermeable barrier, which permitted the retrieval of the leachate. A cumulative EDTA input to the soil of 10.6% wt extracted 49.4% of the total Pb content of the soil. Alternatively, readily biodegradable citric acid barely extracted 2.2% of the total Pb content of the soil, for a cumulative input of 18.1% weight of soil. Different treatments were tested for their effectiveness in concentrating the leached toxic heavy metals into a solid waste. The Pb was best precipitated with Na2S alone, as it provided the most concentrated solid toxic waste. / The environmental sustainability of remediating trace metal contaminated soils was thoroughly examined, as per the amounts of chemical entrants and toxic waste by-products, and per the post-treatment leaching of toxic levels of the remaining and potentially toxic trace metals. (Abstract shortened by UMI.)

One of the most recognised values of tidal salt marshes is the ecosystem service they provide as natural sinks for contaminants such as metals. This study examines net accumulation of metals (As, Cr, Cu, Hg, Ni, Pb, Zn and V) over a 5-yr period, from 1997 to 2002, in surface sediments of salt marshes in the Bay of Fundy, Canada. Metal accumulation has been measured in seven sites that extend from outer to inner Bay and in low and high marsh areas within each site. Overall, sediment metal concentrations are at or near their natural levels. Concentrations of metals show variability among marshes but are not significantly different between low and high marsh. Concentrations of As, Hg, Pb and V appear to be influenced by anthropogenic inputs. Calculated sediment loading rates for these metals generally showed gradients of increased loading from outer to inner Bay. Variability in sediment deposition rate is the driving force behind this spatial pattern. Results of this study suggest that the value of salt marshes as a sink for metals may be enhanced by high sedimentation rates.

The adsorption behaviour of trace metals in soil may provide us with a way to more accurately predict and assess the toxicity of metals in the environment. This thesis reports efforts to apply surface complexation modeling to agricultural and forest soil and to relate model parameters to common soil properties. This study considered Ca, Cd, Cu, Pb and Zn but the methods here could be applied to other metals. In Chapter 2, the surface charge and adsorption behaviour of a set of Ap horizons was characterised using back-titration and batch adsorption techniques. With the objective of simplifying the application of the NICCA model to surface charge and cation adsorption in whole soils the parameters of the NICCA model were related to soil properties (Chapter 3). Four of the six surface charge parameters could be predicted from soil properties and this enabled me to reasonably predict the surface charge of a second group of soils from soil properties. These results suggest that it is possible to make reasonable predictions about the surface charge and adsorption behaviour of a given type of soil using some easily measurable soil properties and a set of generic NICCA adsorption parameters for that soil type. In Chapter 4 this idea is applied to the determination of lime requirement for the agricultural soils.

A major factor complicating the cleanup at many sites is co-contamination by both organic compounds and heavy metals. Whereas much research has focused on the removal of either organic compounds or metals, relatively few studies have investigated simultaneous removal of organic and inorganic pollutants from soil. / The studies reported in this thesis have evaluated a novel technique for the simultaneous mobilization of polychlorinated biphenyl (PCB) compounds and heavy metals (HMs) from a field contaminated soil. Soil extraction with washing aids {surfactants/cyclodextrin in combination with chelating reagent(s)} was optimized for mobilization efficiency, recovery/recycle of washing additives, and in parallel detoxification of mobilized contaminants. PCB extraction efficiencies were determined with a method that converted all the PCB congeners to dicyclohexyl by hydrogenation over palladium. Studies demonstrated that 10 minutes of ultrasonic mixing of field contaminated soil with a combination of surfactant (30 mL L-1) or cyclodextrin (100 g L-1) and a sparing quantity (2 mmoles) of EDTA, simultaneously mobilized appreciable quantities of PCBs and most analyte metals (Cd, Cu, Mn, Pb, Zn, Ni, Cr). / Relative to individual reagents, combinations of surfactant (Brij 98, Triton X-301, or Triton XQS-20) or cyclodextrin (RAMEB or HPCD) with EDTA did not influence PCB extraction efficiencies perceptibly. The presence of surfactant or cyclodextrin in admixture with EDTA did not appreciably change the efficiency of mobilization of most heavy metals (Al, Cd, Cr, Fe, Mn, Ni, and Zn) but did increase the recovery of Cu and Pb with nonionic surfactant and cyclodextrin. When coupled with PCB removal by hexane back-extraction and precipitation of the HMs (mediated by hydrolysis of zero-valent magnesium (Mg0)}, aqueous washing suspension was regenerated and recycled twice to mobilize more contaminants from the soil. Three sonication-washes with the same charge of reagent mobilized appreciable quantities of PCBs (68 - 83%) and virtually all of the available Cd, Cu, Mn, and Pb and lesser amounts of the Zn (56%), Ni (59%), and Cr (50%) but only small quantities of Al (28%) and Fe (30%). / The release of EDTA from heavy metals complexes was efficient for most metals (99%) but was influenced by the nature of surfactant. EDTA recovery (62-65%) post three cycles of soil washing, hexane back-extraction, and Mg 0 treatment was similar for all reagent combinations. Among surfactants and cyclodextrin, only anionic surfactants suffered losses to Mg0 treatment.

Thesis (MTech (Environmental Health))--Cape Peninsula University of Technology, 2018. / Soil ecosystems in urban, rural and agricultural environments receive chemical input from diverse sources of contamination, such as wastewater, industrial discharge, agricultural and urban runoff, fertilizers, vehicle leakages, landfill seepage, and animal waste overspill. Agricultural activities, transportation and industrial activities are suspected to be the highest sources of metal contamination in Cape Town. Although scientists generally have a good understanding of the toxicity of individual chemical pollutants, there is a great need to bridge the gap between our understanding of the toxic effects of exposure to individual contaminants and those effects from exposure to mixtures of chemicals. Woodlice and other soil detritivores have a particularly important ecosystem function in mineralising organic matter. Woodlice experience stress when exposed to toxic levels of metals in the diet, which can reduce feeding rates and may combine with natural stresses to reduce fitness and lower 'performance', thereby possibly resulting in these organisms being unable to completely fulfil their ecological function. The objectives of this study were: to compare how aluminium and manganese are bioaccumulated in Porcellio scaber in terms of the contribution of the hepatopancreas in metal storage compared to the rest of the body; and to determine whether mixtures of aluminium and manganese affect each other’s bioaccumulation and distribution in Porcellio scaber. Woodlice collected from a clean field site (Kirstenbosch Botanical Garden) were experimentally exposed in the laboratory to a range of environmentally relevant aluminium and manganese concentrations. The woodlice were exposed to these metals in single and mixed metal experiments. Oak leaves, collected from a clean site, were contaminated with aluminium and manganese. Therefore, the woodlice were exposed via their food source. A control experiment, where oak leaves were not contaminated, was also prepared. At week 0 and after five weeks of exposure, a sample of the woodlice (5 per exposure group) were dissected to remove the hepatopancreas. Hepatopancreas and rest of the body samples were acid digested and analysed for the metals by means of the ICP-MS. Contrary to the existing knowledge of metals accumulating in the hepatopancreas of woodlice when ingested, this study showed a higher bioaccumulation of aluminium in the rest of the body of woodlice after 5 weeks of exposure than in the hepatopancreas. This result was interpreted as a possible detoxification mechanism by woodlice through the use of the exoskeleton during the moult cycle. A similar result was found when woodlice were exposed to mixtures of aluminium and manganese. This translated to the fact that woodlice were unable to effectively deal with the toxicity caused by the mixture of aluminium and manganese. In the group of woodlice exposed to manganese alone, it was found that manganese concentrations in the rest of the body of woodlice exposed for 5 weeks were statistically higher than the manganese concentrations in the rest of the body of woodlice at the start of the exposure (week 0). However, in the hepatopancreas, there were no statistical differences between the manganese concentrations in week 0 woodlice and the manganese concentrations in week 5 woodlice. Furthermore, manganese concentrations in the rest of the body of week 5 woodlice were statistically higher than manganese concentrations in the hepatopancreas of week 5 woodlice. This was interpreted as further proof that woodlice would accumulate certain metals (aluminium and manganese in this case) in their exoskeleton so that elimination can follow during the moult cycle.

MSc (Chemistry) / Department of Chemistry / In this work, modern pre-concentration techniques, namely dispersive liquid-liquid micro-extraction (DLLME) and QuEChERS, were used to analyse pesticides and heavy metals in complex matrices. The work is divided into six papers. In Papers 1, the recent developments and applications of DLLME during analysis of pesticides in food matrices were reviewed. The DLLME technique has captured the interests of many researchers in recent years. The major advantage, among others, of DLLME is miniaturisation in which the acceptor-to-donor ratio is reduced tremendously leading to high enrichment compared to other sample preparation techniques. In the present work, the different complex matrices where the DLLME technique has been employed for the analysis of pesticides are reviewed as well as the challenges associated with this technique. Papers II reviewed the recent applications and developments of the QuEChERS technique during the analysis of pesticides in food matrices. QuEChERS is a versatile pre-concentration method whose application spans the whole breath of organic compounds. There are three common standard methods used during QuEChERS and these are the original QuEChERS, AOAC and the EN methods. In this paper, recent developments and applications of QuEChERS techniques in the analysis of pesticides in food samples were reviewed. In Paper III, green pre-concentration techniques employed during analysis of pesticides were reviewed. Recently, the parameter of “greenness” during sample pre-concentration of pesticides in food matrices is as important as selectivity in order to avoid using large amounts of harmful organic solvents during sample preparation. Developing new green pre-concentration techniques is one of the key subjects in green chemistry in order to minimize the release of large volume of toxic organic solvents into the environment. Thus, to reduce the impact on the environment during trace analysis of pesticides in food matrices, new developments in pesticide pre-concentration have gone in three separate directions (which are reviewed in this paper): one is the search for more environmentally friendly solvents, the second one is miniaturization and the third one is the development of solvent-free pre-concentration techniques. Eco-friendly solvents such as supercritical fluids, ionic liquids and natural deep eutectic solvents have been developed for use as extraction solvents during pre-concentration of pesticides in food matrices. Also miniaturized pre-concentration techniques such as QuEChERS, dispersive liquid-liquid micro-extraction and hollow-fibre liquid phase micro-extraction have been used during trace analysis of pesticides in food samples as well as solvent-free techniques such as solid phase micro-extraction and stir bar sorptive extraction. All these developments are geared to ensure that pesticide pre-concentration in food matrices is green and were reviewed in this paper. The effect of vehicular emissions on the concentrations of selected heavy metals was investigated in Paper IV. The samples were pre-concentrated using DLLME prior to analysis with flame atomic absorption spectroscopy. Dithizone, chloroform and methanol were used as chelating agent, extraction solvent and dispersion solvent respectively during the DLLME technique. The pH of the sample was adjusted to around 8 using sulphuric acid or sodium hydroxide solution. The influential DLLME parameters, such as pH volume and type of extraction solvent, and voume of disperser solvent, were optimized prior to the application of the developed method to real samples (roadside dust, fruits and vegetables). In Paper V, chromium speciation in fruits and vegetables was studied. The chromium in fruit and vegetable sample juices was pre-concentrated using DLLME prior to analysis with flame atomic absorption spectroscopy. Diphenylcarbazide (DPC) was used as a chelating agent in this study, and salting out of the complex from the aqueous medium into the organic phase was effected using sodium acetate. Chloroform and methanol were used as extraction and dispersion solvents respectively in the DLLME method for the determination of chromium (VI). For total chromium, the trivalent chromium was oxidised using acidified KMnO4 to hexavalent chromium before performing the DLLME technique. The concentration of chromium (III) was determined by finding the difference between total chromium and concentration of chromium (VI). The important parameters that influence the efficiency of the DLLME technique were also optimized using the univariate approach. After optimization, the developed method was applied to real samples. In Paper VI, the concentration of malathion pesticide in fruits was determined using QuECHERS for pre-concentration and UV-Vis spectrophotometry for instrumental analysis. Acetonitrile was used as the extraction solvent and Z-sep+/PSA sorbent combination was used for sample clean-up. The acetonitrile extract from QuEChERS was then hydrolysed using KOH followed by reaction with acidified potassium bromate for colour development. The coloured product formed was then analysed using UV-Vis spectrophotometry. Among the fruits analysed, Oranges had no malathion residue in them. However, trace amounts of malathion, below WHO maximum allowable limits, were found in pears and apples. / NRF

No description available.